1.

BRIEF HISTORY OF AMMONIA [1]

Nitrogen is an essential element for life on Earth and a crucial nutrient to sustain plant life; it
is present in the atmosphere in the form of the diatomic molecule N2 (N≡N). The triple bond
is remarkably strong and its dissociation requires a large amount of energy (945 kcal/mol).
Thus, even though it is abundantly available in the air at about 78% by volume, it is hard to
use. Humans learned how to convert nitrogen into ammonia synthetically over 100 years ago
in a process discovered by Fritz Haber. The technology was purchased by BASF and the
German chemist Carl Bosch scaled it up to industrial level. Both scientists were awarded the
Nobel Prize for their critical research and the synthesis of ammonia is now known as the
Haber-Bosch process, which takes place from the reaction between nitrogen and hydrogen:
N2 (g) + 3H2 (g) ↔ 2NH3 (g) (1)
The conversion typically occurs at temperatures between 300-550 ºC, and under extremely
high pressure between 150-300 bar. Thermodynamically, the formation of ammonia is
favored at low temperatures and high pressure. However, because the reaction rate is very
low, both high temperature and pressure are used in the presence of an iron-based catalyst to
lower the activation energy of the reaction, which is, in the case of ammonia, the energy
required to dissociate molecular nitrogen. Above 750 bar, the conversion to ammonia can
reach 100%. However, the amount of energy required to maintain this exceedingly high
pressure is not practical and presents unreasonable safety concerns. Because of this, 150-300
bar is typically used. For example, at a temperature of 475 ºC and 200 bar, the yield of
ammonia generally ranges from 10-20%, which is low, but the costs of running the plants are
also contained.

2. GLOBAL AMMONIA MARKET [1]

On a global scale, approximately 82% of ammonia is used for the production of fertilizers
and nearly half of this is used for the synthesis of Urea (Figure 1). Ammonium nitrate, di-
ammonium phosphate (DAP) and mono-ammonium phosphate (MAP) are other common
fertilizers that are manufactured from ammonia. Only 18% of ammonia is employed for uses
other than agriculture. This fraction is used as the precursor for the synthesis of important
nitrogen-containing compounds like acrylonitrile, amino acids, hydrogen cyanide, hydrazine,
hydroxylamine and many more. In the United States, because agriculture practices are highly
developed, over 40% of ammonia is used directly for agricultural applications.
 Figure 1: Ammonia is predominantly used for fertilizer production (82% in 2013).

The global market of ammonia is highly fragmented (Figure 2). In 2013, China was the
world’s largest producer of ammonia with a market share of more than 30%, producing
nearly 70 million metric tons per year. India followed with 7.1% market share, Russia with
6.1% and the United States with 6.0%. The I.R. Iran with seven active plants, produced about
3.0 million metric tons per year of ammonia with a market share of more than 1.5%1.

Figure 2: Ammonia production capacity by region- 2013 market share.

1
Iran’s Petrochemical Industry Report, 2014
Historically, the production of ammonia has steadily increased over the past 100 years at a
2% growth rate. However, due to a strong increase in fertilizer demand, the ammonia market
is expected to grow at an unprecedented 3.1% compound annual growth rate (CAGR) in the
next five years and reach global revenues of over $100 billion in 2019.

3. AMMONIA PRODUCTION PROCESSES [2]

The typical size of a large single-train ammonia plant is 1,000-1,500 ton/day, although
capacities of 1,800 ton/day and above are not uncommon for new plants.
Natural gas is the typical feedstock used for ammonia production in all countries, except for
India and China. Steam reforming of natural gas is the most efficient route, with about 77%
of world ammonia capacity being based on steam reforming of natural gas.
The ammonia synthesis process is principally independent of the type of synthesis gas
production process, but synthesis gas quality influences the loop design and operating
conditions. A block diagram of the conventional ammonia plant based on steam reforming
process is shown in Figure 3.

