Modern Ammonia production plant

• In General
• Ammonia is produced from mixture of
hydrogen and Nitrogen. Where the ratio is
maintain approximately 3:1.
• Besides this two components, the synthesis gas
will contain inert gases- such as Argon and
methane to a limited degree.
• The source of H2 is the raw water and
hydrocarbons in natural gas and Naptha and
source of N2 is Air.
Modern process of production of
Ammonia
 Desulfurization section
1. Desulfurization :
• Catalyst used to steam reforming process is highly
sensitive to sulphur compounds therefore these
compounds need to be reduced to a concentration of
the less than 0.15 mg/m3 feed gas.
• To achieve this feed gas to be preheated up to 350-400
deg C and then after sulphur compound to be
hydrogenated to H2S by typically using cobalt
molybdenum catalyst and then finally adsorbed on the
zinc oxide. In this way sulphur is to be removed to
less then 0.1 ppm in the gas feed.
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Reactions:
R-SH + H2 H2S + RH
H2S + ZnO ZnS + H2O
• The hydrogen required for the reaction is
recycled from the synthesis section of the
plant.
 2. Primary reforming
• Gas from the desulfurizer is sent to the primary
reformer for steam reforming (ratio = steam/gas =
3:1). The primary reformer is consists of large
number of high Nickle- chromium alloy tubes
filled with Nickle reforming catalyst.
• Here superheated steam is fed in to the reformer
with methane. The gas mixture heated with
natural gas to 770 deg C in presence of Nickle
catalyst.
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• At this temperature the following equilibrium
reactions are driven to converting the methane
to hydrogen, carbon dioxide and small
quantities of carbon monoxide.
• Reactions:
CH4 + H2O 3H2 + CO
CH4 + 2H2O 4H2 + CO2
CO + H2O H2 + CO2
• The gaseous mixture is known as synthesis
gas.
3. Secondary reforming
• Only 30-40% of the hydrocarbon feed is
reformed in the primary reformer because of
the chemical equilibria at the operating
conditions.
• The temperature must be rise to increase the
conversion. This is done at the secondary
reformer by internal combustion part of the gas
with the process air, which also provides the
Nitrogen gas for final synthesis.
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• Process:
• The process air is to be compressed to the reforming
pressure and heated further in primary reformer
convection section to around 600 deg C. The process
gas is mixed with the air in burner and then passed over
the nickel catalyst in the secondary reformer.
• The reformer outlet temperature is around 1000 deg C,
and up to 99% of the hydrocarbon feed (from primary
reformer) is converted, giving the residual methane
content of 0.2-0.3% (dry base gas) in process gas
leaving the secondary reformer.
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• Reaction:
• CO + H2O CO2 + H2
• O2 + 2CH4 2CO + 4H2
• O2 + CH4 CO2 + 2H2
• 2O2 + CH4 2H2O + CO2
• The process gas is cooled to 350 to 400 deg C in
waste steam boiler.
• As the catalyst used to form the ammonia is pure
iron, the CO, CO2 and water must be removed
from the gas stream to prevent the oxidation of
the iron. This is done next three steps.
 4 Shift conversion
• The process gas from the secondary reformer contain
12 to 15% CO (dry gas base) and most of CO is
converted in shift section according to the reaction.
• CO + H2O CO2 + H2 ΔH = -41 KJ/mol
• In the high temperature shift (HTS) conversion, the gas
is passed through a bed of iron oxide/ chromium oxide
catalyst around 400 deg C, limited by the shift
equilibrium at the actual operating condition. There is
tendency to use copper containing catalyst for increases
conversion.
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• The gas from the HTS is cooled and passed
through the Low Temperature Shift (LTS).
• This LTS converter is filled with copper
oxide/Zinc oxide base catalyst and operates
about 200 to 220 deg 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 efficiency
of process.
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• Condensate: A process gas from the low
temperature shift converter contains mainly
H2, N2, CO2 and excess process steam. The
gas is cooled and most of the excess steam is
condensed before it enters the CO2 removal
system.
• This condensate contain 1500- 2000 ppm of
ammonia and 800-1200 ppm of methanol.
