TRANSPORTASI &

PEMANFAATAN GAS BUMI

AMMONIA & DERIVATIVES

Kelompok IV

Zenda Christian Adhitama

Aep Riyadi
Goffar Utomo
Ragil Priyanto

May 30, 2023

AMMONIA & DERIVATIVES
Overview
• Ammonia (NH3) is a fundamental manufacturing component Figure 1 shows the main categories of ammonia
and the cheapest compound combining nitrogen with raw applications
elements, utilized in more than 76% of all nitrogen based
products
• A translucent product with a distinctive strong odor, NH3 is
mainly produced through the “harsh” reaction of N2 and H2 at
high temperatures and under compression in the presence of
a proper catalyst. When created by this process, it is known
as synthetic ammonia
• NH3 is also obtained as a byproduct in coal coking; however,
this type of NH3, referred to as byproduct ammonia, is
generated in considerably lower amounts than the former
type (synthetic ammonia) [2]. The Haber and Bosch
technique is the most commonly used worldwide; however, it
is also the most expensive.

2 Source : Amhamed et al, 2022. MDPI

AMMONIA & DERIVATIVES
Ammonia Manufacture

• The objective is to obtain an ammonia synthesis gas of

composition 3:1 hydrogen: nitrogen.
3H2 + N2 = 2NH3

• Ammonia is stored and shipped in large pressure

vessels. Some also use cryogenics. Ammonia shipping
is tied into the LPG shipping trade, and many ships are
constructed to carry either LPG or ammonia.

Table 1. Typical gas compositions in ammonia synthesis

3 Source : Sedon, 2006
 AMMONIA & DERIVATIVES
Ammonia Process Flow Diagram

Natural Gas DESULFURIZATI

ON

4 Figure 2. Ammonia Process Flow Diagram

AMMONIA & DERIVATIVES
Ammonia Process Description

• Desulfurization
The concentration of sulfur compounds, primarily hydrogen sulfide (H2S), should be reduced to very low
levels using zinc oxide absorbent, preferably below 1 ppm (parts per million) to preserve the steam-
reforming catalyst. Operating Conditions: Temperature: 300-500°C, Pressure: Atmospheric to moderate
pressure. ZnO + H2S → ZnS + H2O.
• Primary Reformer:
The desulfurized natural gas is then fed into a primary reformer, where it reacts with steam in the
presence of a catalyst, usually nickel-based. This reaction, known as steam reforming, converts
methane (the main component of natural gas) into a synthesis gas, also called a reformate or primary
reformer effluent. The synthesis gas consists mainly of hydrogen (H2) and carbon monoxide (CO).
Operating Conditions: Temperature: 800-900°C, Pressure: High pressure.

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AMMONIA & DERIVATIVES
Ammonia Process Description
• Secondary Reformer
The reformate from the primary reformer is further processed in a secondary reformer. In this step,
additional air or oxygen is introduced to the reformate, and the remaining methane are converted to
hydrogen. This process is known as partial oxidation. The secondary reformer operates at higher
temperatures than the primary reformer, typically utilizing a different catalyst, such as a platinum-
based catalyst.
Operating Conditions: Temperature: 1000-1200°C, Pressure: High pressure
• Water Gas Shift (WGS) Reaction:
The synthesis gas from the secondary reformer contains a high concentration of carbon monoxide,
which needs to be reduced for efficient ammonia synthesis. The synthesis gas is passed through a
water gas shift reactor, where it reacts with steam in the presence of a shift catalyst (usually based on
iron or copper). This reaction converts a significant portion of the carbon monoxide into carbon
dioxide and hydrogen, increasing the hydrogen-to-carbon monoxide ratio.
6
Operating Conditions: Temperature: 200-400°C, Pressure: Moderate pressure.
AMMONIA & DERIVATIVES
Ammonia Process Description
• CO2 Absorber
The gas leaving the water gas shift reactor is rich in hydrogen, carbon dioxide, and water vapor. To
remove the carbon dioxide, the gas is directed to a CO2 absorber or scrubber. In the absorber, a suitable
solvent, such as an amine solution, is used to selectively absorb the carbon dioxide. This process results
in a purified hydrogen (H2) stream with a very low concentration of CO2, preferably below 1%.
• Methanation
The gas stream from the CO2 absorber may still contain traces of carbon monoxide and carbon
dioxide. To further reduce these impurities, the gas is passed through a methanation reactor. In this
step, any remaining carbon monoxide and carbon dioxide are reacted with hydrogen over a
methanation catalyst (often nickel-based) to form methane. This reaction improves the purity of the gas
and prevents carbon monoxide from poisoning the ammonia synthesis catalyst, typically less than 1%.
Operating Conditions: Temperature: 200-400°C, Pressure: Moderate pressure.

