PROBLEM STATEMENT

• To design ammonia production plant for 950 Metric Tonnes/ day

of Ammonia using Natural gas.

The composition of natural gas is taken as-

Component Vol %

CH4 97.97

C2H6 01.79

C3H8 00.14

H2 00

N2 00.10

CO 00.00

CO2 00.00

Ar 00.03

Total 100

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1.1 Ammonia
Ammonia is a compound of nitrogen and hydrogen with the formula NH3. Ammonia is a
colourless gas with a characteristic pungent smell. It is a common nitrogenous waste,
particularly among aquatic organisms, and it contributes significantly to the nutritional needs
of terrestrial organisms by serving as a precursor to food and fertilizers. Ammonia, either
directly or indirectly, is also a building block for the synthesis of many pharmaceutical
products and is used in many commercial cleaning products. It is mainly collected by
downward displacement of both air and water. Ammonia is named for the Ammonians,
worshipers of the Egyptian god Amun, who used ammonium chloride in their rituals.

Although common in nature and in wide use, ammonia is both caustic and hazardous in its
concentrated form. It is classified as an extremely hazardous substance in the United States,
and is subject to strict reporting requirements by facilities which produce, store, or use it in
significant quantities.

The global industrial production of ammonia in 2014 was 176 million tonnes, a 16% increase
over the 2006 global industrial production of 152 million tonnes. Industrial ammonia is sold
either as ammonia liquor (usually 28% ammonia in water) or as pressurized or refrigerated
anhydrous liquid ammonia transported in tank cars or cylinders.

Ammonia is a chemical found in trace quantities in nature, being produced from nitrogenous
animal and vegetable matter. Ammonia and ammonium salts are also found in small
quantities in rainwater.

On smaller, icy planets such as Pluto, ammonia can act as a geologically important
antifreeze, as a mixture of water and ammonia can have a melting point as low as 173 K
(−100 °C; −148 °F) if the ammonia concentration is high enough and thus allow such planets
to retain internal oceans and active geology at a far lower temperature than would be possible
with water alone.Substances containing ammonia, or those that are similar to it, are
called ammonical.

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1.3 Properties

Ammonia is a colourless gas with a characteristic pungent smell. It is lighter than air, its
density being 0.589 times that of air. It is easily liquefied due to the strong hydrogen
bonding between molecules; the liquid boils at −33.3 °C (−27.94 °F), and freezes at −77.7 °C
(−107.86 °F) to white crystals.

Ammonia may be conveniently deodorized by reacting it with either sodium bicarbonate

or acetic acid. Both of these reactions form an odourless ammonium salt.

1.3.1 Structure

The ammonia molecule has a trigonal pyramidal shape as predicted by the valence shell
electron pair repulsion theory (VSEPR theory) with an experimentally determined bond angle
of 106.7°. The central nitrogen atom has five outer electrons with an additional electron from
each hydrogen atom. This gives a total of eight electrons, or four electron pairs that are
arranged tetrahedrally. Three of these electron pairs are used as bond pairs, which leaves one
lone pair of electrons. The lone pair of electrons repel more strongly than bond pairs,
therefore the bond angle is not 109.5°, as expected for a regular tetrahedral arrangement, but
106.7°. The nitrogen atom in the molecule has a lone electron pair, which makes ammonia
a base, a proton acceptor. This shape gives the molecule a dipole moment and makes it polar.
The molecule's polarity, and especially, its ability to form hydrogen bonds, makes ammonia
highly miscible with water. Ammonia is moderately basic, a 1.0 M aqueous solution has a pH
of 11.6 and if a strong acid is added to such a solution until the solution is neutral (pH = 7),
99.4% of the ammonia molecules are protonated. Temperature and salinity also affect the
proportion of NH4+. The latter has the shape of a regular tetrahedron and
is isoelectronic with methane.

The ammonia molecule readily undergoes nitrogen inversion at room temperature; a useful
analogy is an umbrella turning itself inside out in a strong wind. The energy barrier to this
inversion is 24.7 kJ/mol, and the resonance frequency is 23.79 GHz.

1.3.2 Toxicity

The toxicity of ammonia solutions does not usually cause problems for humans and other
mammals, as a specific mechanism exists to prevent its build-up in the bloodstream.
Ammonia is converted to carbamoyl phosphate by the enzyme carbamoylphosphate and then
enters the urea cycle to be either incorporated into amino acids or excreted in the

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urine. Fish and amphibians lack this mechanism, as they can usually eliminate ammonia from
their bodies by direct excretion. Ammonia even at dilute concentrations is highly toxic to
aquatic animals, and for this reason it is classified as dangerous for the environment.

Ammonia is a constituent of tobacco smoke.

1.3.3 Amphotericity

One of the most characteristic properties of ammonia is its basicity. Ammonia is considered
to be a weak base. It combines with acids to form salts; thus with hydrochloric acid it
forms ammonium chloride (sal ammoniac); with nitric acid, ammonium nitrate, etc. Perfectly
dry ammonia will not combine with perfectly dry hydrogen chloride; moisture is necessary to
bring about the reaction. As a demonstration experiment, opened bottles of concentrated
ammonia and hydrochloric acid produce clouds of ammonium chloride, which seem to
appear "out of nothing" as the salt forms where the two diffusing clouds of molecules meet,
somewhere between the two bottles.

NH3 + HCl → NH4C

The salts produced by the action of ammonia on acids are known as the ammonium
salts and all contain the ammonium ion (NH4+).

