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TERM PAPER
BY
IN
SUBMITTED TO:
Dr. A. HAMZA
FACULTY OF ENGINEERING
DECEMBER, 2014.
TABLE OF CONTENTS
LIST OF FIGURES............................................................................................. iii
LIST OF TABLES.............................................................................................. iv
ABSTRACT....................................................................................................... v
ABBREVIATIONS AND ACRONYMS...................................................................vi
CHAPTER 1: INTRODUCTION.........................................................................1
CHAPTER 2: LITERATURE REVIEW.................................................................2
INDUSTRIAL PRODUCTION OF UREA..............................................................2
AVANCORE UREA PROCESS.........................................................................2
ISOBARIC DOUBLE RECYCLE UREA PROCESS.................................................4
CHAPTER 3: COMPARISON BETWEEN PROCESSES.........................................11
COMPARISON BETWEEN THE AVANCORE AND SNAMPROGETTI UREA
PROCESSES................................................................................................ 11
COMPARISON BETWEEN THE MITSUI TOATSU AND ISOBARIC DOUBLE
RECYCLE PROCESSES................................................................................. 11
CHAPTER 4: CONCLUSION...........................................................................13
REFERENCES................................................................................................. 14
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LIST OF FIGURES
Figure 1: Schematic diagram of the Avancore urea process (Chemical Engineering, 2012)......4
Figure 2: Schematic diagram of the full Avancore Urea Process (Stamicarbon, n.d., pgs. 12-13)4
Figure 3: Schematic diagram of the isobaric double recycle urea process (Google Patents,
2012b).............................................................................................................. 6
Figure 4: Schematic diagram of the isobaric double recycle process with ammonia injection in
first heat treatment stage (Google Patents, 2012b)........................................................7
Figure 5: Schematic diagram of the isobaric double recycle urea process with two reaction
zones (Google Patents, 2012b)................................................................................ 9
Figure 6: Schematic diagram of the isobaric double recycle process with two reaction zones and
ammonia injection in first heat treatment stage (Google Patents, 2012b)...........................10
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LIST OF TABLES
Table 1: Comparison between the Mitsui Toatsu and the isobaric double recycle urea processes.
..................................................................................................................... 12
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ABSTRACT
This study was carried out to study urea production processes. In this study, two urea
production processes namely: the Avancore urea process developed by Stamicarbon and
the Isobaric double recycle process developed by Fertimont. The details of the Avancore
process were obtained from the process developer brochure while the details of the
Isobaric double recycle process were obtained from a published patent on the process. A
comparison was then made with two other processes: the Snamprogetti urea process and
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ABBREVIATIONS AND ACRONYMS
HP High Pressure
MP Medium Pressure
LP Low Pressure
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CHAPTER 1: INTRODUCTION
Urea (also called carbamide) is an organic compound with the chemical formula
132.7o C. Urea is also soluble in alcohol and slightly soluble in ether. Urea is found
abundantly in the urine of mammals and in lesser quantities, it is present in the blood,
liver, lymph and serous fluids and also in the excrement of fish and many other lower
animals. Urea is produced mostly in the liver as the end product of protein metabolism.
nitrogen (due to its high nitrogen content) and is also an important source of raw
material for the chemical industry for example, it is used as a stabilizer in nitrocellulose
Urea was first discovered in urine in 1727 by the Dutch scientist Herman Boerhaave. In
1828, the German chemist Friedrich Whler discovered that urea could be synthesised
from inorganic starting materials by treating silver cyanate with ammonium chloride.
This was an important discovery because prior to that it was believed a by-product of
life such as urea, could only be synthesised with biological starting materials (the
doctrine of vitalism).
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CHAPTER 2: LITERATURE REVIEW
The industrial production of urea basically involves two steps: reaction of ammonia and
carbon dioxide at high temperature and pressure to from ammonium carbamate and then
the ammonium carbamate formed is dehydrated to form urea and water. In the
In this process, ammonia and carbon dioxide are introduced to the high pressure
ammonia, as well as the carbamate solution from the downstream recirculation section,
enters the pool reactor. The major part of the carbon dioxide enters the synthesis
leaving the reactor. On the shell side, the high-pressure stripper is heated with steam.