Minor amount of amines, formic acid and
acetic acid could be present in the condensate.
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• All these component should be stripped and
recycle in the process.
 5. CO2 removal
• This process step is removes the CO2 from the
reaction gas. CO2 is removed in the physical
absorption process.
• The solvent used in the chemical absorption
are mainly amine solution e.g. Mono
ethanolamine, activated methyl
diethanolamine, potassium carbonate solution.
• Two typically used physical absorption solvent
are glycol dimethylether and propelene
carbonate which reduces CO2 up to 50 ppm
 6. Methanation
• The small amount of CO and CO2, remaining in the
synthesis gas, are poisonous for ammonia synthesis
catalyst and must be removed by conversion to CH4 in
the Methanator.
• CO + 3H2 CH4 + H2O
• CO2 + 4H2 CH4 + H2O
• The reaction take place at around 300 deg C in reactor
filled with a Nickle containing catalyst. Methan is not
involved in the synthesis reaction, but the water must
be removed before entering the converter.
• This is done by cooling followed by condensation of
down stream of the methanator.
 7. Compression
• Modern ammonia plants use centrifugal
compressors to pressurize to synthesis gas to
the required level (100-250 bar, 350-550 deg
C) for ammonia synthesis.
• Molecular seives are sometimes used after the
first compressor stage to remove the last traces
of H2O, CO and CO2 from the synthesis gas.
• These compressors are working by using steam
turbines which utilize steam produce from the
excess process heat.
 8 NH3 Synthesis
• The synthesis of ammonia take place on an
iron catalyst at the pressure usually in the
range of 100-250 bar and temperature of
between 350 to 500 deg C.
• N2 + 3H2 NH3 ΔH = -46 KJ/mol
• Only 10-20% of synthesis gas is converted per
pass to ammonia, due to unfavourable
equilibrium condition.
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• The unreacted gas is recycled after removing the
ammonia formed and fresh synthesis gas is
supplemented in the loop.
• As exothermic synthesis reaction proceeds, there
is a reduction in volume and so a higher pressure
and lower temperature favours the reaction.
• Conventional reforming with methanation as the
final purification step produces a synthesis gas
containing unreacted gas and inert. (methane and
argon)
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• To prevent the accumulation of these inert, a
continuous purge stream is applied. Purge gas
basically contain ammonia, hydrogen,
nitrogen, inert and unreacted gas.
• The size of purge stream maintain the level of
inert in the loop, keeping this to about 10-15%.
• This purge gas is scrubbed with water to
remove ammonia or sent to hydrogen recovery.
Partial oxidation of Residual fuel oil
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• Here it is a simplified block flow diagram for
producing hydrogen from the partial oxidation
of the residual oil with steam and oxygen using
the Shell or Texaco Process. The gasifier
effluent, at about 500 psig and 2300°F, goes
through the steps of waste heat recovery, soot
removal, carbon monoxide shift, and
methanation. The product hydrogen is at 400
psig and contains 97.5% hydrogen
• CH4 + 1/2O2 CO + 2H2 ΔH= -8.53
Kcal
Ammonia converter ....
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• The converter consists of a high pressure shell
containing a catalyst section and a heat
exchanger.
• The catalyst section is a cylindrical shell which
fits inside the pressure shell, leaving an
annular space between the two.
• The catalyst section contains several beds
supported on screened grids.
• To maintain the catalyst at optimum
temperature for maximum yield, cold feed gas
quench is injected before each catalyst bed.
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• The top bed contains the smallest quantity of
catalyst. Since the temperature gradient is
flatter in succeeding beds, bed size are
graduated with the largest bed at bottom. This
preheat inlet gas against hot reacted gas from
the last catalyst bed.
• The top quench point permits the introduction
of feed gas without preheating and provides
temperature control.
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• The feed gas enters at the top of the converter and
flows downward between the shell and the wall of
the catalyst section. The gas cools the shell and is
heated.
• The gas then enters the exchanger at the bottom
of the converter and, is further preheated against
hot effluent.
