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Chapter 1

Literature Review
FERTILIZERS
INTRODUCTION
Fertilizers fall into three general categories; nitrogen (N) based, phosphorus (P) based, and
Combined nitrogen-phosphorus (N-P) based. The majority of nitrogen based fertilizers are
derived from ammonia. In the 1990s, over 95% of all commercial nitrogen fertilizer was
derived from synthetic ammonia. Worldwide, the annual production of synthetic ammonia is
about 120 million tonnes, of which about 85% is used in fertilizers, including urea.

UREA
OVERVIEW
Urea or carbamide is an organic compound with the chemical formula (NH2)2CO. The
molecule has two amine (-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. It is solid,
colourless, and odorless (although the ammonia which it gives off in the presence of water,
including water vapor in the air, has a strong odor). It is highly soluble in water and non-
toxic. Dissolved in water it is neither acidic nor alkaline. The body uses it in many processes,
most notably nitrogen excretion. Urea is widely used in fertilizers as a convenient source of
nitrogen. Urea is also an important raw material for the chemical industry. The synthesis of
this organic compound by Friedrich Wöhler in 1828 from an inorganic precursor was an
important milestone in the development of organic chemistry, as it showed for the first time
that a molecule found in living organisms could be synthesized in the lab without biological
starting materials.
The terms urea and carbamide are also used for a class of chemical compounds sharing the
same functional group RR'N-CO-NRR', namely a carbonyl group attached to two organic
amine residues. Examples include carbamide peroxide, allantoin, and hydantoin. Ureas are
closely related to biurets and related in structure to amides, carbamates, carbodiimides, and
thiocarbamides.
History of Urea
Historically urea was first noticed by Hermann Boerhaave in the early 18th century from
evaporates of urine. In 1773, Hilaire Rouelle obtained crystals containing urea from dog's
urine by evaporating it and treating it with alcohol in successive filtrations. This method was
aided by Carl Wilhelm Scheele's discovery that urine treated by concentrated nitric acid
precipitated crystals. Antoine François, comte de Fourcroy and Louis Nicolas Vauquelin
discovered in 1799 that the nitrated crystals were identical to Rouelle's substance and
invented the term "urea." Berzelius made further improvements to its purification and finally
William Prout, in 1817, succeeded in obtaining and determining the chemical composition of
the pure substance. In the evolved procedure, urea was precipitated as urea nitrate by adding
strong nitric acid to urine. To purify the resulting crystals, they were dissolved in boiling
water with charcoal and filtered. After cooling pure crystals of urea nitrate form. To
reconstitute the urea from the nitrate, the crystals are dissolved in warm water, and barium
carbonate added. The water is then evaporated and annhydrous alcohol added to extract the
urea. This solution is drained off and allowed to evaporate resulting in pure urea.

INTRODUCTION
Urea is an organic compound with the chemical formula (NH2)2CO. Urea is also known by
the International Nonproprietary Name (rINN) carbamide, as established by the World Health
Organization. For example, the medicinal compound hydroxyurea (old British Approved
Name) is now hydroxycarbamide. Other names include carbamide resin, isourea, carbonyl
diamide, and carbonyldiamine.
Urea (NH2CONH2) is produced from ammonia (NH 3) and gaseous carbon dioxide (CO 2) at
high pressure and relatively high temperature. Both reactants are obtained from ammonia
synthesis. The production of urea involves the formation of ammonium carbamate
(NH2COONH4), which is dehydrated to form urea.
For all practical purposes, these two reactions take place simultaneously.
2NH3 + CO2 NH2COONH4 + heat
NH2COONH4 + heat NH2CONH2 + H2O
Both of these reactions are reversible, and therefore ammonia and carbon dioxide exit the
reactor along with ammonium carbamate and urea. The components of this mixture are then
separated, usually by stripping off gaseous ammonia followed by carbon dioxide, to yield
urea. There are a number of process for handling ammonia in this process, including the once
through, the partial recycle and the total recycle processes.
DISCOVERY
It was the first organic compound to be artificially synthesized from inorganic starting
materials, in 1828 by Friedrich Wöhler, who prepared it by the reaction of potassium cyanate
with ammonium sulfate. Although Wöhler was attempting to prepare ammonium cyanate, by
forming urea, he inadvertently discredited vitalism, the theory that the chemicals of living
organisms are fundamentally different from inanimate matter, thus starting the discipline of
organic chemistry. This discovery prompted Wöhler to write triumphantly to Berzelius:"I
must tell you that I can make urea without the use of kidneys, either man or dog. Ammonium
cyanate is urea." It is found in mammalian and amphibian urine as well as in some fish. Birds
and reptiles excrete uric acid, comprising a different form of nitrogen metabolism that
requires less water.