Although ammonia is well known as a weak base, it can also act as an extremely weak
acid. It is a protic substance and is capable of formation of amides (which contain the
NH2− ion). For example, lithium dissolves in liquid ammonia to give a solution of lithium
amide:

2Li + 2NH3 → 2LiNH2 + H2

1.3.4 Self-dissociation

Like water, ammonia undergoes molecular autoionisation to form its acid and base
conjugates:

2 NH3 (aq) ⇌ NH+4 (aq) + NH−2 (aq)

Ammonia often functions as a weak base, so it has some buffering ability. Shifts in pH will
cause more or fewer ammonium cations (NH+4) and amide anions (NH−2) to be present
in solution. At standard pressure and temperature, K=[NH+4][NH−2] = 10−30

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1.3.5 Combustion

The combustion of ammonia to nitrogen and water is exothermic:

4 NH3 + 3 O2 → 2 N2 + 6 H2O (g)

The standard enthalpy change of combustion,expressed per mole of ammonia and with
condensation of the water formed, is −382.81 kJ/mol. Dinitrogen is the thermodynamic
product of combustion: all nitrogen oxides are unstable with respect to N2 and O2, which is
the principle behind the catalytic converter. Nitrogen oxides can be formed as kinetic
products in the presence of appropriate catalysts, a reaction of great industrial importance in
the production of nitric acid:

4 NH3 + 5 O2 → 4 NO + 6 H2O

A subsequent reaction leads to NO2

2 NO + O2 → 2 NO2

The combustion of ammonia in air is very difficult in the absence of a catalyst (such
as platinum gauze or warm chromium(III) oxide), because the temperature of the flame is
usually lower than the ignition temperature of the ammonia–air mixture. The flammable
range of ammonia in air is 16–25%.

1.4 USES OF AMMONIA:

1.4.1 Fertilizer

Globally, approximately 88% (as of 2014) of ammonia is used as fertilizers either as its salts,
solutions or anhydrously. When applied to soil, it helps provide increased yields of crops
such as maize and wheat. 30% of agricultural nitrogen applied in the USA is in the form of
anhydrous ammonia and worldwide 110 million tonnes are applied each year.

Precursor to nitrogenous compounds

Ammonia is directly or indirectly the precursor to most nitrogen-containing compounds.

Virtually all synthetic nitrogen compounds are derived from ammonia. An important
derivative is nitric acid. This key material is generated via the Ostwald
process by oxidation of ammonia with air over a platinum catalyst at 700–850 °C (1,292–
1,562 °F), ~9 atm. Nitric oxide is an intermediate in this conversion:

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 NH3 + 2 O2 → HNO3 + H2O

Nitric acid is used for the production of fertilizers, explosives, and many organonitrogen
compounds.

Ammonia can also be used to make compounds in reactions which are not specifically
named. Examples of such compounds also include the following: ammonium
perchlorate, ammonium
nitrate, formamide, dinitrogentetroxide, alprazolam, ethanolamine, ethylcarbamate, hexameth
ylenetetramine, and ammonium bicarbonate.

1.4.2 As a cleaner

Household ammonia is a solution of NH3 in water (i.e., ammonium hydroxide) used as a

general purpose cleaner for many surfaces. Because ammonia results in a relatively streak-
free shine, one of its most common uses is to clean glass, porcelain and stainless steel. It is
also frequently used for cleaning ovens and soaking items to loosen baked-on grime.
Household ammonia ranges in concentration by weight from 5 to 10% ammonia. United
States manufacturers of cleaning products are required to provide the product's material
safety data sheet which lists the concentration used.

1.4.3 Fermentation

Solutions of ammonia ranging from 16% to 25% are used in the fermentation industry as a
source of nitrogen for microorganisms and to adjust pH during fermentation.

1.4.4 Antimicrobial agent for food products

As early as in 1895, it was known that ammonia was "strongly antiseptic ... it requires 1.4
grams per litre to preserve beef tea." In one study, anhydrous ammonia destroyed 99.999%
of zoonotic bacteria in 3 types of animal feed, but not silage. Anhydrous ammonia is
currently used commercially to reduce or eliminate microbial contamination of beef. Lean
finely textured beef in the beef industry is made from fatty beef trimmings (c. 50–70% fat) by
removing the fat using heat and centrifugation, then treating it with ammonia to kill E.Coli.
The process was deemed effective and safe by the US Department of Agriculture based on a
study that found that the treatment reduces E.coli to undetectable levels. There have been
safety concerns about the process as well as consumer complaints about the taste and smell of

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beef treated at optimal levels of ammonia.The level of ammonia in any final product has not
come close to toxic levels to humans.

1.4.5 Minor and emerging uses

Refrigeration

Because of ammonia's vaporization properties, it is a useful refrigerant. It was commonly

used before the popularisation of chlorofluorocarbons (Freons). Anhydrous ammonia is
widely used in industrial refrigeration applications and hockey rinks because of its
high energy efficiency and low cost. It suffers from the disadvantage of toxicity, which
restricts its domestic and small-scale use. Along with its use in modern vapor-compression
refrigeration it is used in a mixture along with hydrogen and water in absorption refrigerators.
The Kalina cycle, which is of growing importance to geothermal power plants, depends on
the wide boiling range of the ammonia–water mixture. Ammonia coolant is also used in the
S1 radiator aboard the International Space Station in two loops which are used to regulate the
internal temperature and enable temperature dependent experiments.