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AMMONIA & DERIVATIVES
Ammonia Process Description
• Drying
After methanation, the gas is usually dried to remove any remaining water vapor. This step is crucial
because water can negatively affect the performance of the downstream catalysts. Drying is typically
achieved using molecular sieves or other desiccant materials. ensuring that the concentration of water
is minimized to very low levels, typically below 1 ppm
• Ammonia Synthesis Reactor
The dried gas, consisting primarily of hydrogen and nitrogen, is then directed to the ammonia
synthesis reactor. Inside the reactor, the gas is passed over an iron-based catalyst, usually promoted
with small amounts of other metals. Under high pressure and temperature, the hydrogen and nitrogen
react to form ammonia (NH3) according to the Haber-Bosch process. The ammonia synthesis reaction
is exothermic, and the heat generated is typically removed through a cooling system. Operating
Conditions: Temperature: 350-550°C, Pressure: High pressure. N2(g) + 3H2(g) ⇌ 2NH3(g)
The separation of ammonia from the unreacted gas occurs in in the facilities using refrigerated
8 chilling. Ordinarily, the temperature is lowered to around 25 K, and the liquefied NH3 in the elevated-
pressure separators is flashed at 2000 kPa.
UREA
Overview
• Urea is an organic chemical compound which is also
referred sometimes as Carbamide.
• Historically urea is a significant chemical compound
because it was the first organic chemical which is naturally
found in human body to be synthesized using inorganic
chemicals in a laboratory by Friedrich Wöhler.
• The most popular and most common use of urea is as a
fertilizer not only because it has the highest nitrogen
content of 46% compared to other fertilizers but also
because it dissolves readily in water and leaves no salt
residues on the soil and crops.
• The major disadvantage of using urea as a fertilizer is that
it may contain a chemical compound named biuret which is
formed during manufacturing of urea. Figure 3. Integrated Ammonia and Urea Plant
Urea is made by reacting the carbon dioxide and
• . ammonia produced in ammonia plant
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UREA
Process Flow Diagram
Two chemical reactions are primarily
involved in the process:
• Reaction of Ammonia and Carbon
Dioxide to form Ammonium
Carbamate.
2NH3 + CO2 <=>NH2COONH4

• Decomposition of Ammonium
Carbonate to form Urea and Water.
NH2COONH4 <=> H2O+
NH2CONH2
(urea)
Total Reaction:
2NH3 + CO2 <=> NH2.CO.NH2 + H2O

The pressure and temperature is

maintained at 14 Mpa and 170-190°C
for the first reaction to occur
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UREA
Process Flow Diagram
• The raw materials which are used in urea manufacturing process are ammonia and carbon
dioxide hence generally urea is manufactured in an ammonia plant because it yields ammonia
as a product and carbon dioxide as a byproduct and this carbon dioxide can be used directly for
manufacturing urea.
• Liquid ammonia is pumped and carbon dioxide is compressed and transported to an equipment
called reaction chamber.
• The major impurity in urea is water and also unreacted ammonia, carbon dioxide and
ammonium carbamate. These are removed using distillation tower and evaporator. Essential
condition is to keep temperature high and pressure low during stages of separation.
• The evaporator is used to concentrate the molten urea, which is passed through nozzles in a
prilling tower. Compressed air is then passed in the tower to shape the urea into prills or
granules. The urea is then stored and ready to be sold.