• Some feed gas is introduced directly to the top of
the first bed, where it meets the preheated feed.
• The combined stream at a temperature 700 to 800
deg F is then introduced in to the top catalyst bed.
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• The gas passes downward through the catalyst,
with a rapid temperature rise as the ammonia
reaction, proceeds, and then through the catalyst
supporting grid in to a space between the first and
second beds.
• Here the temperature is reduced and the ammonia
content diluted by injection of cold feed gas.
• This permits control throughout the catalyst beds
to obtain optimum temperature for maximum
yield.
• In like way gas flows downward from catalyst
bed.
 Urea production... Introduction
• Urea is in many ways the most convenient
form for fixed nitrogen. It has the highest
nitrogen content available in a solid fertilizer
(46 %). It is easy to produce as prills or
granules and easily transported in bulk or bags
with no explosive hazard. It leaves no salt
residue after use on crops. Its specific gravity
is 1.335, decomposes on boiling and is fairly
soluble in water.
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• The principal raw materials required for this purpose are
NH3 & CO2.Two reactions are involved in the manufacture
of urea. First, ammonium carbamate is formed under
pressure by reaction between CO2 & NH3.
• CO2 + 2NH3 → NH2COONH4 ΔH= -37.4 Kcal

• This highly exothermic reaction is followed by an

endothermic decomposition of the ammonium carbamate.
NH2COONH4 ↔ NH2CONH2 + H2O
ΔH= + 6.3 Kcal
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• Various processes for the manufacture of urea
are:
1. Snamprogetti ammonia stripping process
2. Stamicarbon CO2 stripping process
3. Once through urea process
4. Mitsui Toatsu total recycle urea process
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• Uses of Urea:
• About 56 % of Urea manufactured is used in solid
fertilizer.
• About 31 % of Urea manufactured is used in liquid
fertilizer.
• Urea-formaldehyde resins have large use as a plywood
adhesive.
• Melamine-formaldehyde resins are used as dinnerware
& for making extra hard surfaces.
 In general process
• Ammonia & CO2 are compressed separately and fed to
the high pressure (180 atms) autoclave as shown in
figure which must be water cooled due to the highly
exothermic nature of the reaction. A mixture of urea,
ammonium carbamate, H2O and unreacted ( NH3+CO2)
is produced.
• This liquid effluent is let down to 27 atms and fed to a
special flash-evaporator containing a gas-liquid
separator and condenser. Unreacted NH3, CO2 & H2O
are thus removed & recycled. An aqueous solution of
carbamate-urea is passed to the atmospheric flash drum
where further decomposition of carbamate takes place.
The off gases from this step can either be recycled or
sent to NH3 processes for making chemical fertilizer.
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• The 80 % aqueous urea solution can be used as
it is, or sent to a vacuum evaporator to obtain
molten urea containing less than 1 % water.
The molten mass is then sprayed into a prilling
tower. To avoid formation of biuret and keep it
less than 1 %, the temperature must be kept
just above the melting point for processing
times of 1-2 seconds in this phase of the
operation.
•
THE VARIABLES THAT AFFECT THE AUTOCLAVE
REACTIONS ARE
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1. Temperature
• Process temperature (185 oC) favours equilibrium yield
at a given pressure (180 atm). The conversion of
ammonium carbamate to urea gradually increases as the
temperature increases. However, after a particular
temperature, depending upon the pressure, the
conversion suddenly drops with further increase in
temperature. The pressure corresponding to this
temperature which is usually in the range of 175-185oC,
is known as the decomposition pressure which is about
180 atm.
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2. Pressure
• The main reaction is sufficiently slow at
atmospheric pressure. However, it starts almost
instantaneously at pressure of the order of 100
atm and temperature of 150 oC. There is reduction
in volume in the overall reaction and so high
pressure favours the forward reaction. This
pressure is selected according to the temperature
to be maintained & NH3:CO2 ratio.
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3. Concentration:
• Higher the concentration of the reactants,
higher will be the forward reaction according
to the law of mass action. CO2 being the
limiting reagent higher NH3:CO2 ratio favours
conversion. Since, dehydration of carbamate
results in urea production, lesser H2O:CO2
ratio favors conversion. Water intake to the
reactor should therefore be minimum.