The potential importance of ammonia as a refrigerant has increased with the discovery that
vented CFCs and HFCs are extremely potent and stable greenhouse gases. The contribution
to the greenhouse effect of CFCs and HFCs in current use, if vented, would match that of all
CO2 in the atmosphere.

For remediation of gaseous emissions

Ammonia is used to scrub SO2 from the burning of fossil fuels, and the resulting product is
converted to ammonium sulfate for use as fertilizer. Ammonia neutralizes the nitrogen oxide
(NOx) pollutants emitted by diesel engines. This technology, called SCR (selective catalytic
reduction),.
Ammonia may be used to mitigate gaseous spills of phosgene.

As a stimulant

Ammonia, as the vapor released by smelling salts, has found significant use as a respiratory
stimulant. Ammonia is commonly used in the illegal manufacture
of methamphetamine through a Birch reduction. The Birch method of making
methamphetamine is dangerous because the alkali metal and liquid ammonia are both
extremely reactive, and the temperature of liquid ammonia makes it susceptible to explosive
boiling when reactants are added.

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Textile

Liquid ammonia is used for treatment of cotton materials, giving properties

like mercerisation, using alkalis. In particular, it is used for prewashing of wool.

Lifting gas

At standard temperature and pressure, ammonia is less dense than atmosphere and has
approximately 45-48% of the lifting power of hydrogen or helium. Ammonia has sometimes
been used to fill weather balloons as a lifting gas. Because of its relatively high boiling point
(compared to helium and hydrogen), ammonia could potentially be refrigerated and liquefied
aboard an airship to reduce lift and add ballast (and returned to a gas to add lift and reduce
ballast).

Woodworking

Ammonia has been used to darken quartersawn white oak in Arts & Crafts and Mission-style
furniture. Ammonia fumes react with the natural tannins in the wood and cause it to change
colours.

Energy carrier

Ammonia can be manufactured from solar energy, air and water. This is an efficient way to
package hydrogen into a chemical that is much cheaper to store and transport than pure
hydrogen be it as gas or as liquid. In fact, per volume ammonia holds more hydrogen than
does liquid hydrogen. Ammonia may be the key to overcome not only the daily but also the
seasonal fluctuations of renewable energy sources.

1.5 AMMONIA PRODUCTION PROCESSES:

All processes for synthesis of ammonia are based on the pressure catalytic reaction of N2 and
H2. The principle variation is in the operating pressure.

1.5.1 Born Haber process invented by German chemist Fritz Haber in 1908.

N2 +H2 → 2NH3. promoted iron catalyst

400-450 deg. C

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 150-200 atm 17% conversion.

1.5.2 Du Pont process;

Very high Pressure (900-1000 atm)

500-600deg C;

15-25% conversion.

1.5.3 Casale;

High Pressure(600 atm)

500 deg C;

15-25% conversion.

1.5.4 Mont Cenis;

Low pressure (100atm)

400-425 deg C;

8-20% conversion

1.6 HABER PROCESS:

FRITZ HABER

Theory:

NH3 is manufactured by Haber’s process. In this process, pure nitrogen and hydrogen gases
react in the ratio of 1:3 by volume in 400°C-500°C temperature, 200-900 atm pressure in
presence of iron as catalyst & molybdenum as promoter.

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 Fe/Mo (400-500°C)

N2+3H2——————–> 2NH3+ heat

(200-900atm)

Conditions for maximum yield:

1. Low Temperature:

Since the reaction isexothermic, it favors low working temperature for maximum yield of
product i.e. around 500°C.

2. High Pressure:

Four volume reactant gives two volume of product i.e. volume is reduced to half. Hence there
is maximum production of ammonia at 200-900 atm pressure (high).

3. Use of Catalyst:

Use of catalyst makes the reaction faster in forward direction. Hence the catalyst like iron
(Fe) &promoter like molybdenum (Mo) is used for maximum yield of the product.

4. Purity of Reactant:

The purity of the reactants Hydrogen (H2) & Nitrogen (N2) helps in the more yielding of the
product.

5.Concentration of Reactants:

More the concentration of reactant, more the production. So, high concentration of hydrogen
and nitrogen is used.

2. PROCESS DESCRIPTION

2.1 FEED GAS COMPRESSION , PREHEATING & DESULFURIZATION

Natural gas for feed and fuel is supplied at the plant battery limit at 300 0C and 40.5 kg /cm2
natural gas is initially directed to a Feed Gas Knockout Drum , where any entrained liquid are
removed. Part of the natural gas from the outlet of Feed gas knockout drum is sent to the
primary reformer furnace as fuel.

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The remaining natural gas is compressed to 57.3 kg/cm2 in the Feed Gas compressor, which
is driven by an electric motor. To allow the compressor to operate over a wide range of
operating conditions without going into surge, it is provided with Kickback line with a
Kickback cooler. This allows some of the compressor discharge gas to be recycled back to
the compressor suction through Feed gas knockout drum. This is typically required during
plant start-up and turn down conditions when the feed gas flow is much lower than normal.

After compression in feed gas compressor , natural gas feed is mixed with a small amount of
sy-ngas recycled from the synthesis loop which provides the required hydrogen for the
downstream hydrotreater. If the synthesis loop is not in operation, the hydrogen recycle
stream can be taken from the Methanator Effluent Separator overhead, and added at the
suction to Feed gas compressor. There is also a provision to generate hydrogen via ammonia
cracking in the primary reformer during initial plant start-up.