STRUCTURE
Urea is highly soluble in water and is, therefore, an efficient way for the human body to expel
excess nitrogen. Due to extensive hydrogen bonding with water (up to six hydrogen bonds
may form - two from the oxygen atom and one from each hydrogen) urea is very soluble. The
urea molecule is planar and retains its full molecular point symmetry, due to conjugation of
one of each nitrogen's P orbital to the carbonyl double bond. Each carbonyl oxygen atom
accepts four N-H-O hydrogen bonds,[citation needed] a very unusual feature for such a bond
type. This dense (and energetically favourable) hydrogen bond network is probably
established at the cost of efficient molecular packing: The structure is quite open, the ribbons
forming tunnels with square cross-
section.
PROPERTIES OF UREA
Molecular and Crystal Structure
The urea molecule is planar in the crystal structure, but the geometry around the nitrogens is
pyramidal in the gas-phase minimum-energy structure. In solid urea, the oxygen center is
engaged in two N-H-O hydrogen bonds. The resulting dense and energetically favourable
hydrogen-bond network is probably established at the cost of efficient molecular packing:
The structure is quite open, the ribbons forming tunnels with square cross-section. The
carbon in urea is described as sp2 hybridized, the C-N bonds have significant double bond
character, and the carbonyl oxygen is basic compared to, say, formaldehyde. Urea's high
aqueous solubility reflects its ability to engage in extensive hydrogen bonding with water.
Physical Appearance
Urea appears to be a light brown or light yellow. It is normally translucent and comes in the
form of a liquid or solid (pellets).
Odor
The smell of urea is almost non-existent. If a sample of urea is not odorless, it will have a
slight ammonia scent.
Density
The density of this mineral is 1.33 g/cm3. Density is the ratio between the mass and volume.
Specific Gravity
The specific gravity of urea is 1.34 at room temperature: 68 degrees Fahrenheit or 20 degrees
Celsius. This makes the mineral heavier than water.
Solubility
Urea is soluble in water. Its solubility ratio is 119 grams per 100 grams water at a temperature
of 77 degrees Fahrenheit or 25 degrees Celsius.
Molecular Weight
The molecular weight, or molar mass, of urea is measured at 60.06 grams. This measurement
indicates the mass of one mole of urea.
Decomposition
Urea decomposes at 270.8 degrees Fahrenheit (132.7 degrees Celsius); it decomposes into
ammonia and carbon dioxide. If burned, it emits small amounts of nitrogen oxides
USES
Agriculture
More than 90% of world production of urea is destined for use as a nitrogen-release fertilizer.
Urea has the highest nitrogen content of all solid nitrogenous fertilizers in common use.
Therefore, it has the lowest transportation costs per unit of nitrogen nutrient. The standard
crop nutrient rating of urea is 46-0-0. Ammonia and nitrate are readily absorbed by plants,
and are the dominant sources of nitrogen for plant growth. Urea is also used in many multi-
component solid fertilizer formulations.
Urea is highly soluble in water and is, therefore, also very suitable for use in fertilizer
solutions (in combination with ammonium nitrate: UAN), e.g., in 'foliar feed' fertilizers. For
fertilizer use, granules are preferred over prills because of their narrower particle size
distribution which is an advantage for mechanical application.
In grain and cotton crops, urea is often applied at the time of the last cultivation before
planting. In high rainfall areas and on sandy soils (where nitrogen can be lost through
leaching) and where good in-season rainfall is expected, urea can be side- or top-dressed
during the growing season.
Chemical Industry
Urea is a raw material for the manufacture of many important chemical compounds, such as
1. Various plastics, especially the urea-formaldehyde resins.
2. Various adhesives, such as urea-formaldehyde or the urea-melamine-formaldehyde
used in marine plywood.
3. Potassium cyanate, another industrial feedstock.
Explosive
Urea can be used to make urea nitrate, a high explosive which is used industrially and as part
of some improvised explosive devices.
Automobile Systems
Urea is used in SNCR and SCR reactions to reduce the NOx pollutants in exhaust gases from
combustion from diesel, dual fuel, and lean-burn natural gas engines. The BlueTec system,
for example, injects water-based urea solution into the exhaust system. The ammonia
produced by the hydrolysis of the urea reacts with the nitrogen oxide emissions and is
converted into nitrogen and water within the catalytic converter.
Laboratory Uses
Urea in concentrations up to 10 M is a powerful protein denaturant as it disrupts the
noncovalent bonds in the proteins. This property can be exploited to increase the solubility of
some proteins. A mixture of urea and choline chloride is used as a deep eutectic solvent, a
type of ionic liquid.
Urea can in principle serve as a hydrogen source for subsequent power generation in fuel
cells. Urea present in urine/wastewater can be used directly (though bacteria normally
quickly degrade urea.) Producing hydrogen by electrolysis of urea solution occurs at a lower
voltage (0.37V) and thus consumes less energy than the electrolysis of water (1.2V)
Medical use
Urea-containing creams are used as topical dermatological products to promote rehydration
of the skin. Urea 40% is indicated for psoriasis, xerosis, onychomycosis, ichthyosis, eczema,
keratosis, keratoderma, corns and calluses. If covered by an occlusive dressing, 40% urea
preparations may also be used for nonsurgical debridement of nails. Urea 40% "dissolves the
intercellular matrix" of the nail plate. Only diseased or dystrophic nails are removed as there
is no effect on healthy portions of the nail. This drug is also used as an earwax removal aid.
Certain types of instant cold packs (or ice packs) contain water and separated urea crystals.
Rupturing the internal water bag starts an endothermic reaction and allows the pack to be
used to reduce swelling.

INCREASING GLOBAL GROWTH


Global urea production increased by 3.6% in 2009 to reach 146m tonnes, estimated the
International Fertilizer Industry Association (IFA).
Global demand for urea is forecast to grow at 3.8%/year to around 175m tonnes in 2014.
Much of the increase was from fertilizer demand while industrial applications for urea,
accounting for 12% of total consumption, is expected to grow at 7%/year.
Looking at the urea supply/demand balance from 2010 to 2014, the IFA concluded that there
will be a sustained surplus, averaging 5m tonnes/year through to 2012.
Urea demand in China remained firm in 2009, despite a slowdown in the industrial and
fertiliser sectors, growing at 7% over 2008.
India ranks as the world’s second largest urea producer as well as a major importer. Capacity
increases will take place in the 2009-2014 period, with the IFA estimating that the country’s
capacity will reach 32m tonne/year by 2014.
The Middle East is expected to become the world’s largest exporting region as capacity is
expected to reach 23m tonne/year by 2014.
In the US, apparent consumption is estimated by the IFA at 10.4m tonnes in 2009 and
production at 5.8m tonnes. With growing demand and unchanged capacity, urea imports are
likely to grow to around 7m tonnes/year.

FERTILIZER INDUSTRY OF PAKISTAN


OVERVIEW
The fertilizer sector in Pakistan currently comprises of 10 companies that are;
1. Hazara Phosphate Fertilizer (Pvt) Limited
2. Lyallpur Chemical & Fertilizer Limited
3. Pak Arab Fertilizer Limited
4. Pak American Fertilizers Limited
5. Engro Chemicals Pakistan Limited
6. Dawood Hercules Chemicals Limited
7. Fauji Fertilizer Company Limited
8. FFC-Jordan Fertilizer Company Limited
9. Pak China Fertilizer
10. Pak Saudi Fertilizer Company Limited.
A new market for the urea industry is its use in a process called selective catalytic reduction
to reduce NOx emissions from diesel engines.
According to US-based consultants SRI Consulting, the advantage of urea is that it can meet
the new near-zero NOx emission requirements imposed in the US and Europe, while at the
same time achieving 3–5% greater fuel efficiency.