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4 Residence time:
• Since, urea reaction is slow and takes about 20
mins to attain equilibrium, sufficient time is to
be provided to get higher conversion. Reactor
is designed to accommodate this with respect
to the other parameters of temperature,
pressure and concentration.
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5. Biuret formation:
• A problem faced during manufacture of urea is
the formation of biuret during the production of
urea. It is not a desirable substance because it
adversely affects the growth of some plants. Its
content in urea should not be more than 1.5 % by
weight.
2NH2CONH2 ↔ NH2CONHCONH2 + NH3
(Biuret)
Snamprogatti process....
• The unreacted carbamate & the excess
ammonia are stripped from the urea synthesis
reactor effluent by means of gaseous hot CO2
or NH3 at the reactor pressure, instead of
letting the reactor effluent down to a much
lower pressure. The NH3 & CO2 gas, thus
recovered at reactor pressure, is condensed and
returned to the reactor.
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• This process is based on the principle of the
internal carbamate recycle technique and is
commonly called the Snam NH3 stripping
process.
• The basic difference between the Snam process &
the conventional carbamate solution recycle urea
processes is the fact that in this case the
unconverted carbamate is stripped and recovered
from the urea synthesis reactor effluent solution at
reactor pressure, condensed to an aqueous
solution in a steam producing high pressure
condenser, & recycle back to the reactor.
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• Part of the liquid NH3 reactor feed, vaporized
in a steam heated exchanger, is used as inert
gas to decompose & strip ammonium
carbamate in the steam heated high pressure
stripper.
• The reactor operates at about 130 atm & 180-
190 o C. The stripper operates at about 130 atm
& 190 o C. The stripper off-gas is condensed in
a vertical shell & tube condenser, operating at
about 130 atm & 148-160 o C.
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• Low pressure steam is produced in the high
pressure carbamate condenser. The urea
product solution, leaving the stripper & still
containing 2-3 % of residual unreacted
carbamate, is further degassed in a low
pressure decomposition-absorption system.
The recovered ammoniacal solution of
ammonium carbamate is pumped back to the
reactor.
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Total recycle process...
• This total recycle urea process is a
conventional carbamate solution recycle
process with three pressure-staged carbamate
decomposition & recovery systems. The
reactor is operated at about 195 o C, 240 atm,
& with a NH3 to CO2 molar ratio of about 4.3.
About 67 % of the total ammonium carbamate
present in the reactor is converted to urea.
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• The unconverted carabamate is decomposed and
stripped from the urea solution together with
excess NH3 in a series of three pressure-stage
decomposers, operating respectively at about 18
atm & 150 oC, 3.06 atm & 130 oC, & atmospheric
pressure & 120 o C.
• The main feature of the total recycle process is
the fact that the gaseous phase in each
decomposition stage is contacted in counter
current flow with the urea product solution
issuing from the preceding decomposition stage.
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• Either a packed section or a sieve tray section
is used for this purpose. The effect is that the
NH3 & CO2 gaseous mixture obtained from the
decomposition of carbamate is considerably
reduced in vapor content. Thus the amount of
water recycled to the reactor is maintained at a
relatively low level and a relatively high
conversion in the reactor is attained.
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• The off-gas from each decomposition stage is
condensed to solution in its respective water cooled
condenser and the solution thus obtained is pumped to
the next high pressure staged condenser.
• Excess NH3 is separated from the aqueous solution of
carbamate & scrubbed from the last traces of CO2 in
counter current flow with reflux liquid, NH3, fed to the
top of the high pressure absorber. The pure excess NH3
thus obtained is condensed to liquid with cooling water
& recycled to the reactor. The carbamate solution is
recycled back to the reactor for total recovery.
 Significance of Potassium in plant
growth
• Potassium is an indispensable constituent for
the correct development of plants. It is
important in photosynthesis, in the regulation
of plants responses to light through opening
and closing of stomata. Potassium is also
important in the biochemical reactions in
plants. Basically, potassium (K) is responsible
for many other vital processes such as water
and nutrient transportation, protein, and
starch synthesis.