The mixture of natural gas and hydrogen is heated to 3710C, first using condensing LP steam
in the LP steam/Feed Gas Preheater , and then in the Feed Gas Coil located in the convection
section of the primary reformer . The hot gas then enters a two-step desulfurization system. In
the first step, the hot gas passes through Hydrotreater, which contains cobalt/molybdenum
(CoMo) catalyst. The catalyst ensures hydrogenation of organic sulphur compounds, if
present in the feed gas, such as mercaptans (RSH), carbonyl sulfide (COS), to hydrogen
sulfide.

COS + H2 CO + H2S

RSH + H2 RH + H2S

In the second step, hydrogen sulfide in the feed gas is removed in two desulfurizers. Each
desulfurizer contains a bed of zinc oxide. Hydrogen sulfide reacts with the zinc oxide and is
retained as zinc sulfide, thereby producing an effluent stream containing less than 0.1 ppmv
of sulphur.

H2S + ZnO ZnS + H2O

The two desulfurizer vessels are arranged in series, in a lead-lag configuration such that
either vessel can be taken out of service to replace the zinc oxide while the other vessel
remains in service and plant operation is not interrupted. Each vessel contains enough zinc
oxide to last for at least one year of continuous service at the design inlet sulfur concentration
of 10 ppmv hydrogen sulfide in the feed gas.

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2.2 PRIMARY REFORMING

Desulfurized feed gas is mixed with process steam from the overhead of the Process
Condensate Stripper to give a steam to organic carbon molar ratio of 2.7:1. The feed gas flow
is controlled by ratio to the process steam flow. This feature protects the reforming catalysts
in case of loss of process steam. The mixture is preheated to about 495 0 C in the convection
section of the Primary Reformer . The preheated mixed feed is distributed over tubes packed
with reforming catalyst and suspended in the radiant section of Primary reformer. Steam
Reforming reactions takes place over the Nickel based reforming catalyst in the radiant tubes
to form carbon monoxide, carbon dioxide and hydrogen. Steam reforming reaction for any
hydrocarbon can be written as

CnHm + nH2O nCO + (2n+m)/2 H2

For methane the above reaction becomes:

CH4 + H2O CO + 3H2

The water gas shift reaction converts carbon monoxide to carbon dioxide and additional
hydrogen:

CO + H2O CO2 + H2

The Primary reformer effluent gas at 48.0kg/cm2 (a) and 72loC contains about 29.9 mole%
(dry basis) of unreacted methane. The Primary reformer effluent is sent to the Secondary
Reformer via the Primary Reformer Effluent Transfer line .

Heat for the endothermic steam reforming reactions in Primary reformer is supplied by the
combustion of fuel gas in burners located at the top of the furnace. The burners are located
between rows of catalyst tubes and operate with downward firing. Thus, the heat flux is
highest at the top of tubes, where the process temperatures are the lowest and most of the
reforming reaction is being done. The outlet manifolds and riser tubes are located inside the
radiant box, for heat conservation. The primary reformer uses the latest refractory and
insulation technology.

Ceramic fiber lining in the radiant section provides rapid thermal response due to low heat
storage. Super duty hard factory is used where flames may contact the sidewalls. The

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reformer is designed with 2% oxygen (dry basis) in the flue gas at the outlet of the radiant
section. This ensures complete combustion of the fuel in the burners.

The Purifier process uses excess air in the secondary reformer. This feature reduces the size
of the primary reformer furnace by about one third, and lowers the process gas outlet
temperature from the reformer substantially, as compared to a conventional ammonia plant.
The lower outlet temperature results in longer tube and catalyst life.

The primary reformer is designed to obtain maximum thermal efficiency by recovering heat
from the flue gas in the convection section. The heat recovered is used for the following
services:

• Mixed Feed Preheating

• Process Air Preheating
• Steam Superheating
• Feed Gas Preheating
• Combustion Air Preheating

2.3 PROCESS AIR COMPRESSION

Process air is drawn in through an Air Filter which removes any dust particles. Process air is
then compressed in an integrally geared Process Air Compressor to a pressure of 50.8kg/cm2
(a). Inter Stage cooling and condensate separation is provided in process air compressor.
Process air compressor is controlled to maintain a constant pressure drop across the
downstream process air control valve. During plant startup or turndown operation, enough
compressed air is vented to maintain the minimum load on the compressor to prevent it from
going into surge. Compressed process air is then preheated to about 5100C in Air preheat Coil
located in the convection section of Primary reformer, and sent to the secondary reformer.
Steam is continuously added to the process air to the inlet of the coil. This feature prevents
backflow of hot gas from the secondary Reformer in the event of Process air compressor trip.
Process air compressor also provides plant and instrument air which is required for the entire
plant from one of the intermediate stages of the compressor.

2.4 SECONDARY REFORMING

Hot compressed process air and primary reformer effluent are sent to the top section of the
Secondary Reformer where spontaneous combustion occurs. The resulting hot gas mixture

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then flows down through a bed of Nickel based reforming catalyst in the lower section of
Secondary reformer. The heat released from the combustion reactions in the upper section
supplies the heat for the steam reforming reactions in the lower section, converting methane
to more carbon oxides and hydrogen. The unreacted methane content in the gas leaving
Secondary reformer is about 1.8mole% (dry basis).