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AMMONIUM NITRATE
Overview
• Ammonium nitrate is the nitrate salt of the
ammonium cation (NH4NO3, sometimes written as
N2H4O3) that is a white crystal solid and is highly
soluble in water. It is produced by neutralizing
nitric acid (HNO3) with ammonia (NH3).
• Ammonium nitrate is marketed in several forms,
depending upon its use.
• Liquid ammonium nitrate may be sold as a
fertilizer, generally in combination with urea.
Liquid ammonium nitrate may be concentrated to
form an ammonium nitrate "melt" for use in solids
formation processes.
• Solid ammonium nitrate may be produced in the
form of prills, grains, granules, or crystals. Prills
can be produced in either high or low density form,
depending on the concentration of the melt. High
density prills, granules, and crystals are used as
fertilizer, grains are used solely in explosives, and
low density prills can be used as either.
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AMMONIUM NITRATE
Process Flow Diagram
• The manufacture of ammonium
nitrate involves several major unit
operations including solution
formation and concentration; solids
formation, finishing, screening, and
coating; and product bagging and/or
bulk shipping
• All ammonium nitrate plants produce
an aqueous ammonium nitrate
solution through the reaction of
ammonia and nitric acid in a
neutralizer as follows:
NH3 + HNO3 → NH4NO3

13
Source, Inorganic Chemistry Industry, 2027
AMMONIUM NITRATE
Process Flow Diagram
• The manufacture of ammonium nitrate involves several major unit operations, such as solution formation
and concentration, solids formation, finishing, screening, and coating, and product bagging and/or bulk
shipping.
• Plants producing ammonium nitrate solutions alone use only the solution formation, solution blending,
and bulk shipping operations.
• To produce a solid product, the ammonium nitrate solution is concentrated in an evaporator or
concentrator. This melt is then used to make solid ammonium nitrate products. Prilling and granulation are
the most common processes used to produce solid ammonium nitrate.
• Additive such as magnesium nitrate or magnesium oxide may be injected into the melt stream to raise the
crystalline transition temperature, act as a desiccant, and allow solidification to occur at a low
temperature.
• Rotary drum or fluidized bed cooling prevents deterioration and agglomeration of solids before storage
and shipping.
• Screening for consistently sized prills and granules is done before cooling. Products can be coated in a
rotary drum to prevent agglomeration during storage and shipment. Solid ammonium nitrate is stored and
shipped in either bulk or bags.
14
Source, Inorganic Chemistry Industry, 2027
AMMONIUM SULPHATE
Overview
• Ammonium sulfate ((NH4)2SO4) is an inorganic salt with a number of commercial uses.
• The most common use is as a soil fertilizer since the chemical contains 21% (w/w) nitrogen and 24% (w/w)
sulfur.
• The chemical has also been used in flame retardant chemicals because, as a flame retardant, it increases the
combustion temperature of the material, decreases maximum weight loss rates, and causes an increase in the
production of residue or char.
• Ammonium sulfate has been used as a wood preservative, but due to its hygroscopic nature, this use has
been largely discontinued because of associated problems with metal fastener corrosion, dimensional
instability, and finish failures.
• Typically, ammonium sulfate is produced by combining anhydrous ammonia and sulfuric acid:
2NH3 + H2SO4 → (NH4)2SO4

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AMMONIUM SULPHATE
Process Flow Diagram

The neutralizer evaporator and the crystallizer are interconnected so that the heat released during neutralization is
utilized to evaporate water in the ammonium sulphate slurry. These units operate under partial vacuum. The salt is
separated by centrifugation and the mother liquor is recycled. The wet salt passes through rotary drier and cooler to
obtain the product. The flow diagram for ammonium sulphate production by direct neutralization process is given
in figure below.

16 https://www.sciencedirect.com/topics/earth-and-planetary-
sciences/neutralizers
TERIMA KASIH