Figure 3: Block diagram of ammonia production based on the steam reforming process.
The primary and secondary reformers in ammonia plants are almost the same as methanol
plants. The main difference is that, the air is used instead of oxygen in the secondary reformer
(ATR). In addition no CO2 sources is used as reformer feed, because the objective of
reformer units is to maximize the H2 and minimize the CO and CO2 production.
Water, carbon monoxide and carbon dioxide, all of which poison the iron catalyst used in the
ammonia synthesis, must be removed from the synthesis gas.

Carbon monoxide removal (water-shift conversion)

The process gas from the secondary reformer contains 12-15% CO (dry gas base) and most of
the CO is converted in the shift section according to the reaction:
CO + H2O ↔ CO2 + H2 ΔHR = –41 kJ/mol (2)
In the High Temperature Shift (HTS) conversion, the gas is passed through a bed of iron
oxide/chromium oxide catalyst at around 400°C, where the CO content is reduced to about
3% (dry gas base), limited by the shift equilibrium at the actual operating temperature. There
is a tendency to use copper containing catalyst for increased conversion.
The gas from the HTS is cooled and passed through the Low Temperature Shift (LTS)
converter. This LTS converter is filled with a copper oxide/zinc oxide-based catalyst and
operates at about 200-220°C. The residual CO content in the converted gas is about 0.2-0.4%
(dry gas base). A low residual CO content is important for the efficiency of the process.

Water removal
The gas mixture is further cooled to about 40oC, at which temperature the water condenses
and is removed.

Carbon dioxide removal

The CO2 is removed in a chemical or a physical absorption process. The solvents used in
chemical absorption processes are mainly aqueous amine solutions; Mono Ethanolamine
(MEA), Activated Methyl Di-Ethanolamine (aMDEA) or hot potassium carbonate solutions.
Physical solvents are glycol di-methylethers (Selexol), propylene carbonate and others. The
MEA process has a high regeneration energy consumption and is not regarded as a good
process.
For new ammonia plants the following CO2 removal processes are currently recommended:
– aMDEA 2-stage process, or similar
– Benfield process (HiPure, LoHeat), or similar
– Selexol or similar physical absorption processes
Residual CO2 contents are usually in the range of 100-1,000 ppmv, dependent on the type and
design of the removal unit. Contents down to about 50 ppmv are achievable.
Methanation
The small amounts of CO and CO2, remaining in the synthesis gas, are poisonous for the
ammonia synthesis catalyst and must be removed by conversion to CH4 in the methanator:
CO + 3H2 ↔ CH4 + H2O (3)
CO2 + 4H2 ↔ CH4 + 2H2O (4)
The reactions take place at around 300°C in a reactor filled with a nickel containing catalyst.
Methane is an inert gas in the synthesis reaction of ammonia.

Synthesis gas compression and ammonia synthesis

Modern ammonia plants use centrifugal compressors for synthesis gas compression, usually
driven by steam turbines, with the steam being produced in the ammonia plant. The
refrigeration compressor, needed for condensation of product ammonia, is also usually driven
by a steam turbine.
The synthesis of ammonia takes place on an iron catalyst at pressures usually in the range of
100-250 bar and temperatures in the range of 350-550°C:
N2 + 3H2 ↔ 2NH3 ΔHR = – 46 kJ/mol (5)
Only 20-30% is reacted per pass in the converter due to the unfavorable equilibrium
conditions.
The ammonia that is formed is separated from the recycle gas by cooling/condensation, and
the reacted gas is substituted by the fresh make-up synthesis gas, thus maintaining the loop
pressure. In addition, extensive heat exchange is required due to the exothermic reaction and
the large temperature range in the loop. A newly developed ammonia synthesis catalyst
containing ruthenium on a graphite support has a much higher activity per unit of volume and
has the potential to increase conversion and lower operating pressures.
Synthesis loop arrangements differ with respect to the points in the loop at which the make-
up gas is delivered and the ammonia and purge gas are taken out. The best arrangement is to
add the make-up gas after ammonia condensation and ahead of the converter. The loop purge
should be taken out after ammonia separation and before make-up gas addition. This
configuration is dependent on the make-up gas being treated in a drying step before entering
the loop. A make-up gas containing traces of water or carbon dioxide must be added before
ammonia condensation, with negative effects both to ammonia condensation and energy.
Conventional reforming with methanation as the final purification step, produces a synthesis
gas containing inerts (methane and argon) in quantities that do not dissolve in the condensed
ammonia. The major part of these inerts is removed by taking out a purge stream from the
loop. The size of this purge stream controls the level of inerts in the loop to about 10-15%.
The purge gas is scrubbed with water to remove ammonia before being used as fuel or before
being sent for hydrogen recovery.
Ammonia condensation is far from complete if cooling is with water or air and is usually not
satisfactory (dependent on loop pressure and cooling medium temperature). Vaporizing
ammonia is used as a refrigerant in most ammonia plants, to achieve sufficiently low
ammonia concentrations in the gas recycled to the converter. The ammonia vapors are
liquefied after recompression in the refrigeration compressor.