In a conventional ammonia plant, the amount of process air introduced in the secondary
reformer is controlled carefully to produce a stoichiometric 3:1 molar ratio of hydrogen to
nitrogen at the inlet to the ammonia converter.

In the Purifier process, about 50 percent excess air is used in the secondary reformer with the
excess nitrogen being removed in the Purifier Cold box. The excess air produces additional
combustion heat for the reforming reactions in the Secondary reformer. Thus the reforming
load is shifted from the primary reformer to the secondary reformer. This feature lowers the
primary reformer outlet temperature and furnace duty. In addition, the methane leakage from
the reforming section is relaxed as the unreacted methane is removed in the Purifier Cold
box. This reduces the overall reforming severity and lowers the secondary outlet temperature
to about 906 0C. The lower reformer results in milder conditions for the downstream waste
heat boiler as compared to conventional plants.

The heat in the Secondary reformer effluent is recovered by generating HP steam (104kg/cm2
(g)) in the Secondary Reformer Waste Heat Boiler is a KBR proprietary design. It is vertical
water tube, themosyphon boiler.

For safety reasons, Secondary reformer, Primary Reformer Effluent Transfer line and waste
heat boiler are provided with water jackets. The water jackets keep the metal walls cooler,
and provide an early warning system against any possible refractory failure which allows an
orderly shutdown of the plant in such a scenario.

2.5 SHIFT CONVERSION

The cooled secondary reformer effluent is sent to high Temperature shifter (HTS) Converter
reactor. Here , the gas flows over a bed of HTS catalyst (Fe based catalyst ) and carbon
monoxide reacts with steam to form carbon dioxide and hydrogen via the water gas shift
reaction.

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 CO + H2O CO2+ H2

About 72% of the carbon monoxide is shifted to carbon dioxide in HTS converter. The
carbon monoxide content in the HTS effluent is about 2.9% (dry basis). The water gas shift
reaction is exothermic. The gas leaving the HTS converter is cooled by generating high
pressure steam in the HTS effluent and by heating high pressure boiler feed water in the HTS
effluent.

The gas then passes through a LTS guard bed which is packed with LTS catalyst. Catalyst
volume is based on 2.5 years of catalyst life. LTS guard effluent is cooled by the BFW in the
LTS guard bed effluent and is then sent to LTS shift converter at about 208 degree celcius.
Most of the remaining carbon monoxide is carbon dioxide in LTS, leaving a residual carbon
monoxide content about .25 mole% (dry basis) in the LTS effluent. LTS effluent is cooled
against BFW in the LTS effluent and by raising low pressure steam in the LTS effluent low
pressure steam generator. The gas is then sent to CO2 stripper and further cooled in LTS
effluent to about 70 degree celcius. The overhead of raw gas separator is sent to carbon
dioxide removal unit

2.6 CARBONDIOXIDE REMOVAL

The carbon dioxide removal unit uses two stage aMDEA process licensed BASF. The process
gas enters the bottom of CO2 absorber at 70 degree celcius. It is contacted counter-currently
with the semi-lean aMDEA solution. The gas then flows upward into top section of CO2
absorber tower where it is contacted with lean aMDEA solution. The gas is then passed
through a water wash section,a demister pad and is sent to CO2 absorber overhead knockout
drum to remove traces of entertained aMDEA solution.

Rich aMDEA solution from the bottom of CO2 absorber is first Passed through a power
recovery hydraulic turbine. The power recovered in the hydraulic turbine is used to drive one
of the semi-lean solution pump. The rich aMDEA solution is then sent to high pressure flash
where most of the dissolved inert are flashed out from the rich solution.

As the flash gas from the high pressure flash contain a fair amount of the carbon dioxide .this
gas is further scrubbed with the slipstream of lean aMDEA solution in the high pressure gas
scrubber to recover almost all of the carbon dioxide.

The high pressure gas scrubber bottoms are mixed with the high pressure flash bottom and
sent to the CO2 low pressure flash. The low pressure flash operates about 1.8kg/cm2 .at this

15
low pressure most of the carbon dioxide from the rich aMDEA solution is flashed. The
solution flows down through the packed bed where it is contacted with rising vapor from
CO2 stripper.condensate is separated from the CO2 low pressure flash overhead knockout
drum and pumped by the CO2 low pressure reflux pump to provide wash water for CO2
absorber. CO2 low pressure flash and high pressure flash gas scrubber .the makeup water
required for the CO2 removal unit is also added to the suction of reflux pump.

Semi lean aMDEA solution is drawn from the bottom of the low pressure flash. Most of the
semi-lean solution is pumped by the pumps to the bottom section of CO2 absorber about 17%
of the semi-lean solution is pumped by the semi lean solution circulating pump heated to
about 111 degree celcius in the lean/semi-lean solution exchanger and then sent to CO2
stripper. LTS effluent gas supplied heat to the CO2 stripper which is used to strip carbon
dioxide from the aMDEA solution. The stripped carbon dioxide flows up to the stripper and
is then sent to low pressure flash. Lean aMDEA solution is drawn from the bottom of CO2
stripper .the lean solution is cooled by the exchanging heat with the semi-lean solution is then
pumped by the lean solution pump to the top section of CO2 absorber.

The carbon dioxide removal unit is designed with a slightly negative water balance to
maintain the concentration of aMDEA solution in the system , a continuous make-up of about
220kg/hr of demineralized water is required. This design eliminate the discharge of any
aMDEA solution loss. Given the composition of natural gas , the steam reforming front end
does not produce sufficient amount of carbon dioxide ,when producing syn-gas sufficient for
950 MTPD of ammonia. hence additional feed gas to be reformed and passed through to meet
requirement of the carbon dioxide.