WORLD LARGEST UREA PLANT IN PAKISTAN


Karachi, January 04, 2011: Engro Fertilizers Limited has begun operation of its new fertilizer
plant, the world’s largest single train ammonia-urea plant, in Daharki.
The plant has a production capacity of 1.3 million tons per annum and takes Engro
Fertilizer’s total annual urea production capacity to 2.3 million tons. The expansion project,
which is the largest private sector industrial investment in Pakistan worth USD 1.1 billion, is
a state of the art structure and is the most energy efficient fertilizer plant in the country with
the lowest consumption of gas per ton of urea.
In this project, Engro Fertilizer has continued its tradition of maintaining the highest
benchmarks of Health, Safety & Environment (HSE) by being 100% environmentally
compliant and recording 29.8 million man hours without lost work day injury – a new record
for the country.
Khalid Siraj Subhani, CEO Engro Fertilizers Limited, highlighted, “With this expansion,
Pakistan will have the production capacity to become self sufficient in urea, and the Pakistani
farmer will reap the benefit of cheaper urea produced domestically.”

FERTILIZER CONSUMPTION IN PAKISTAN


Fertilizer consumption has increased threefold during the past 30 years. It reached one
million nutrient tonnes in 1980/81, two million tonnes in 1992/93 and three million tonnes in
2002/03 (Figure). Nitrogen accounts for 78 percent of the total nutrients, phosphate for 21
percent and potash for less than one percent. The average N, P 2O5, K2O nutrient ratio between
1999/2000 and 2001/02 was 1:0.28:0.01.

Total fertilizer nutrient consumption in Pakistan

FERTILIZER PRODUCTION AND IMPORTS


Fertilizer requirements in the country are met from both domestic production and imports.
Currently, there are 14 production units, with a combined design capacity of 2 233 thousand
tonnes of N and 239 thousand tonnes of P2O5. The annual production capacities are as
follows: urea 4.3 million tonnes, DAP 450 thousand tonnes, CAN 450 thousand tonnes, NP
compounds 305 thousand tonnes, SSP 180 thousand tonnes and for NPK compounds 100
thousand tonnes(total 5.78 million tonnes). The overall capacity utilization varies, but it is
always more than 100 percent in the case of urea.
Prior to 1980/81, the country imported well over 50 percent of its annual fertilizer
requirements. However, the situation changed following the expansion of the local industry
during the 1980s.
Figures 5 and 6 illustrate the development of domestic production and consumption of
nitrogen and phosphate fertilizers during the period from 1981 to 2003. Nitrogen production
has the advantage of domestic natural gas resources. Imports as a percentage of deliveries for
the last five years (1998/99 to 2002/03) averaged about 11 percent for nitrogen and 72.5 for
phosphate. Urea has not been imported for the last three years; 46 thousand tonnes of urea
was exported in 2002/03. The total imports of the different products during the past three
years were: DAP 940 thousand tonnes, SOP 18 thousand tonnes, MOP 11 thousand tonnes,
AS 23 thousand tonnes, NP 34 thousand tonnes and small quantities of NPKs. Total imports
thus amounted to about 1.1 million tonnes.

FERTILIZER DELIVERIES AND CONSUMPTION


The consumption of fertilizers in Pakistan is determined by geography, weather (water
availability), prices and the timely availability of the various products. Punjab has the largest
agricultural area and therefore consumes the greatest share of fertilizers, followed by Sindh,
NWFP and Balochistan, in that order.
Provincial crop areas and fertilizer deliveries 2002/03
Province Cropped area Percent of Fertilizer Percent of
(million ha) total deliveries total
(‘000 tonnes)
Punjab 16.10 72.8 2 063 68.3
Sindh 3.16 14.4 674 22.4
NWFP 2.01 9.0 204 6.7
Balochistan 0.85 3.8 77 2.6
Total 22.12 100 3 019 100
Fertilizer consumption by product (percentages)

FERTILIZER POLICY
The government has privatized and deregulated fertilizer imports and prices. In 1986, all
subsidies on nitrogenous fertilizers were abolished followed by phosphates in 1993 and
potash in 1997. Provincial quotas were abolished, provincial supply organizations in the
public sector abandoned and import controls were lifted. All imports are effected by the
private sector. In 2001, the government imposed a 15 percent general sales tax on all fertilizer
products. Farmers have to pay international prices for imported products, apart from urea.
The share of the private sector in fertilizer marketing is 89 percent, compared to 11 percent
for the public sector. The private sector handles about 90 percent of the urea and 100 percent
of the DAP, the two major fertilizer products consumed in the country. A dealer network of
about 8000 retailers exists in the country. Fertilizer companies select and train the dealers.
There is no government intervention. However, under ‘Fertilizer Acts promulgated by
provinces, fertilizer quality is monitored by the provincial governments.

