Cement, Fertilizer, Pulp and Paper

Technology
ChE 4049
Instructor : Md. Faisal Ferdous
Lecturer, Department of Chemical
Engineering , KUET.
Introduction

HCNO is cyanic acid or fulminic acid

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 Uses of Urea

1. Main Nitrogen based fertilizer.

2. Urea is a raw material for the manufacture of urea-formaldehyde
resins, used mainly in wood-based panels such as particleboard,
fiberboard and plywood.
3. Urea can be used to make urea nitrate, a high explosive that is
used industrially and as part of some improvised explosive devices.
4. A component of animal feed, providing a relatively cheap source
of nitrogen to promote growth.

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Properties of urea

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Reaction of urea in soil

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Reaction of urea in soil

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Reaction of urea in soil

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Reaction of urea in soil

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Reaction of urea in soil: Some parameter
2 things you need to know about the conversion from urea to Ammonium

• Urease enzyme is active in the soil between -20°C and +30°C. So, it is still active when the
temperature drops below zero.
• Moderately dry soils and soils with high pH levels tend to have lower hydrogen content, and are at
higher risk for volatilization. With less free hydrogen, the conversion from Ammonia to Ammonium
takes longer.

• As the temperature drops, aerobic bacteria (including Nitrosomonas and Nitrobacter) experience a drop in
activity.

• Denitrification is most common in damp, moist climates with temperatures about 5°C and clay soil
structures.

• The presence or absence of oxygen is one of the largest factors determining the extent and duration of
Denitrification. Denitrification can occur in aerobic (adequate oxygen) conditions, but to a relatively
insignificant degree. As the oxygen deficit increases, microbes tend to convert more of the nitrate to N2
gas. Denitrification proceeds rapidly when water-filled pore space in soils exceeds 60%.

• When the oxygen (O2 ) supply in soil becomes limited, a variety of bacteria use the oxygen in nitrate for
respiration. 9
Urea Process Reactions

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Impact of biuret

In botany, chlorosis is a condition in which leaves produce insufficient chlorophyll. As chlorophyll

is responsible for the green color of leaves, chlorotic leaves are pale, yellow, or yellow-white.
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Biuret formation

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Biuret formation

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Variable that affect the reaction

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Variable that affect the reaction

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Major problems

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Optimum Condition

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Urea Process

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Urea Process :Once through

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Urea Process :Once through

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Urea Process : Partial Recycle

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Urea Process : Partial Recycle

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PBD of Urea process

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 Snamprogetti Process (ITALY)

1. High pressure section ( at a pressure of 150 bar

and at 188 deg C and 34 wt% urea )
2. Medium pressure section (62-65 wt% urea, 17
barg pressure)
3. Low pressure section (72-86 wt% urea, 3.3 barg -
pressure)
4. Evaporation section (99 % urea)
5. Process condensate section

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Snamprogetti Process (ITALY)

The Snamprogetti Urea Process is basically a total

recycle stripping process using ammonia as a self-
stripping agent. The Snamprogetti process used the
excess ammonia present in the urea solution
leaving the reactor to strip CO2 from urea solution
in a falling film steam heated heat exchanger operated
at the urea reactor pressure. The separated CO2 and
NH3 are recombined as ammonium carbamate in the
carbamate condensers, also operating at urea reactor
pressure and then returned to the reactor for
conversion to urea. the carbamate condenser that
condenses these vapours; the ejector that recycles the
ammonium carbamate solution to the reactor.

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Snamprogetti Process (ITALY)

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Snamprogetti Process (ITALY)

Ammonia (NH3) and carbon dioxide (CO2) react

at 150 bar to yield urea and ammonia carbamate.
The conversion in the reactor is very high due to
a favorable NH3/CO2 ratio of 3.3~ 3.5:1 and
operating temperature of 185°C to 190°C. These
conditions prevent corrosion problems.

Carbamate is decomposed in three stages at

different pressures: in the stripper at the same
pressure as the reactor, in the medium-pressure
decomposer at 18 bar and in the low-pressure
decomposer at 4.5 bar. Reactants not
transformed into urea are recycled to the reactor
by an ejector. Main equipment is installed at
ground level. This layout is essential for large
plants. Heat recoveries are particularly
developed to have low-energy usage.