2.7 METHANATION:

The vapor CO2 absorber Overheated Knockout Drum is preheated to methanation reaction
temperature .using the methanator effluent in the Feed/Effluent ex-changer and using
condensing high pressure start-up heater. The preheated gas then flows through the
methanator where carbon dioxides converted to methane by reaction with hydrogen over Ni
catalyst .Residual carbon oxides leaving the methanator are less than 5ppmv(dry basis)

CO2 +4H2 ------------- CH4 + 2H2O

CO + 3H2 -------------- CH4 + H2O

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The methanation reactions above are slightly exothermic and could potentially over heated in
methanator. This could occur if an upset in the shift (LTS/HTS) or carbon dioxide to
methanator an automatic shutdown system is provided to prevent overheating

2.8 DRYING:

In prepration for drying the methanator effluent is cooled by heat exchange with methanator
feed ex-changer to 79C and against cooling water in methanator effluent cooled to 38C the
methanator effluent then combines with recycle synthesis loop purge gasfrom high pressure
ammonia scrubber and the mixture is chilled using ammonia refrigerant in the methanator
effluent chiller to about 4C.The chilled gas is sent to methanator effluent separator where the
process condensate is separated out

Then two dryers the packed with zeolites based dessicant and operate cyclically .Each dryer
sized to remove traces of ammonia. Residual carbon dioxide and the water in 24-hours
drying cycle

The dryer regeneration facilities are designed for a 20hrs heating and cooling cycle to
provide a comfortable safely margin of 4 hours of stand-by time .Regeneration and cooling of
driers are done using waste gas from the purifier .During dryer regeneration the waste gas is
heated to 265C in the molecular sieve Regeneration heater by condensing steam from the
63kg/cm2 steam heater.

2.9 CRYOGENIC PURIFICATION:

Dried raw synthesis gas is then sent to cryogenic purification section. The gas is cooled by
heat exchange with make-up synthesis gas and with purifier waste gas is the top section of the
purifier Feed/Effluent ex-changer .The gas then flows through the purifier expander where
work is remove to provide net refrigeration duty required for purifier .THE expander effluent
is further cooled and partially condensed in bottom section of effluent ex-changer and enter
the purifier rectifier at 171C .Liquid from the bottom of rectifier is partially evaporated at
reduced pressure in the shell side of purifier rectifier condenser and provides cooling for
condenser and re-flux for the column. the rectifier contain nitrogen ,methane and some of
hydrogen.

The partially evaporated liquid leaving the shell side of purifier rectifier condenser is
reheated and the vaporize ineffluent exchanger and leave as purified waste gas, the waste gas
is used as carrier gas to regenerate the molecular sieve drier and then sent to fuel system, the

17
makeup syn-gas from the top of purifier rectifier is heated ineffluent exchanger and send to
the synthesis gas compressor at 1.8 degree celcius, the operation of purifier to maintain and
control the exact molar ratio of hydrogen and nitrogen of 3:1 the other impurities in make-up
gas is 32% argon and less then 50ppmv of methane

2.10 SYNGAS COMPRESSION

The process for syn-gas compression and ammonia synthesis section of the plant are
identical, except for new mechanical refrigeration system and purge gas ammonia recovery
system all the existing equipment in the syn-gas compression and ammonia synthesis sections
will be reused.

The purified syn-gas is compressed in four stages, steam turbine driven synthesis gas
compressor, recycle gas is added to the syn-gas before the fourth stagesuction , and the
combined flow leaves the compressor at about 197.2kg/cm2.

The syn-gas compressor is driven by turbine that is rotated with the help of 91 ata steam
pressure.

2.11 AMMONIA SYNTHESIS

Ammonia is produced in fixed – bed , vertical converter. Effluent in the hot exchanger. It
then flow to the ammonia converter. Ammonia concentration in the feed to the converter is
about 2.7 mole %. Ammonia is synthesized in two adiabatic beds provided with an inter
cooler and after cooloer.

The converter effluent containing about 17.70 mole% ammonia at 726 K .it is cooled by
generating high pressure steam in the syn – loop Waste heat Boiler and by heating boiler feed
water in the converter effluent BFW Preheater. After recovery of heat, the converter effluent
is cooled to 311 K by cooling water in the converter effluent cooler. The converter effluent is
then sent to the cold Ex – changer where it is chilled by heat exchangerwith the recycle gas.
The gas is finally chilled to 269 K against the ammonia refrigerant in the ammonia chiller.

Liquid ammonia is separated out from the converter by the separator while the vapor is
recycled to the last stage of compression by line. A small fraction of the vapor stream from
purged from the synthesis loop is control the inerts (methane or argon) concentration inlet to

18
the ammonia converter at 3.20 mole% liquid ammonia is depressurized to about 37.0kg/cm2
in a flash drum. This reduction in pressure dissolve most of the gas in liquid ammonia. Than
this recovery ammonia is sent to the Horton Sphere as product of capacity 2500m3. The
expected purity of the ammonia is 99.85wt% ammonia. The Horton Sphere is operate about
4.2kg/cm2 pressure and it is used to pump ammonia to Urea Plant at 283 K which passes
through the ex-changer.