SAFETY
Urea can be irritating to skin, eyes, and the respiratory tract. Repeated or prolonged contact
with urea in fertilizer form on the skin may cause dermatitis. High concentrations in the blood
can be damaging. Ingestion of low concentrations of urea, such as are found in typical human
urine, are not dangerous with additional water ingestion within a reasonable time-frame.
Many animals (e.g., dogs) have a much more concentrated urine and it contains a higher urea
amount than normal human urine; this can prove dangerous as a source of liquids for
consumption in a life-threatening situation (such as in a desert). Urea can cause algal blooms
to produce toxins, and its presence in the runoff from fertilized land may play a role in the
increase of toxic blooms. The substance decomposes on heating above melting point,
producing toxic gases, and reacts violently with strong oxidants, nitrites, inorganic chlorides,
chlorites and perchlorates.
Chapter 2 Processes
Industrial methods
On industrial scale various processes used world wide. Few of them are;
Bosch-Meiser Urea Process
ACES 21 Urea Process
SNAM Process
Bosch-Meiser urea process
Introduction
The basic process, developed in 1922, is also called the Bosch-Meiser urea process after its
discoverers. The various urea processes are characterized by the conditions under which urea
formation takes place and the way in which unconverted reactants are further processed.
description
The process consists of two main equilibrium reactions, with incomplete conversion of the
reactants. The first is an exothermic reaction of liquid ammonia with dry ice to form
ammonium carbamate (H2N-COONH4)
2 NH3 + CO2 ↔ H2N-COONH4
The second is an endothermic decomposition of ammonium carbamate into urea and water:
H2N-COONH4 ↔ (NH2)2CO + H2O
Both reactions combined are exothermic.
Unconverted reactants can be used for the manufacture of other products, for example
ammonium nitrate or sulfate, or they can be recycled for complete conversion to urea in a
total-recycle process.
Urea can be produced as prills, granules, pellets, crystals, and solutions. Solid urea is
marketed as prills or granules. The advantage of prills is that, in general, they can be
produced more cheaply than granules. Properties such as impact strength, crushing strength,
and free-flowing behaviour are, in particular, important in product handling, storage, and bulk
transportation. Typical impurities in the production are biuret and isocyanic acid:
2 NH2CONH2 → H2NCONHCONH2 + NH3
NH2CONH2 → HNCO + NH3
The biuret content is a serious concern because it is often toxic to the very plants that are to
be fertilized. Urea is classified on the basis of its biuret content.
Development of the ACES 21 Process
INTRODUCTION

Toyo Engineering Corporation (TEC), a worldwide engineering contractor and


one of three major urea process licensers, has firstly announced the
development of an advanced version of the ACES urea process named ACES 21
at an international conference Nitrogen 99 held in Caracas, Venezuela in March
1999. Since its establishment 40 years ago, TEC has engineered and
constructed, as of the end of 1999, 93 urea plants in 24 countries based on TEC
own urea technologies, giving a quarter of the world’s total production capacity
by the three major urea processes licensors. P. T. Pupuk Sriwidjaja (PUSRI) of
Indonesia, one of the largest ammonia-urea producers in the world, joined from
the beginning of the R & D for the ACES 21. The final process evaluation and
the engineering study for ACES 21 have completed in 1999 and the ACES 21
Process is now ready for commercial application.

DEVELOPMENT HISTORY OF TEC UREA PROCESS

TEC has made continual efforts to improve the urea process as the process
licenser and the E-P-C contractor, and has contributed to the fertilizer industry
by supplying reliable, efficient and economical urea plants. Realizing the future
technical demands for the urea process technologies during the 21st Century,
TEC has improved the existing ACES Process to realize further reducing
investment costs while maintaining all features of the ACES Process. The
improved process has been named the ACES 21 Process.

Traditionally, TEC has concentrated its process development activities on


energy saving, preventing pollution and improving product quality. As a result
of these efforts, the ACES Process and Spout-Fluid Bed Granulation Process
have been developed and came into operation in the early 1980’s. In the middle
of 1990’s, TEC commenced R & D work on a new urea process, aiming to
reduce plant investment cost and save energy consumption further. The new
process, ACES 21, has become ready for industrial application in late 1999.
THE ACES PROCESS

The main concept of the original ACES Process was to minimize energy input
to the urea plant by combining the features of solution recycle process and
stripping process i.e. a high CO2 conversion and the highly efficient separation
of unreacted materials. The ACES Process drastically reduced steam
consumption compared to Total Recycle Process (See Table 1).
The ACES Process, by ensuring NH3 to CO2 molar ratio (N/C ratio) of 4.0 and
an operating temperature of 190 °C in the reactor give CO 2 conversion of 68%,
the highest among modern urea processes. The high CO 2 conversion reduces the
energy required for decomposition of unconverted materials. The proprietarily
designed tray -falling film Stripper efficiently decomposes and separates
ammonium carbamate and excess ammonia in urea synthesis solution from the
reactor. Fig. 2 shows the simplified flow diagram of the ACES Process
synthesis section.
The unique heat integration between the synthesis section and downstream sections
further reduces energy requirement. MP steam is supplied to synthesis section to
decompose and separate excess NH3 and carbamate in the stripper. The stripped NH 3
and CO2 gas mixture is sent to the carbamate condenser and the condensation heat is
recovered by the two parallel carbamate condensers. One is utilized for
decomposition in the medium pressure section and the other is for low pressure steam
generation to be utilized in the low pressure and evaporation sections. Condensation
heat in medium pressure section is also utilized in evaporation section. This multiple
heat integration concept, originally invented and developed by TEC, gives the most
energy efficient urea process.
PRACTICAL IMPLENTATION OF ACES 21 WORLD WIDE
The ACES Process has been employed in 12 urea plants since its first application in
1983. Over last 10 years, 10 urea plants in 5 countries have employed this process.

List of TEC ACES Urea Plant


R & D for ACES 21 Process

In CO2 stripping technology, the reactor, the largest and the heaviest vessel in urea
plant, is normally installed at 20- 22 meter level so as to feed urea synthesis solution
to the stripper by gravity. If the reactor is installed on the ground level, civil and
erection cost can be greatly reduced. R & D work aimed at installing the reactor on
ground level in CO2 stripping technology has started from its process concept study
and pilot plant planning in 1996. Since the beginning of the R & D, P. T. Pupuk
Sriwidjaja (PUSRI) of Indonesia, one of the largest ammonia and urea producers in
the world with four large scale urea plants based on TEC urea technologies, joined
the project as a partner. The pilot plant has been operated at PUSRI’s plant site in
Palembang, Indonesia and the operating data have been analyzed concurrently using
a PC-based DCS and process analysis software at the plant site since June 1998.
Shows the pilot plant constructed beside the ACES Process urea plant of PUSRI-1B
(see Fig. 8). In the pilot plant, main equipment of the synthesis section of the ACES
21 Process, the carbamate condenser, reactor, stripper and ejector have been tested
and verified in the process performances and the corrosion environment. Electro-
chemical tests and immersion test of possible construction materials have also been
carried out in the pilot plant to select most suitable materials. Process evaluation has
been carried out based on the pilot plant test and very positive performance results
have been obtained.
Chapter 3 Selection of process

Features of the ACES 21 Process are summarized below:

1. The horizontal layout of HP vessels has the following advantages compared to the
vertical layout:

(a) less HP piping and construction materials are used;