The off-gas of the high pressure stripper, containing the carbon dioxide, together with
the ammonia and carbon dioxide resulting from dissociated carbamate, is fed into the
pool reactor. The minor part of the carbon dioxide entering the synthesis as a feed enters
the vertical reactor at the bottom in order to produce sufficient heat for the endothermic
urea reaction. In the pool reactor, ammonia and carbon dioxide are condensed to form
carbamate and a substantial part of the conversion to urea is already established here.
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The heat released by condensation and subsequent formation of carbamate is used to
produce re-usable low-pressure steam. Downstream from the pool reactor, the urea-
carbamate liquid enters the vertical reactor located at ground level. Here, the final part
of the urea conversion takes place. The urea solution then leaves the top of the reactor,
all by gravity flow (via an overflow funnel) before being introduced into the high-
pressure stripper. Gases leaving the vertical reactor are combined with the gases leaving
the pool reactor and are fed into the scrubber operating at a reduced pressure. Here, the
gases are washed with the carbamate solution from the low-pressure recirculation stage.
The enriched carbamate solution is then fed into the pool reactor. This enriched
-stripping plants, meaning that the conversions in the synthesis section are as high as
ever. Inert gases leaving the scrubber at reduced pressure containing some ammonia and
carbon dioxide are then released into the atmosphere after treatment in a low pressure
absorber.
Optional is a flash at a reduced pressure of the liquid leaving the high-pressure stripper,
after which the resulting vapor is mixed with the vapor leaving the urea synthesis and
the carbamate solution coming from the downstream low pressure recirculation section.
Additional carbamate condensation in this mixture is done at the shell side of the first
stage evaporator. This option allows for a decreased high-pressure steam consumption
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Figure 1: Schematic diagram of the Avancore urea process (Chemical Engineering, 2012)
Figure 2: Schematic diagram of the full Avancore Urea Process (Stamicarbon, n.d., pgs.
12-13)
In this process, NH3 and CO2 are reacted at a temperature of between 170 to 205 C
(preferably from 180 to 200 C); and pressure of between 100 and 250 kg/cm 2
(preferably between 180 and 225 kg/cm2) with an NH3:CO2 molar ratio during the
synthesis ranges from 2.5 to 10 (preferably from 4 to 7). The reactor type is a vertical
cylindrical reactor equipped with conventional sieve trays in order to maintain the axial
flow homogeneous or uniform throughout the reactor thus avoiding any back-mixing of
the reaction liquid. The reaction produces ammonium carbamate which is then
completely decomposed; the products of decomposition are urea, water, NH 3 and CO2.
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The decomposition gases and a portion of the excess NH 3 flow back to the reactor after
the liquid (solution of urea in water) is separated. The separated liquid passes to a
second heat exchanger (which is a conventional falling film stripper type) where 75% of
the required CO2 is used to remove almost all the residual NH3 thereby leaving an
almost pure urea solution which is then taken to further purification steps. The overhead
gas from the second heat exchanger is subjected to a condensation and to a residual
purge before being also recycled, in the liquid state (carbamate) to the synthesis stage.
The two heat exchangers are operated at the same temperature as the reactor as are the
two recycle streams that go back to the reactor, hence the name isobaric double recycle
process.
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Figure 3: Schematic diagram of the isobaric double recycle urea process (Google Patents,
2012b)
the isobaric heat treatment under certain operating conditions by the injection of
stripping ammonia.