Steam and power system

Steam reforming ammonia plants have high-level surplus heat available for steam production
in the reforming, shift conversion, and synthesis sections, and in the convection section of the
primary reformer. Most of this waste heat is used for high pressure steam production for use
in turbines for driving the main compressors and pumps and as process steam extracted from
the turbine system.
A modern steam reforming ammonia plant can be made energetically self-sufficient if
necessary, but usually a small steam export and electricity import are preferred.

4. UREA PRODUCTION PROCESSES [3]

The commercial synthesis of urea (CON2H4) involves the combination of ammonia and
carbon dioxide at high pressure to form ammonium carbamate (CO2N2H6) which is
subsequently dehydrated by the application of heat to form urea and water.
2NH3 + CO2 ↔ NH2COONH4 (6)
NH2COONH4 ↔ CO(NH2)2 + H2O (7)
Reaction (6) is fast and exothermic and essentially goes to completion under the reaction
conditions used industrially. Reaction (7) is slower and endothermic and does not go to
completion. The conversion (on a CO2 basis) is usually in the order of 50-80%. The
conversion increases with increasing temperature and NH3/CO2 ratio and decreases with
increasing H2O/CO2 ratio.
The design of commercial processes has involved the consideration of how to separate the
urea from the other constituents, how to recover excess NH3 and decompose the carbamate
for recycle. Attention was also devoted to developing materials to withstand the corrosive
carbamate solution and to optimize the heat and energy balances.
The simplest way to decompose the carbamate to CO2 and NH3 requires the reactor effluent
to be depressurized and heated. The earliest urea plants operated on a “Once Through”
principle where the off-gases were used as feedstocks for other products. Subsequently
“Partial Recycle” techniques were developed to recover and recycle some of the NH3 and
CO2 to the process. It was essential to recover all of the gases for recycle to the synthesis to
optimize raw material utilization and since recompression was too expensive an alternative
method was developed. This involved cooling the gases and re-combining them to form
carbamate liquor which was pumped back to the synthesis. A series of loops involving
carbamate decomposers at progressively lower pressures and carbamate condensers were
used. This was known as the “Total Recycle Process”. A basic consequence of recycling the
gases was that the NH3/CO2 molar ratio in the reactor increased thereby increasing the urea
yield.
Significant improvements were subsequently achieved by decomposing the carbamate in the
reactor effluent without reducing the system pressure. This “Stripping Process” dominated
synthesis technology and provided capital/energy savings. Two commercial stripping systems
were developed, one using CO2 and the other using NH3 as the stripping gases.
Since the base patents on stripping technology have expired, other processes have emerged
which combine the best features of Total Recycle and Stripping Technologies. For
convenience total recycle processes were identified as either “conventional” or “stripping”
processes. Block flow diagram for CO2 stripping total recycle processes is shown in Figure 4.

Figure 4: Block diagram of a Total Recycle CO2 Stripping Urea Process.