(b) easier erection using commonly available construction equipment and
techniques;

(d) easier operation and maintenance

2. Combining the functions for carbamate formation, heat recovery, urea synthesis,
and inert gas scrubbing into one vertical submerged carbamate condenser has the
following advantages in comparison with conventional separate reactor and
falling film carbamate condenser:

(a) fewer and smaller sized HP vessels;


(b) a smaller heat transfer area for heat recovery;
(c) less HP piping and construction material are required

3. Simplified synthesis loop offers the followings advantages over conventional


stripping technologies:

(a) less HP piping and construction materials are required;


(b) easier operation and maintenance

4. Improved design for the reactor and the stripper give the following advantages in
comparison to conventional ones:

(a) less volume and weight for both the reactor and the stripper;
(b) easier reactor and stripper fabrication

5. Optimizing N/C ratios at different levels for the carbamate condenser and the
reactor at lower synthesis pressure results in the following advantages over the
ACES Process:

(a) lower mechanical design pressure of HP vessels and rotating equipment;


(b) less energy consumption

TEC and PUSRI confirmed the combined effect of the above improvements, by one-
year operation of the pilot plant and the following engineering study for an industrial
scale plant, greatly reduces plant cost, energy consumption and operating cost.

ACES 21 ENGINEERING STUDY FOR INDUSTRIAL SCALE PLANT

Engineering study for a typical industrial scale plant has been carried out
concurrently with the pilot plant test to estimate and evaluate process performance
and plant investment cost of ACES 21. The engineering study includes:

z process simulation based on the pilot plant operation to compute the material and
heat balance of the overall urea plant and to optimize process conditions

z process basic design for a typical ACES 21 grass roots plant


z preparation of the standard process engineering package
z estimation of the overall energy consumption of the typical plant including the
performances for CO2 compressor and HP pumps based on manufacturers’
information
z detailed study on mechanical design and engineering of critical HP vessels and
exchangers including investigation on fabrication technology in cooperation with
fabricators

z equipment layout and piping planning study including bill of quantity of piping
materials
z civil design based on the equipment layout and the loading data including bill of
quantity of concrete structure, steel structure and piling

z study on construction and erection to be evaluated in comparison to that for the


existing ACES process
z preparation for instructions for operation and maintenance
z cost estimation of a typical plant investment to be evaluated in comparison to that
of the existing ACES process.

As the result of the engineering study, the ACES 21 process has been confirmed to be
sufficiently advantageous for industrial scale plant application in both the process
performance and the plant investment cost in comparison to the existing
technologies.

Process Performance

About 10% reduction of energy consumption from the existing ACES process has
been confirmed based on the pilot plant test results, the engineering study for an
industrial scale plant, computed process material and heat balance and performance
data of CO2 compressor, HP pumps and steam turbines provided by the major
manufactures.

Mechanical Design and Fabrication of HP Equipment

Mechanical design and fabrication of critical HP vessels and exchangers have been
verified to be sufficiently feasible by applying the proven and available present
technologies, in cooperation with some major vessel fabricators. Total erection
weight of HP vessels and exchangers comprising the synthesis section decreases by
about 10 % in comparison to the existing ACES process. During the course of the
study, design and fabrication of HP vessels and exchangers for 3,500 mtpd ACES 21
single train urea plant, which is equivalent to 2,000 mtpd ammonia plant capacity,
has been confirmed to be feasible based on present available technologies.
Civil and Erection

Concrete and steel structure, and piling for a typical plant excluding the prilling tower
and the granulation plant are estimated to be reduced by 50 % and 40 % respectively
from the original ACES Process. More commonly available construction equipment
and technique can be applied for erecting HP vessels in the synthesis section than the
case for a urea plant based on conventional urea process technologies. For example,
construction equipment and technique applied for erecting HP vessels such as the
reactor, the carbamate condensers, the stripper and the scrubber for a 1,750 mtpd
ACES urea plant can be applied for erecting HP vessels for up to a 3,000 – 3,500
mtpd ACES 21 urea plant owing to the smaller-sized, less weight and lower elevation
of equipment. The required period for the erection work can also be reduced
significantly.

Plant Investment Cost

Plant investment cost has been estimated 10% less than the existing ACES process,
based on TEC in-house cost database and the price estimated by major equipment
vendors and subcontractors of construction and erection works.
FIG. 12: A BIRD’S-EYE VIEW OF

ACES 21 UREA PLANT (3D GRAPHIC)


CONCLUSION

TEC, the only urea process licenser that covers by itself all the proven essential
technologies, i.e. urea synthesis, prilling, granulation and pollution abatement, has
jointly developed a new process ACES 21 cooperating with PUSRI. TEC and PUSRI
has carried out detailed engineering study and final evaluation of the ACES 21
Process with the result of 10% reduction in both plant investment cost and energy
consumption. Now the ACES 21 Process is in the full commercial status and TEC
and PUSRI are jointly starting intensive study to realize the ACES 21 Process for a
large scale plant from the beginning of the year 2000.
Chapter 4

Process description
ACES 21 Process description
The plant uses gaseous carbon dioxide and ammonia as a raw material for urea production. The plant is
designed to yield 1050 MTPD of urea product of the specified quality.

Urea specification
The agriculture grade and uncoated pilled urea has the following specification

Total nitrogen content 46.4 wt %min


Moisture content 0.25 wt %min
Biuret content 0.8 wt %max
Iron and other metal 1 ppm wt %max
Urea prill size(1.25mm) 96 wt %min
Free ammonia 100 wt ppm max

Process description for urea production


The urea process is comprised of the following six sections

 Synthesis section
 Purification section
 Concentration section
 Pilling section
 Recovery section
 Process condensate treatment section

Synthesis section
This section consist of the following steps

 Carbon dioxide compressor


 Ammonia feed pump
 Carbamate feed pump
 Ammonia pre-heater
 Reactor
 Stripper
 Carbonated condenser#1
 Carbamate condenser#2
 Scrubber
Carbon dioxide compressor
The make –up CO2 OF 0.8 kg/cm2 min. and 38oC enter the urea plant and is introduced to the first stage
section separator, where the condensate water is separated from CO 2 and drained to sewer. CO2 gas from
the first stage suction separator is composed up to about 185kg/cm 2 by steam turbine driven, centrifugal
pump type CO2 compressor and most of the CO2 gas is fed to the bottom of the part of the stripper for CO 2
stripping purpose. Anti corrosion air from the synthesis loop is also fed by CO 2 compressor. The air is
injected at the intermediate stage of CO 2 stage of CO2 compressor. The quantity for starting purpose a CO 2
blow off line with pressure controlled is installed to vent the co 2 via vent Silence into Atmosphere.