 Important uptake
• Bio-availability and uptake of K by plants from the soil vary
with a number of different factors. The rate of respiration
by plants is largely the determining factor for proper uptake
and transport of potassium by plants. Its uptake is
dependent on sufficient energy (ATP). Potassium plays a
vital role in the trans-location of essential nutrients, water,
and other substances from the roots through the stem to
the leaves. It is also made available through fertilizers in the
form of K2O.
• Plant tissues analyze the form in these fertilizers and
convert it in a more bio-available form. It is absorbed in the
form of ions- K+.
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• Potassium (K) essentially plays a major role in
plant physiological processes. Therefore, it is
required in large amounts for proper growth and
reproduction in plants. It is considered vital after
nitrogen as far as nutrients needed by plants is
concerned. It is also termed "the quality nutrient"
for its contributing factor in a number of
biological and chemical processes in plants. Here
is why Potassium is important in plants:
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• Potassium regulates the opening and closing of stomata
thus regulating the uptake of CO2 thus enhancing
photosynthesis.
• It triggers activation of important biochemical enzymes for
the generation of Adenosine Triphosphate (ATP). ATP
provides energy for other chemical and physiological
processes such as excretion of waste materials in plants.
• It plays a role in osmo regulation of water and other salts in
plant tissues and cells.
• Potassium also facilitates protein and starch synthesis in
plants.
• It activates enzymes responsible for specific functions.
 Potassium deficiency to plant
• Regardless of its availability from soils,
potassium deficiency may occur and might
start from the lower leaves and progress
towards other vital parts of the plants.
Deficiency might cause abnormalities in plants
affecting reproduction and growth. Severity
depends on with the type of plant and soil.
Some of the potassium deficiency symptoms
may include:
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• Chlorosis: May cause yellowing of leaves, the margin of
the leaves may fall off, and also lead to shedding and
defoliation of the leaves.
• Stunted growth: Potassium being an important growth
catalyst, its deficiency or insufficient might lead to slow
growth or poor developed roots and stems.
• Poor resistance to ecological changes: Reduced
availability of potassium will directly result in less fluid
circulation and trans-location of nutrients in plants.
This will directly make plants susceptible to
temperature changes.
 Potassium sulphate
• Potassium sulphate is a good source of
potassium for farms. It gives potassium in a
very stable condition, the PH is neutral form.
There even brands that indicate the potassium
sulfate as purely organic. Organic farmers
usually have limited choice when it comes to
when it comes to potassium fertilizers.
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• formulated composts are a great source of potassium, but the
potassium in this composts leaches easily when it rains heavily.
Another great source of potassium is hardwood. As a matter of fact,
the word POTASH refers to the act of dissolving as in water so as to
use as fertilizer. However, wood ash is not ideal because it as a very
high PH and can have a negative impact on alkaline soils. Other
great sources of potassium include granite dusts and greensand, but
unfortunately, they are easily soluble and may take a very long time
to become available to the plants. If a small amount of potassium is
needed, potassium chloride can be used instead but it is also soluble,
the chloride content is also dangerous because it can destroy
essential microorganisms. The good thing about potassium sulfate is
that it get rids of all the disadvantages. Therefore, a great potassium
sulfate fertilizer is the ideal choice for both organic and
conventional gardeners.
Potassium sulphite physical properties
• Compound Formula : K2O4S
• Appearance : White Powder
• Melting Point: 1,069° C (1,956° F)
• Boiling Point : 1,689° C (3,072° F)
• Density : 2.66 g/cm3
 Important properties of potassium
sulphate wrt agriculture
• Potassium sulfate contains about 50% potassium and
about 17% sulfate. The sulfur that is in this compound
is highly soluble in water. Potassium is a very important
element that helps plants a great deal. It has so many
functions in plants. It strengthens the plants by helping
them use nitrogen compound efficiently. It helps the
plants produce stronger stems, leaves as well as
flowers. It also helps strengthen the immune of the
plants, so that they are resistant to drought and
diseases.