Ministry of Higher Education and

Scientific Research
Al-Muthanna University
Engineering College
Chemical Engineering Department

Controlling of evaporator in the

production Urea

Report done by: tariq fareed abdullah

Class: 4th class
Subject: first course report

Supervised by: Dr. Forat Yasir AlJaberi

Introduction

Urea (NH2CONH2) or carbamide is an organic compound has two —

NH2 groups joined by a carbonyl (C=O) functional group. Urea serves an
important role in the metabolism of nitrogen containing compounds by
animals and is the main nitrogen containing substance in the urine of
mammals.

Urea was first discovered in urine in 1727 by Herman Boerhaave, though

this discovery is often credited to Hilaire Rouelle.

Friedrich Wöhler synthesized urea from an inorganic precursor in 1828. It

was the first time that the molecule found in living organisms could be
synthesized in the laboratory without biological starting materials. Due to
this discovery, Wöhler is considered as the father of organic chemistry by
many scientists.

Urea has the highest nitrogen content available in a solid fertilizer (46%).
It is easy to produce as pills or granules and easily transported in bulk or
bags with no explosive hazard. It dissolves readily in water. It leaves no
salt residue after use on crops and can often be used for foliar feeding.

Urea is an acceptable fertilizer for rice and preferable to nitrates for

flooded rice because of the reduction of nitrates to N2O and/or nitrogen
(in anaerobic conditions) which is lost to the atmosphere. Also, rice can
utilize the ammonium form of nitrogen efficiently. Hydrolysis and
nitrification (in aerobic conditions) are rapid in tropical, sub-tropical and
warm climates

Urea can be sprayed on leaves and can also be mixed with insecticides or
herbicides for soil application. A urea ammonium nitrate mixture with
herbicide is also used for weed control.

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Disadvantages

 When applied to a bare soil surface, urea hydrolyzes rapidly result into
loss of significant quantity of ammonia by volatilization. Such losses vary
from soil to soil and are greater for urea in a pellet form rather than in
solution form.

 It is phytotoxic due to rapid hydrolysis of urea in soils can cause injury

to the seedlings by ammonia,
 The fertilizer grade urea may contain toxic biuret which is formed
during urea manufacture by an excessive temperature rise. Above 2%
concentration of biuret in urea is harmful to plants.

Feed grade urea is sometimes referred to by the number 262 which is the
product of its nitrogen content (42%) multiplied by 6.25, the latter being
the factor used by chemists to convert nitrogen to its protein equivalent.

PROPERTIES

 Molecular formula : CH4N2O

 Molecular weight : 60.06gm/mole
 Appearance : White granules
 Odour : Odourless
 Bulk density : 673-721kg/m3
 Angle of repose : 300
 Melting point : 132-1350C
 Density : 1.32gm/ml
 Solubility : Solubility in water, ethanol, glycerol
 Moisture : 1% by wt. (Max.)

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It is highly soluble in water and practically non-toxic (LD50 is 15 gm/kg
for rat). Dissolved in water, it is neither acidic nor alkaline. As soon as
urea dissolves in the soil, it forms around it a zoning layer of high pH and
ammonia concentration turning the soil to be acidic and toxic at the same
level. Urea is high moisture absorbent therefore it should be stored in
sealed and well enclosed bags.

USES
 As a fertilizer
 As a protein food supplements for ruminant
 As an ingredient in the manufacture of resins, plastics, adhesive,
coatings
 Textiles anti-shrink agents and ion exchange resins
 In melamine production
 It is an intermediate in the manufacture of ammonium sulfamate,
sulfamic acid and pthalocyanines.

MANUFACTURE
Raw materials
Basis: 1000kg prilled urea

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Reaction
CO2 + 2NH3 NH2COONH4 ΔH = - 37,021 Kcal
NH2COONH4 NH2CONH2 + H2O ΔH = + 6.3 kcals

Urea is always made in an ammonia plant because it produces CO 2 as by

product, which can be used directly without further treatment.

Two reactions are involved in the manufacture of urea. First ammonium

carbonate is formed under pressure by highly exothermic reaction
between carbon dioxide and ammonia followed by the endothermic
decomposition reaction. While the former reaction under pressure,
reaches to almost completion and the decomposition reaction incomplete.
Unconverted carbon dioxide and ammonia, along with un decomposed
carbamate, must be recovered and reused. The synthesis is further
complicated by the formation of a dimer called biuret,
NH2CONHCONH2.H2O which must be kept low because it adversely
affects the growth of some plants.