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Figure 4: Schematic diagram of the isobaric double recycle process with ammonia
injection in first heat treatment stage (Google Patents, 2012b)
It is also possible to operate the isobaric double recycle process with a slight
modification to the reactor. The synthesis may be carried out in two different subsequent
and superimposed reaction zones, with the two isobaric recycles fed to the first zone,
where the dehydration to urea of the greater part of the ammonium carbamate is done,
while in the second zone, operating at a higher NH 3:CO2 ratio than the preceding zone,
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the completion of the dehydration is carried out substantially until the equilibrium level
is reached. When this alternative is used, the NH3:CO2 ratio is preferably from 4 to 7 in
the first and uppermost zone and from 5 to 8 in the second. By increasing the molar
ratio between the two zones, the level of the ammonium carbamate dehydration is raised
because of the dehydrating effect of ammonia, which combines with the resulting water
of reaction and forms a little dissociated ammonium hydroxide (NH 4OH) thus
promoting the completion of the synthesis. The residence time of the synthesis mixture
8
Figure 5: Schematic diagram of the isobaric double recycle urea process with two reaction
zones (Google Patents, 2012b)
Just as with the previous configuration, it is also possible to improve the decomposition
of ammonium carbamate in the first stage of the isobaric heat treatment under certain
9
Figure 6: Schematic diagram of the isobaric double recycle process with two reaction
zones and ammonia injection in first heat treatment stage (Google Patents, 2012b)
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CHAPTER 3: COMPARISON BETWEEN PROCESSES
From the study and discussions carried out in order to compare the urea processes that
were studied, it was observed that in all of these processes, urea is formed basically in
two steps; first ammonium carbamate is formed from the reaction between ammonia
and carbon dioxide and then the ammonium carbamate is dehydrated to form urea. In
the Snamprogetti process, only one reactor is used while the Avancore employs the use
of two reactors: a vertical reactor and a horizontal pool reactor. A similar feature
between the two processes is that after leaving the reactor, the urea formed contains a
large amount of unconverted reactant gases (ammonia and carbon dioxide); these are
stripped off using CO2 gas in a high pressure stripper in both processes. In the
Snamprogetti process, the effluent gases from the high pressure stripper are condensed
into carbamate in the carbamate condenser and then carbamate is recycled to the
reactor; in the Avancore process however, the effluent gases are sent to the pool reactor
where carbamate and subsequently urea are formed. The urea formed is then drawn off
It was mentioned earlier that all the urea processes usually involve the reaction of
ammonia and carbon dioxide to form ammonium carbamate after which the ammonium
carbamate is dehydrated to form urea; the two compared here are no different. In both of
the processes compared, the urea synthesis melt from the reactor is obtained with
ammonium carbamate and some unconverted reactant gases and is thus subjected to
heat treatment and stripping with carbon dioxide. Both processes employ this heat
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treatment/stripping step and also a subsequent step that strips off the remaining
ammonia using carbon dioxide gas but the in the Isobaric Double Recycle process, both
of the stripping/heat treatment steps are performed at the same pressure while in the
Mitsui Toatsu process, the pressure in the second stripping step is lower than that in the
temperature is used in a third CO2-stripping gas step to enhance the separation between
urea and unconverted ammonia and carbon dioxide gases. In both processes, unreacted
ammonia and carbon dioxide as well as ammonium carbamate recovered in the heat
reaction zone(s). The isobaric double recycle process can be operated with two reaction
zones but the Mitsui Toatsu process does not have this provision. Table 1 shows other
Table 1: Comparison between the Mitsui Toatsu and the isobaric double recycle urea
processes.
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CHAPTER 4: CONCLUSION
From the study carried out, it is observed that all industrial urea production processes
basically proceed according through the same reaction; that is, ammonia and carbon
dioxide are reacted to form ammonium carbamate which is then dehydrated to obtain
Because of this decomposition reaction, it is observed that all the urea production
processes considered in this study employ one or more recycle(s) that recover the
After the urea is formed, it usually contains unreacted reactants; these unreacted
reactants are separated from the urea through gas stripping. In all of the processes that
were studied, the stripping gas was CO 2. In some processes like the Mitsui Toatsu urea
The study was carried out sourcing literature mainly from two sources: the process
developer brochure and published patent information. It was observed that the product
process making it easy to understand while the patent described the process to a greater
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REFERENCES
Chemical Engineering (2012). Making Urea Heaps. Retrieved January 14, 2015 from:
http://www.chemengonline.com/making-urea-heaps/
Google Patents (2012b). Process for the synthesis of urea US 4208347 A. Retrieved
Matar, Sami and Hatch, Lewis F. (2000). Chemistry of Petrochemical Processes. 2nd ed.
http://www.saipem.com/site/download.jsp?idDocument=1321&instance=2
http://www.stamicarbon.com/documents/ot/urea-brochure.pdf
Urea (2014). Wikipedia, the free encyclopaedia. Retrieved December 19, 2014 from:
http://en.wikipedia.org/wiki/Urea
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