3. MATERIAL BALANCE OF AMMONIA PLANT:

3.1 Knockout Drum:

Inlet: Natural gas(F)=23938Kg/hr

Outlet: D1=2883Kg/hr and D2
F=D1+D2
D2=21055Kg/hr

3.2 Hydrotreater:

Inlet DA=357Kg/hr and D2=21055Kg/hr

DA+D2=D3
Outlet D3=21412Kg/hr

3.3 Primary Reformer:

Steam reforming reaction for any hydrocarbon can be written as:

CnHm + nH2O nCO + (2n+m)/2 H2

For methane the above reaction becomes:

CH4 + H2O CO + 3H2

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The water gas shift reaction converts carbon monoxide to carbon dioxide and
additional hydrogen:

CO + H2O CO2 + H2

Inlet:
D3(after adding process steam)=85448 Kg/hr
D1=2883 Kg/hr

D1+D3=D4

Outlet:

D4=88281 Kg/hr

Methane balance:

Inlet Composition Total moles

D3 0.9531 4679.1

D1 0.9797 1291.4

Outlet:

D4 0.29 19740.8

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3.4 Secondary Reformer:

Inlet:

D4=88281 kg/hr; J1(process air)=74225 Kg/hr

D4+J1=D5

D5=162506 Kg/hr

Methane Balance:

Inlet: Composition total moles

D4 0.29 19740.8

J1 0 2653.7

Outlet:

D5 0.018 9435.6

3.5 High temperature shift convertor:

Carbon monoxide balance:

Inlet:
D5=9435.6 Kg mole/hr, composition: 0.1094
Outlet:
D6=10323.7 Kg mole/hr, Composition: 0.0287

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3.6 Low temperature shift convertor:

Inlet:
D6=10323.7 Kg mole/hr, composition: 0.0287
Outlet:
D7= 9763.6 Kg mole/hr, composition: 0.0025

3.7 Carbon dioxide absorber tower:

Inlet:
D7 =159673 Kg/hr, D8=1535900 Kg/hr
Outlet:

D9; D10=64205 Kg/hr

D7+D8=D9+D10

D9=1590100 Kg/hr

Carbon dioxide balance:

Inlet:
Composition Total moles
D7 0.1691 9435.6
D8 0.0261 13105.3
Outlet:
D9 0.111 13831.51
D10 0.0005 5812.5

3.8 High Pressure – Low Pressure flash drum:

High Pressure:
Inlet:
D9=1590100 Kg/hr
Outlet:
D11, D12=1588400 Kg/hr
D9=D11+D12
D11=1700 Kg/hr

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 Low Pressure:

Inlet:

D13=1609700 Kg/hr, D14=500 Kg/hr

Outlet:

D15=1593700 Kg/hr,D16

D13+D14=D15+D16

D16=58036 Kg/hr

This amount of Carbon dioxide goes to urea section for production of urea.

3.9 Methanator:

CO2 +4H2 ------------- CH4 + 2H2O

CO + 3H2 -------------- CH4 + H2O

Methane balance:
Inlet:
Composition Total moles

D10 0.0193 5812.5

Outlet:

D17 0.023 5627.5

3.10 Cryogenic Purification:

Inlet:
D17=62403 Kg/hr
Outlet:
D18=43198 Kg/hr, D19
D17=D18+D19

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 D19=19205 Kg/hr
Hydrogen Balance:
Composition Total Moles
Inlet:
D17 0.6443 5627.5
Outlet:
D18 0.7474 5011.8
Nitrogen Balance:
Inlet:
D17 0.3240 5627.5
Outlet:
D18 0.2493 5011.8

3.11 Ammonia Synthesis Convertor:

Nitrogen Balance:

Composition Total moles

Inlet:

D19 0.2493 18323.4

Outlet:

D20 0.1956 15997.9

Hydrogen Balance:

Inlet:

D19 0.7051 18323.4

Outlet:

D20 0.5897 15997.9

Ammonia Balance:

Inlet:

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 D19 0.0276 18323.4

Outlet:

D20 0.177 15997.9

4. ENERGY BALANCE OF AMMONIA PLANT:

4.1 Primary Reformer

Steam Reforming Reaction in Primary Reformer

CH4+ H2O CO + 3H2 H1= 224.588 Kilo Joule/Mole

CO + H2O CO2 + H2 H2= -36.534 Kilo Joule/Mole

Components Inlet(Temperature=768K) Outlet( T = 993.7 k )

Kmol/hr Heat Capacity Kmol/hr Heat Capacity

(J/mol.K) (J/mol.K)
H2 25.884 29.360 1634.111 28.960

N2 9.956 31.248 9.956 32.676

CH4 1311.337 57.512 878.596 71.600

Ar 1.593 - 1.473 -

CO 0 31.710 122.738 33.180

CO2 0 50.952 310.003 55.176

Heat consumed in reforming reaction for the conversion of methane upto 33% (Q1) =
37.818635Gcal/hr.

Heat evolved in shift reaction (Q2) = - 3.525 Gcal/hr.

Qreaction = Q1+Q2 = 34.293 Gcal/hr.

Heat consumed by nitrogen = 0.019 Gcal/hr.

Net heat duty of primary reformer = 34.312 Gcal/hr.