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Liquid ammonia, gaseous carbon dioxide and recycle materials charged
in the heat exchanger-reactor at the pressure of 14MPs at 170 - 1900C to
form carbamate, with most of the heat of reaction carried away as useful
process steam. The carbamate decomposition reaction is both slow and
endothermic. The mixture of unreacted reactants and carbamate flows to
the decomposer. The stoichiometric ratio of CO2/NH3 conversion to urea
is essentially about 55%, but by using an excess of CO2 (or NH3) the
equilibrium can be driven as high as 85%. The reactor must be heated to
force the reaction to proceed. CO2 is introduced at process pressure
followed by stripper. All the unreacted gases and undecomposed
carbamate to be removed from the product, the urea must be heated at
lower pressure (400kPa). The reagents are reacted and pumped back into
the system. Evaporation and prilling or granulating produces the final
product. Overall, over 99% of both CO2 and NH3 are converted to urea,
making environmental problems to minimum. Carbamate is highly
corrosive to both ordinary and stainless steel, but with oxygen present,
300 series stainless steel resist it very well, so some air is introduced
along with CO2 reagent to reduce system corrosion.

Developments in urea process technologies

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a) Montedison's IDR process

Montedison's process employing two specially designed stripping

columns. Ammonia and CO2 are used as the stripping agent in 1st and
2nd column respectively. The reactor constructed in two sections
having perforated trays and also a down comer meant for circulation
solution. High NH3 to CO2 ratio results in increased conversion
efficiency and lower carbamate recycle duty of the plant. Excess NH3
is removed by CO2 stripping instead of distillation as practiced in
conventional total recycle processes, minimizing the energy
requirement.

b) TEC-ACES process

This is typically CO2 stripping process employing higher ratio (4:1) of

NH3 to CO2, and higher synthesis pressure leading to high conversion
efficiencies as compare to total recycle process. Stripping is carried
out in a two stage stripper constructed of special steel. The upper part
of the stripper is a tray column for the removal of excess ammonia
whereas the lower part is a falling film exchanger for the stripping
action.

c) Stamicarbon stripping process

Consumption of steam is decrease by employing a pool condenser of

new design featuring high resistance time and direct heat exchange
between condensing vapours from stripper and the stripped urea
solution; and an evaporator of improved design which allows better
utilization of multiple effect principle in heat transfer.
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d) Ammonia casale's SRR process

Split reaction recycle (SRR) process of ammonia casale is specifically

developed for revamping plants based on stripping technology of
either snamprogetti or stamicarbon and includes installation of
secondary high pressure section consisting of feed pump, reactor,
supplementary decomposer and separator which extend the urea
formation reaction. The operating conditions are same as traditional
ones. The new secondary section added to the synthesis loop can be
prefabricated on skid mounted units and can be erected at site without
any modification on the layout of the existing synthesis section.

Granulation
Now a day, granular urea has gained importance since it minimize air
pollution and granules has higher strength larger sizes and is more
compatible with other granular fertilizers.

Following commercial processes are available for granulation of

urea:
 Pan granulation and falling curtain granulation process of
Tennessee Valley Authority (TVA)

 High temperature pan granulation (GTPG) process of Norsk Hydro.

 Fluidized bed granulation process of Hydro Agri Licensing &
Engineering.
 Fluidized bed granulation process of TEC.

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Major Engineering problems Autoclave variables

The objective of autoclave reaction is to produce the optimum

economic yield. The conditions which affects rate of reactions are
temperature, pressure, NH3/CO2 ratio and feed rate. The urea
production rate can be varied as follows

 Increase with increasing pressure

 Increase with temperature to maximum at 175-1800C, then falls of

sharply. The operating pressure should be above the dissociation
pressure (dissociation pressure is 180atm at 190°C) for the carbamate.
 Use no excess ammonia.

Reasons for not operating at maximum temperature and pressure

without excess ammonia

 Increased pressure increases capital and operating cost of

compression and reaction equipment.

 At higher temperature urea decomposed to biuret, which is

detrimental to germinating seeds and toxic to animals.

 The above process conditions enhance corrosion rates to machinery

Carbamate decomposition and recycle

It is optimized by short residence times in a stripping column

operating at low pressure and high temperature. Later should be below
1100C if hold up time exceeds 1-2 seconds to avoid biuret formation.
Use of millisecond contact time in a flash evaporator allows 1400C
operating temperatures in the high recycle design. Main difference in

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competing processes is in the recycle design. Since conversion is only
40-50% per pass, the unreacted off gases must be recirculated or used
economically elsewhere. Recompression of off gases is virtually
impossible because of corrosion and formation of solid carbamate in
compressors. A solution is formed and pumped into the autoclave.

