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UREA PRODUCTION PROCESSES.

TERM PAPER

BY

VICTOR ALI MENTA

IN

PETROCHEMICAL PROCESSING (CHEN 808)

SUBMITTED TO:

Dr. A. HAMZA

DEPARTMENT OF CHEMICAL ENGINEERING

FACULTY OF ENGINEERING

AHMADU BELLO UNIVERSITY, ZARIA.

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

the Mitsui Toatsu urea process.

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ABBREVIATIONS AND ACRONYMS

IDR Isobaric Double Recycle

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

CO(NH2)2 with the structural formula:

It is a colourless crystalline compound highly soluble in water with melting point of

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.

Urea is widely used in manufacture of agricultural fertilizers as a convenient source of

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

explosives and is a basic constituent of synthetically prepared resins.

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

INDUSTRIAL PRODUCTION OF UREA

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

dehydration step, conversion of carbamate to urea is of the order of 50 to 75%. The

remainder is decomposed to ammonia and carbon dioxide. Variations among processes

are directed primarily to economic disposal of this gaseous mixture.

Formation of ammonium carbamate: 2NH3 + CO2 NH2COONH4 (H < 0)

Dehydration of ammonium carbamate: NH2COONH4 NH2CONH2 + H2O (H > 0)

Decomposition ammonium carbamate: NH2COONH4 2NH3 + CO2 (H > 0)

AVANCORE UREA PROCESS

In this process, ammonia and carbon dioxide are introduced to the high pressure

synthesis using a high-pressure ammonia pump and a carbon-dioxide compressor. The

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

through the high-pressure stripper counter-current to the urea/carbamate solution

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

carbamate flow contains no more water than in earlier generations of Stamicarbon CO 2

-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

in the high-pressure stripper, while low-pressure steam consumption is decreased due to

the carbamate condensation supplying heat to the first stage evaporator.

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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)

ISOBARIC DOUBLE RECYCLE UREA PROCESS

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

transferred to a conventional vertical tube bundle heat exchanger where it is almost

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)

It is possible to improve the decomposition of ammonium carbamate in the first stage of

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

in the second and lowermost zone is from 3 to 15 (preferably from 5 to 8) minutes.

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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

operating conditions by the injection of stripping ammonia.

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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

COMPARISON BETWEEN THE AVANCORE AND


SNAMPROGETTI UREA 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

for further purification and processing.

COMPARISON BETWEEN THE MITSUI TOATSU AND ISOBARIC


DOUBLE RECYCLE PROCESSES

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

first. In Mitsui Toatsu process, a further reduction in pressure and increase in

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

treatment/stripping and condensation sections respectively are recycled back to the

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

comparisons of the two processes.

Table 1: Comparison between the Mitsui Toatsu and the isobaric double recycle urea
processes.

Property Mitsui Toatsu process Isobaric double recycle process


Reactor operating temperature 170 - 195o C 170 - 205o C
Reactor operating pressure 160 190 kg/cm2 100 250 kg/cm2

NH3:CO2 molar ratio 3.5 5.0 2.5 10

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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

urea. The dehydration step is usually accompanied (in series) by an unwanted

decomposition reaction of ammonium carbamate to ammonia and carbon dioxide.

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

products of decomposition and returns them to the reactor(s).

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

process however, ammonia is also used as a stripping gas.

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

developer information in most cases was described basically as a summary of the

process making it easy to understand while the patent described the process to a greater

detail thereby making the process description more intricate.

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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 (2012a). Process for synthesizing urea US 4504679 A. Retrieved

January 6, 2015 from: http://www.google.com/patents/US4504679

Google Patents (2012b). Process for the synthesis of urea US 4208347 A. Retrieved

January 6, 2015 from: http://www.google.com/patents/US4208347

Matar, Sami and Hatch, Lewis F. (2000). Chemistry of Petrochemical Processes. 2nd ed.

Houston, TX: Gulf Publishing Company

Saipem S.p.A (n.d.) The Snamprogetti urea technology. Available from:

http://www.saipem.com/site/download.jsp?idDocument=1321&instance=2

Stamicarbon (n.d.). Licensing Urea Technology. Retrieved from:

http://www.stamicarbon.com/documents/ot/urea-brochure.pdf

Urea (2009) Microsoft Encarta 2009. Microsoft Corporation.

Urea (2014). Wikipedia, the free encyclopaedia. Retrieved December 19, 2014 from:

http://en.wikipedia.org/wiki/Urea

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