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4.2 Secondary Reformer:

CH4 + O2 CO2 + 2H2O H1= -793.329 Kilo Joule/Mole

2CH4 + 3O2 2CO + 4H2O H2 = -1024.068 Kilo Joule/Mole

Components Inlet(Temperature= 993.85K) Outlet( T = 1178.15 k )

Kmol/hr Heat Capacity Kmol/hr Heat Capacity

(J/mol.K) (J/mol.K)
H2 1618.383 28.960 3106.058 30.590
N2 1892.890 32.676 1892.890 33.600
CH4 880.209 71.600 113.863 78.4
O2 506.426 34.912 0 35.584
CO 126.712 33.180 691.739 34.048
CO2 310.003 55.176 511.326 56.100

Heat consumed in reforming reaction for the conversion of methane upto 91% (Q1) = 49.270
Gcal/hr.

Heat evolved in shift reaction (Q2) = - 1.574 Gcal/hr.

Qreaction = Q1+Q2 = 47.696 Gcal/hr.

Heat consumed by nitrogen = 3.092 Gcal/hr.

Net heat duty of primary reformer = 50.788 Gcal/hr.

4.3 High Temperature shift Converter:

CO + H2O CO2 + H2 H= -36.694 Kilo Joule/Mole

26
Components Inlet(Temperature=1178K) Outlet( T = 698 k )

Percent Heat Capacity Percent Heat Capacity

composition (cal/mol.K) composition (cal/mol.K)
H2 49.01 7.57 52.72 7.18
N2 29.84 7.68 27.67 7.19
CH4 1.77 18.87 1.65 13.36
Ar 0.38 4.97 0.35 4.97
CO 10.94 8.01 2.87 7.43
CO2 8.06 13.4 14.74 11.85

Total Molar inlet flow rate = 6344 Kmol/hr,

Average Heat Capacity(inlet) = 34.74 J/mol.K.

Hin = mcT = 259620079.7 KJ/hr.

Total Molar outlet flow rate = 6841.6 Kmol/hr,

Average Heat Capacity(outlet) = 33.32 J/mol.K.

Hout = mcT = 159094758 KJ/hr.

Hr = - 4478377.478 KJ/hr.

Hin – Hr + Hsupply = Hout

Hsupply = - 105003699.2 KJ/hr.

4.4 Low Temperature Shift converter:

CO + H2O CO2 + H2 H= -40.351 Kilo Joule/Mole

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Components Inlet(Temperature=698K) Outlet( T = 499.1 k )

Percent Heat Capacity Percent Heat Capacity

composition (cal/mol.K) composition (cal/mol.K)
H2 52.72 7.18 53.93 7.025
N2 27.67 7.19 26.96 7
CH4 1.65 13.36 1.6 11.09
Ar 0.35 4.97 0.35 4.97
CO 2.87 7.43 0.25 7.2
CO2 14.74 11.85 16.91 10.93

Total Molar inlet flow rate = 6841.6 Kmol/hr,

Average Heat Capacity(inlet) = 33.32 J/mol.K.

Hin = mcT = 159094758 KJ/hr.

Total Molar outlet flow rate = 7020.4 Kmol/hr,

Average Heat Capacity(outlet) = 32.33J/mol.K.

Hout = mcT = 113484766 KJ/hr.

Hr = - 5736409.75 KJ/hr.

Hin – Hr + Hsupply = Hout

Hsupply = - 39873582.25 KJ/hr.

4.5 Methanator

CO + 3H2 CH4 +2H2O H1= -206.835 Kilo Joule/Mole

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Components Inlet(Temperature=323K) Outlet( T = 596.2 k )

Percent Heat Capacity Percent Heat Capacity

composition (cal/mol.K) composition (cal/mol.K)
H2 64.82 6.88 64.43 7.1
N2 32.49 6.82 32.85 7.11
CH4 1.93 9.05 2.3 12.19
Ar 0.42 4.97 0.42 4.97
CO 0.3 6.96 - -
CO2 0.05 9.35 - -

CO2 + 4H2 CH4 +2H2 O H2= -165.694Kilo Joule/Mole

Total Molar inlet flow rate = 5812.5 Kmol/hr,

Average Heat Capacity(inlet) = 28.83 J/mol.K.

Hin = mcT = 54126523.13 KJ/hr.

Total Molar outlet flow rate = 5587.3 Kmol/hr,

Average Heat Capacity(outlet) = 30.13J/mol.K.

Hout = mcT = 100367497.1 KJ/hr.

Hr = - 414733601.9 KJ/hr.

Hin – Hr + Hsupply = Hout

Hsupply = - 0.595 GJ/hr.

4.6 Ammonia synthesis

N2 + 3H2 2NH3 H= 91.8 Kilo Joule/Mole

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Components Inlet(Temperature=503K) Outlet( T = 726.1 K )

Percent Heat Capacity Percent Heat Capacity

composition (cal/mol.K) composition (cal/mol.K)
H2 70.51 7.02 58.97 7.2
N2 23.52 7 19.68 7.226
CH4 0.05 11.12 0.05 13.69
Ar 3.15 4.97 3.6 4.97
NH3 2.76 9.86 17.7 11.27

Total Molar inlet flow rate = 18323.4 Kmol/hr,

Average Heat Capacity(inlet) = 29.39 J/mol.K.

Hin = mcT = 270877937.2 KJ/hr.

Total Molar outlet flow rate = 15997.9 Kmol/hr,

Average Heat Capacity(outlet) = 32.8J/mol.K.

Hout = mcT = 381007266.2 KJ/hr.

Hr = - 119363513 KJ/hr.

Hin – Hr + Hsupply = Hout

Hsupply = - 9.23 GJ/hr

30