Ammonia fed pump


The make –up ammonia 25kg/cm3 min. and 30oC is jumped up to 180 kg/ cm 3 and is fed reactor through
ammonia pre heating by ammonia feed pump. The pump is reciprocating type and is provided with
100%stand by pump, both are driven by motor. The pump is equipped with a capacity control device to run
discharge rate from 100% to 50% of design capacity. Liquid ammonia pre- heater the ammonia pre- heater
heats the liquid ammonia to rector by recovering.

Carbamate feed pump


The recycle carbamate solution coming from the recovery section is pumped up to 185kg/cm2 by carbamate
and is fed to scrubber and carbamate condenser#2. Carbamate feed pump is centrifugal pump driven by
motor and is provided with a 100% stand by pump.

Reactor
Reactor is operated at 175kg/cm2 and 190oC and at NH3/CO2 molar ratio which is regulated by feed rate of
liquid ammonia. Reactor is a vertical tower with 9 internal baffles plated to avoid back mixing and its wall is
linked with 316 stainless steel urea grade. The operation pressure of stripper, carbamate condenser # 2 and
scrubber is substantially the same as that of reactor.

The synthesis urea solution, after attaing high concentration CO 2 conversion of 68%, pass through the down
pipe in the reactor and is led to stripper by gravity through control valve by which liquid level of reactor is
adjusted.

Stripper
The liquid level in the reactor is kept above the overflow funnel in the reactor to prevent reversible flow of
CO2 flow from stripper to reactor. In the upper part of the stripper , the synthesis solution from the reactor
contacted with the separated gas from the lower the part through the sieve tray , by which the composition is
adjusted adiabatically suitable for effective CO 2 stripping.

In the lower part of stripper, ammonium carbamate and excess ammonia contained in the urea synthesis
solution and decomposed and separated by CO2 stripping and steam heating in the falling film type heater.
20kg/cm2 steam, saturated in the steam saturation drum, is admitted around the tube to supply the required
heat.

The pressure of the steam is controlled by pressure controller of steam saturation drum in such a way that the
solution leaving the stripper contains 12.5-14.5% by weight of ammonia. The over head gas from the stripper
is sent the carbamate condenser. After CO 2 stripping in stripper, the solution is sent to the purification
section. The recycle carbamate solution is sent to the top of the scrubber and carbamate condenser#2.

Steam drum
The condensate from steam drum is fed to the steam drum. The condensate circulated through steam drum
and shell side of carbamate condenser # 1 to produce 5kg/cm 2 steam. The produced steam in carbamate
condenser #1 is return to steam drum along with condensates, where steam the stem is separated and
discharged to low pressure steam system.

Carbamate condenser
In the carbamate condensers, the overhead gas of stripper is mixed with recycle carbamate solution at the
top, and distributed over the tube and condensed. The condensation heat and absorption heat thus evolved are
utilized for generation 5kg/cm2 saturated steam in carbamate condenser #1 and for heating the stripper outlet
urea solution in the carbamate condenser#2. The feed rate of gas to No.2 Carbamate condenser is required so
as to heat the urea solution from stripper to 155oC. Condensers are operated at 175kg/cm2 and 175OC.

Both gas and solution from the bottom of carbamate condensers are fed to bottom of the reactor. Changing
the steam pressure of steam , drum, means changing the boiling temperature in the shell of carbamate
condenser #1. Therefore the temperature difference between tube and shell side effects the quantity of heat
exchanged over the tubes and hence the carbamate reaction in the tubes. The unreacted condensed gas will
react with ammonia in reactor to supply the required heat for urea synthesis reaction. The steam pressure is
normally set to such that reactor top temperature I regulated at 188 oC-190oC

Scrubber
The rector gas top, containing small quantities of ammonia and carbon dioxide, is sent to the scrubber
operated at 1 75kg/cm2 for recovery. In scrubber ammonia and carbon dioxide are recovered at the recovery
rate of about 50%, using the recycle carbamate solution which is sent to #1 carbamate condenser as
absorbent. The scrubber top gas is sent to HP decomposer for further recovery of ammonia and carbon
dioxide. Part of scrubber top gas is fed to #2 carbamate condenser shell and HP decomposer falling film
heater to rescue the oxygen in the gas for passivation.

Purification section
This section consist of

 HP decomposer
 LP decomposer
 Flash separator
 Urea solution tank
 Urea solution pump
Synthesis urea solution produced at the synthesis section is fed to the purification section ,
ammonium carbamate solution and excess ammonia contained in the synthesis urea solution are
decomposed and separated by pressure reduction and heating in HP decomposer LP decomposer.
Urea solution is purified to about 70 wt% concentration with residual ammonia about 0.4wt% and is
sent to concentration section

Overhead gases from these decomposers are condensed and absorbed in the respective absorber in
the recovery section namely HP absorber, washing column and LP absorber. Pressure of synthesis
urea solution is reduced from175kg/cm2 to 17.5 kg/cm2 then heated to 155oC in #2 carbamate
condenser before being fed to HP decomposer.

High pressure decomposer


The synthesis urea solution is thus heated enter the upper part of HP decomposer, flashed and
decomposed gas is separated and the urea solution is flow down to falling film heater In falling film
heater , the solution is further heated by steam condensate. The solution temperature is controlled at
58oCthe liquid level at the bottom is controlled by level controller. The falling film heater
minimizes the residence time of solution in heater that is; reduce the biuret formation and urea
hydrolysis.

The pressure is controlled at 17.5 kg/cm 2 by a pressure controller on the top of washing column
through HP absorber. A small part of the gas from the scrubber is fed to the falling film heater for
passivation at the rate of 1000 ppm as oxygen.