Production of granular urea (Prilling)

Problem again is biuret formation. Vacuum drying of 80% urea to >

99% and spraying to air cooled and solidify must be done just above
the melting point of urea and with a minimum residence time.

Heat dissipation in the autoclave

The exothermic heat of reaction can be removed by coils, wall

cooling, or by adding excess reactant to provide sensible heat pick up.
Corrosion
It can be minimized by use of the corrosion resistant metals and
maintaining the proper reaction conditions. High cost silver or
tantalum liners are used in the autoclaves with titanium, stainless
(321SS) and aluminum alloys used in other parts of the plant.
Minimum temperature and pressure with excess NH3 are desirable to
reduce the severe corrosion rates.

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 Process control

Each equipment has a control system that consists of several control

loops. The loops adjust process variables as needed to compensate for
changes due to disturbances during plant operation. Each of the
process variables has its own control loop, which typically consists of
a sensor and transmitter, controller and control valve.

EVAPORATOR CONTROLS

In the following paragraphs the load variable will be assumed to be the

flow rate and concentration of the feed stream. A later paragraph, Other
Control Loops, will discuss the control of other variables, such as steam
enthalpy, material balance, and absolute pressure controls. The control
systems to be considered in achieving final product concentration include
(1) feedback, (2) cascade, and (3) feedforward, (4) auto-select, and (5)
advanced controls. For ease of illustration, a double-effect, co-current
flow evaporator will be used. Extension to more or fewer effects will not
change the basic control system configuration.

Selective control can be superimposed on either control configuration,

which will stay inactive until a limit is reached (such as running out of
steam), at which point control is transferred to keep the operation (the
demand for steam) under that limit. Advanced controls usually combine

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all the previous features and add to it a multivariable model-based
predictive capability.

The choice of the control system should be based on the needs and
characteristics of the process. Evaporators as a process class tend to be
capacious (mass and energy storage capability) and have significant dead
time (30 sec or greater). If the major process loads (feed rate and feed
density) are reasonably constant and the only corrections required are for
variations in heat losses or tube fouling, feedback control will suffice. If
steam flow varies because of demands elsewhere in the plant, a cascade
configuration will probably be the proper choice. If, however, the major
load variables change rapidly and frequently, it is strongly suggested that
feedforward in conjunction with feedback be considered.

Feedback Control

A typical feedback control system (Figure 2) consists of measuring the

product concentration with a density sensor and controlling the amount of
steam to the first effect by a three mode controller. The internal material
balance is maintained by level control on each effect.

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Internal Material Balance

The internal balance is maintained by liquid level control on the

discharge of each effect. Analysis of the performance of level loops
indicates that a narrow proportional band (<10%)can achieve stable
control. However, because of the resonant nature of the level loop it can
cause the process to oscillate at its natural frequency, Therefore, in most
installations a much lower controller gain must be used (proportional
bands 50 to 100%).5 Because of such wider proportional bands, the
addition of the integral mode is required to help maintain the set point. A
valve positioner and booster relay are also recommended to overcome the
usual limit cycle characteristics of an integrating process and the
nonlinear nature of valve hysteresis (figure 3).

Figure 3

If a valve actuator cannot move as fast as the speed at which the control signal changes (velocity
limited), a step change in the control signal (left) will result in a delayed straight-line response,
while a sine wave in the control signal (right) will result in cycling

PRODUCT DENSITY MEASUREMENT

Perhaps one of the most controversial issues in any evaporator control

scheme is the method used to measure the product density. Common
methods include (1) temperature difference, boiling-point rise;

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(2) conductivity; (3) differential pressure; (4) gamma gauge; (5) U-tube
densitometer; (6) buoyancy float; (7) refractive index; and (8) oscillating
Coriolis (see Chapter 6 in the first volume of this handbook). Each
method has its strengths and weaknesses (Table 1). In all cases, however,
care must be taken to select a representative measurement location to
eliminate. entrained air bubbles or excessive vibration, and the instrument
must be mounted in an accessible location for cleaning and calibration.
The relative location of the product density transmitter with respect to the
final effect should also be considered. Long runs of process piping for
transporting the product from the last effect to the density transmitter
increase dead time, which in turn reduces the effectiveness of the control
loop.

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References

 Heavy and Fine Chemicals (Chemical Process Technology)

 Fundamentals of Industrial Instrumentation and Process Control
 Process Systems Analysis And Control By Vart

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