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 Snamprogetti Process (ITALY)

The impurities are removed by adding medium pressure steam to the shell of the stripper which allows for the
endothermic decomposition of ammonium carbamate. The released ammonia and CO2 act as stripping
agents for the down-coming liquid, which pools in the bottom of the stripper to prevent gas from flowing to the
medium pressure decomposer.

The gasses released from the stripper are fed into the high pressure carbamate condenser together with the
carbamate solution coming from the separation column. The carbamate condenser is a kettle reboiler with the
carbamate solution flowing through the tubes and the hot water residing in the shell. Inside the carbamate
condenser the ammonia and carbon dioxide are condensed to form ammonium carbamate through an
exothermic reaction.

By using the exothermic carbamate formation within the condenser to heat LP condensate, it is possible to
almost completely regain the heat lost in the decomposition of ammonium carbamate in the medium
pressure decomposer. This vastly increases the overall efficiency of the plant and diminishes the amount of
fuel needed in the boilers

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Snamprogetti Process (ITALY)

The carbamate solution coming from the carbamate condenser is transported to the carbamate
separator where the remaining gases are separated from liquid. The only function of this vessel is to
separate the gases and liquids coming from the carbamate condenser. The liquids are then
recycled back to the reactor through the ejector. The gases on the other hand are fed into the
medium pressure decomposer, to act as stripping agents and to reduce the heat requirement for the
decomposition of ammonium carbamate.

The 42 wt% urea solution exiting the bottom of the HP stripper at 150 bar is let down to 18 bar through an
expansion valve, before it enters the MP decomposer. The purpose of the MP decomposer is to concentrate
the solution to 62 wt% urea, by decomposing residual carbamate.

Upon exiting the MP decomposer, the 62 wt% urea solution passes through an expansion
valve to the LP purifying section.

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 Snamprogetti process (Medium pressure section)
The top product of the MP decomposer consists of free gases (mainly NH3) released during initial flashing of the urea solution coming from the HP stripper,
and the NH3 and CO2 resulting from the decomposition of carbamate. These gases are transferred to the shell of the pre-heater, found at the beginning of
the vacuum section, in order to save utility cost.

The gases are mixed with a solution of carbamate exiting the LP carbamate receiver and are partially condensed, thereby partially reacting to form
carbamate. By performing this condensation and exothermic reaction in the shell of the preheater, the heat required to further concentrate the urea
solution therein must not be supplied by steam.

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Snamprogetti process
Upon exiting the pre-heater shell, the partially condensed gases enter the MP carbamate condenser where the corrosive stream is further
condensed, leaving at 75°C to enter the bottom of the ammonia-carbamate separation column.
The separation column is an integral part of the NH3 recovery section operating within the MP section of the plant. It is designed to separate
carbamate solution and CO2 from pure NH3, thereby providing the pathway for unreacted NH3 liquid to be returned to the reactor. The resulting
bottom product is ammonium carbamate solution, which is recycled via a centrifugal multistage HP carbamate pump to the HP carbamate
condenser.

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Snamprogetti process: Low pressure section
The solution coming from the medium pressure decomposer which contains 62 wt% of urea, is led to the top part of the low pressure decomposer
and rectifier In the top part of the vessel, the released flash gasses are removed. while the remaining liquid flows down the tube side of the falling
film part of the low pressure decomposer. While flowing down the decomposer, the remaining ammonium carbamate is decomposed to ammonia
and carbon dioxide.

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Snamprogetti process: Low pressure section
The released flash gasses, which are mainly composed of ammonia, water and carbon dioxide, are then mixed with the gasses coming from
the wastewater treatment section and condensed in the tube side of the low pressure carbamate condense. The condensed stream (with a
vapor fraction around 11%) then flows to the low pressure ammonium carbamate receiver. This vessel, which is kept at 40 deg C and the
same pressure as the low pressure decomposer and rectifier and the low pressure carbamate receiver (4.5 bar), is designed in such a way
that, in case of shutdown, the vessel could hold the carbonate solutions in the entire plant. The bottom effluent of the receiver is then pumped
to the shell side of the preheater ,where it is mixed with the released flash gases from the medium pressure decomposer.

In the shell side of the preheater, the

remaining ammonia and carbon
dioxide are reacted to ammonium
carbamate, and the whole solution
is condensed. This way, heat is
supplied to the tube side of the
preheater.

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Thank you

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