The overhead gas from the HP decomposer is fed to HP absorber. The bottom solution of HP
decomposer containing residual ammonia and carbon dioxide of 7wt% and 3wt% respectively flow
the upper part of LP decomposer.

Low pressure decomposer


The urea solution , after the most part of the ammonium carbamate is separated in HP decomposer ,
is fed to up to LP decomposer is operated at the reduced pressure of 2.5kg/cm 2 and 123oC where the
solution is further purified to continual residual ammonia and carbon dioxide of 0.5 wt% and 0.4wt
% respectively.

LP decomposer consists of four sieve trays, falling film heater and packed bed. On the sieve trays,
the high temperature gas from falling film heater and process condensate stripper with the liquid
falling film down. The sensible heat of the gas and condensation heat of water vapors are utilized to
evaporate the excess ammonia and decomposed the ammonium carbamate. By this process, the
evaporation of water is minimizes, is making it possible to keep a minimum content water in the
recycle carbamate solution and resulting in lower steam consumption.

Then the solution is heated in the falling film heater by LP steam for further decomposition. The
temperature of the middle part of LP decomposer is controlled by a temperature controller.

CO2 gas from the stripping is injected from CO2 compressor inter stage to the bottom of the packed
bed, where the remaining ammonia in the solutions stripped out by the CO 2 gas. The liquid level of
the bottom part is controlled by a controller.
The gas separated in the LP decomposer is sent to LP absorber of the recovery section. The pressure
of LP decomposer is controlled at 2.5kg/cm2 by a pressure controller at the top of LP absorber. The
urea solution, after separation of gas in LP decomposer is fed for the final stage purification to urea
solution tank through flash separator.

Flash separator
The remaining small amount of ammonia and CO2 are removed by pressure reduction. The pressure
in flash separator is adjusted at 430mmHg by control valve at flash gas condenser gas exit. The
overhead gas from flash separator is condensed in flash gas condenser and the condensate is treated
in process condensate stripper together with condensate from vacuum generation system.

Urea solution tank


The urea solution at urea solution tank outlet contain about 70% of urea and about 0.4 wt% of
ammonia , is sent to the subsequent concentration section by urea solution pump. Then come to
concentration section.

Concentration section
This section consists of;

 Vacuum concentration
 Urea solution circulating pump
 Urea solution feed pump
 Urea solution heater
 Final concentrator
 Final separator

After unconverted ammonia and CO2 are separated from the synthesis urea solution the
purification section, the urea solution is concentrated to 99.9 wt% concentration of urea including
biuret in the concentration section, before it is sent to Prilling Tower.

Vacuum concentration system is adopted for this concentration section in order that future
environmental pollution control regulations are fully met.

VACUUM CONCENTRATOR

Vacuum concentrator consists of upper part and lower part .The urea solution from the
Purification section is first fed to lower part of Vacuum Concentrator, which is operated at the
pressure of 150 mmHg and at the temperature of 77 0C, for concentration to about 84 wt% of
urea .The heat required for HO evaporation is obtained by the recovery of absorption and
condensation heat of gaseous ammonia and CO in HP absorber of the Recovery Section, circulating
the solution by Urea Solution Circulation Pump.

This recovery of the absorption and condensation heat in HP Absorber is also a characteristic
feature of the TEC/MTC C-Improved Process, and has traditionally constituted an essential energy
saving in the urea process design.

Then the 84 wt% urea solution leaving the lower part of vacuum concentrator is heated up to
about 950C in urea solution heater by recovering heat of steam condensate. Then the solution is
further heated to 1320C in the heater by low pressure steam, and is fed to upper part of vacuum
concentrator, where the evaporated water is separated from the urea solution. Urea
concentration in the solution leaving vacuum concentrator is 97.5 wt% including biuret.

At the last stage of this section, the concentrated urea solution is heated to 138 0C in Final
concentrator by low pressure steam, and is fed to Final Separator. After the solution is
concentrated to 99.9 wt% of urea including biuret under 25 mmHg vacuum in Final Separator, it is
pumped up to Prilling Tower top by Molten Urea Pump. The water vapor separated in Final
separator is treated in process Condensate Treatment Section.

PRILLING SECTION

The molten urea concentrated to 99.9 wt% of urea at the concentration section is sprayed, cooled
and solidified to produce product prilled urea in the Prilling Tower.

The Prilling Tower is designed to have the free fall height of 73.5 meters and the inside diameter of
17 meters. Cooling air is sucked through the intake at the tower bottom and rises inside the tower
before it is blown out of the tower by Four Induced Fans installed at the tower top. Dust scrubbing
system is provided at the upper part of the Prilling Tower to recover urea dust in the cooling air.

Droplets of molten urea of 99.9 wt% concentration are formed prilling device which uses
centrifugal force of spinning type basket. While descending in the Tower, the urea droplets come
into contact with the rising air, get cooled and solidified before reaching the Tower Bottom.

The urea prills thus produced are collected by scraper and are sent to Belt Scale through Trommel
by which urea product is weighed and transferred to the Urea Storage as product.
The product air containing urea dust from the Prilling Tower is treated at the Dust Recovery
System located at the top of the tower to meet pollution regulation. Spray nozzles and packed bed
are provided for scrubbing the air. Then the air is exhausted into the atmosphere by the Induced
for Prilling Tower after the water mist from the scrubbing section eliminated by demister. The
Circulating Pump for Dust Recovery is installed is tower top section to circulate urea solution from
the sump to packed bed for Dust Recovery. The concentration of urea solution is maintained at
about 20 wt% by regulating the amount of feed water. The over-flow pipe to Dissolving Tank is
provided to maintain the solution level in sump. Finally the urea dust emission in the effluent air
from the Tower is 30 mg/Nm 3 –air or less which meets fully to pollution regulation. The recovered
aqueous urea solution is recycled to Urea Solution tank.

RECOVERY SECTION

This section consists of;

 LP Absorber
 HP Absorber
 Washing Column
 HP Absorbent Pump
 Carbamate Boost-up Pump
 Carbonate Solution Tank
 Carbonate Solution Pump

In this section, the NH-CO-HO mixture gases from the decomposers are absorbed in lean urea
solution in the absorbers, and recycled back to Reactor. This inert gas with small amount of
ammonia is scrubbed in Washing Column to be vented to atmosphere.