The urea solution arising from the synthesis/recycle stages of the process is subsequently
concentrated to a urea melt for conversion to a solid prilled or granular product.
Improvements in process technology have concentrated on reducing production costs and
minimizing the environmental impact. These included boosting CO2 conversion efficiency,
increasing heat recovery, reducing utilities consumption and recovering residual NH3 and
urea from plant effluents. Simultaneously the size limitation of prills and concern about the
prill tower off-gas effluent were responsible for increased interest in melt granulation
processes. Some or all of these improvements have been used in updating existing plants and
some plants have added computerized systems for process control. New urea installations
vary in size from 800 to 2,000 mtd and typically would be 1,500 mtd units.

Carbon dioxide stripping process

NH3 and CO2 are converted to urea via ammonium carbamate at a pressure of approximately
140 bar and a temperature of 180-185°C. The molar NH3/CO2 ratio applied in the reactor is
2.95. This results in a CO2 conversion of about 60% and an NH3 conversion of 41%. The
reactor effluent, containing unconverted NH3 and CO2 is subjected to a stripping operation at
essentially reactor pressure, using CO2 as stripping agent. The stripped-off NH3 and CO2 are
then partially condensed and recycled to the reactor. The heat evolving from this
condensation is used to produce 4.5 bar steam some of which can be used for heating
purposes in the downstream sections of the plant. Surplus 4.5 bar steam is sent to the turbine
of the CO2 compressor.
The NH3 and CO2 in the stripper effluent are vaporized in a 4 bar decomposition stage and
subsequently condensed to form a carbamate solution, which is recycled to the 140 bar
synthesis section. Further concentration of the urea solution leaving the 4 bar decomposition
stage takes place in the evaporation section, where a 99.7% urea melt is produced.

Prilling and Granulation

In urea fertilizer production operations, the final product is in either prilled or granular form.
Production of either form from urea melt requires the use of a large volume of cooling air
which is subsequently discharged to the atmosphere. A block diagram of the prilling and
granulation processes is shown in Figure 5.
 Figure 5: Block Diagram for Urea Granulation and Prilling Processes.

Prilling
The concentrated (99.7%) urea melt is fed to the prilling device (e.g. rotating bucket/shower
type spray head) located at the top of the prilling tower. Liquid droplets are formed which
solidify and cool on free fall through the tower against a forced or natural up-draft of ambient
air. The product is removed from the tower base to a conveyor belt using a rotating rake, a
fluidized bed or a conical hopper. Cooling to ambient temperature and screening may be used
before the product is finally transferred to storage.
The design/operation of the prilling device exerts a major influence on product size. Collision
of the molten droplets with the tower wall as well as inter-droplet contact causing
agglomeration must be prevented. Normally mean prill diameters range from 1.6-2.0 mm for
prilling operations.

Granulation
Depending on the process a 95-99.7% urea feedstock is used. The lower feedstock
concentration allows the second step of the evaporation process to be omitted and also
simplifies the process condensate treatment step. The basic principle of the process involves
the spraying of the melt onto recycled seed particles or prills circulating in the granulator. A
slow increase in granule size and drying of the product takes place simultaneously. Air
passing through the granulator solidifies the melt deposited on the seed material. Processes
using low concentration feedstock require less cooling air since the evaporation of the
additional water dissipates part of the heat which is released when the urea crystallizes from
liquid to solid.
All the commercial processes available are characterized by product recycle, and the ratio of
recycled to final product varies between 0.5 and 2.5. Prill granulation or fattening systems
have a very small recycle, typically 2 to 4%. Usually the product leaving the granulator is
cooled and screened prior to transfer to storage. Conditioning of the urea melt prior to
spraying may also be used to enhance the storage/handling characteristics of the granular
product.

References
1- Varotto, A., Enhanced catalytic performance for global ammonia production,
Quantum Sphere Inc., 2015.
2- European Fertilizer Manufactures’ Association, Booklet No. 1: Production of
ammonia, 2000.
3- European Fertilizer Manufactures’ Association, Booklet No. 5: Production of urea and
urea ammonium nitrate, 2000.