The gases from the LP Decomposer are completely condensed and absorbed in LP Absorber, being
bubbled into absorbent solution through the sparger pipe equipped on the bottom of the absorber
shell. LP Absorber is operated at 2.3 Kg/cm2 and 500C.
The recycle solution from LP absorber is pumped by HP Absorbent Pump the lower packed bed of
Washing Column. The low rate of the recycle solution is measured with a flow indicator. In HP
Absorber and washing Column which are operated at 17.3 Kg/cm 2, all gases from HP Decomposer
are absorbed as ammonium carbamate into the recycle solution from LP Absorber.

This absorption is achieved in the following three steps. First the gas from HP Decomposer is
bubbled through the sparger pipe in the lower cooler of HP Absorber where nearly 75% of the
gases are absorbed. Secondly the gas from the lower cooler goes up to the upper cooler of HP
absorber, where the remaining 19% of the gas is absorbed into the mixture of HP Absorber
solution. Finally, the inert gas from HP Absorber is scrubbed with the recycle solution from LP
Absorber and process condensate from process Condensate Tank, while rising through the packed
bed in Washing Column in order to remove the remaining 6% of ammonia and CO. The
temperature of the upper cooler of HP Absorber is controlled at around 91 0C.

The temperature of the lower cooler of HP Absorber is controlled at 108 0C by TICA which regulates
the cooling water flow rate, by the urea solution circulated from Vacuum Concentrator and by the
circulation of the hot water from the Hot Water Tank. Nearly 50% of heat of ammonium cabamate
formation in the cooler is absorbed by the circulating urea solution to provide the heat for water
evaporation in the Vacuum Concentrator. About 6% of the heat is absorbed by the hot water for
jacketing. The remaining 44%of heat is absorbed by the cooling water. The concentration of CO 2 in
the solution should be kept at around 40%of regulating the flow rate of solution to the synthesis
section. The carbamate solution thus formed in the HP Absorber is pumped up by the carbamate
Boost-up Pump, and then recycled to Carbamate Condensate # 1 & 2, by Carbamate Feed Pump
while a part of it via scrubber of the Synthesis Section. The flow rate of Carbamate Solution to
condensers is controlled by FIC respectively.

PROCESS CONDENSATE TREATMENT SECTION

The water evaporated while processing urea solution to final urea concentration of 99.7 wt% at
the Concentration Section is condensed by Surface Condensers in Vacuum Generation system
along with accompanying urea mist, gaseous ammonia and CO 2 to become process condensate.
The process condensate is then sent to Process Condensate Stripper and Urea Hydrolyzer for
treatment.
The condensate after treatment (clean process condensate) is discharged from the battery limits
of Urea Plant to utilize as cooling water make-up. The gaseous ammonia and CO 2 separated from
the process condensate by stripping are recycled to LP Decomposer of the Purification Section for
recovery.

VACUUM GENERATION SYSTEM

The water vaporized under 25mmHg vacuum in Final Separator of the Concentration Section is
boosted up by Ejector and sent to surface Condenser operated at 81 mmHg and 40 0C for
condensation. The residual water vapor uncondensed in Surface Condenser is boosted up by
Ejector be fed to Surface Condenser operated at 288 mmHg and 43 0C for condensation. The
pressure of uncondensed gas from the Surface Condenser is elevated by the last stage Ejector to
atmospheric pressure for washing by the process condensate in Final Absorber operated at 68 0C
bottom temperature and atmospheric pressure to recover ammonia and CO 2 before the gas is
vented to atmosphere. The water vaporized under 150mmHg vacuum in Vacuum Concentrator of
the Concentration Section is sent to first Surface Condenser operated at 140 mmHg and 36 0C.

The residual water vapor uncondensed in the First Surface Condenser is boosted up by First
Ejector be fed to Second Surface Condenser operated at 312 mmHg and 43 0C for condensation.
The pressure of uncondensed gas from the Second Surface Condenser is elevated by the last stage
Second Ejector to atmospheric pressure for washing by the process condensate in Final Absorber
operated at 680C bottom temperature and atmospheric pressure to recover ammonia and CO 2
before the gas is vented to atmosphere. Vent gas from the Urea Solution Tank is also introduced
to Final Absorber. The process condensate as absorbent is cooled in Final Absorber Cooler before
fed to Final absorber.

The gas containing NH3 and CO2 from FLASH SEPARATOR is sent to Flash Gas Condenser, operated
at 408 mmHg and 430C for condensation. The uncondensed gas from the Flash Gas Condenser is
sent to the vacuum Generation System above mentioned for further recovery of NH 3 and CO2.

PROCESS CONDENSATE TREATMENT SYSTEM


Apart of the process condensate collected and stored in Process Condensate Tank is sent LP
Absorber as makeup absorbent, and the rest is sent to Process Condensate Stripper. The process
condensate is to be treated is sent to the top of Process Condensate Stripper by Process
Condensate Pump.

Process Condensate Stripper has internal sieve trays and is operated at 3.0 Kg/cm 2. The
condensate is stripped off ammonia and carbon dioxide by steam stripping by directly injected
steam to the bottom of Process Condensate Stripper. The overhead gas sent to LP Decomposer of
the Purification Section for the recovery ammonia and carbon dioxide. Process Condensate from
the upper part of Process Condensate Stripper is sent to Urea Hydrolyzer after treating at pre-
heater by Urea Hydrolyzer Feed Pump. Urea Hydrolyzer is operated at 18 Kg/cm 2 and 2000C, to
hydrolyze urea into ammonia and carbon dioxide. The process condensate is then returned to the
lower part of Process Condensate Stripper for further removal of ammonia and carbon dioxide by
stripping, and a part of treating process condensate is sent to Dust Chamber for make-up water of
dust recovery system. The clean process condensate after treatment contains a maximum 5 ppm
of residual urea and ammonia respectively. After heat exchanging with feed process condensate at
Pre-heater, clean process condensate is discharged from the battery limits of Urea Plant to utilize
as cooling water make-up.

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