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Author’s full name: Muhammad Faisal Sultan, Zuneeb Nazir, Muhammad Umer
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SUPERVISOR’S DECLARATION
“I hereby declare that I have read this thesis and in my opinion this thesis is sufficient in
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June, 2016
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ACKNOWLEDGEMENT
In preparing this thesis, we were in contact with many people and teachers. They
have contributed towards our understanding and thoughts. But in particular, we like to
express our sincere appreciation to our supervisor, Engr. Muhammad Sarfraz Akram,
for giving us initiative of this study. His Inspiring guidance, remarkable suggestions, keen
interest and friendly discussions enabled us to complete this thesis. Without his support
and interest this thesis would not have been the same as presented here.
vii
ABSTRACT
Until about the beginning of nineteenth century, world agriculture depends upon on
empirically developed agricultural practices. About that time, however the growth in
understanding of plant physiology, and thus of plant growth needs and fertilization
possibilities, began to parallel the rapid advance of general chemical knowledge and
scientific study of the plant needs become possible.
To determine the feasibility of or need for fertilization requires knowing (1) which of the
required elements if any are deficient in soil; (2) what chemical forms of the deficient
elements are assailable by the plant s thus suitable as fertilizers; (3) what quantity of
fertilizer material is required to meet the needs of the crop; and (4) whether the crop yield
increase resulting from fertilizer application would warrant the cost of fertilizer production
and application.
Phosphorus plays major role in photosynthesis and some other vital processes. It stimulates
early growth and root formation, promotes seed formation and contributes to the general
hardness of the plants. Without phosphorus seeds would be sterile.
The TVA process has been in operation since 1960s and since greater profitability and
economy have been the driving factors for industrial research and development, the journey
to obtain a better process to produce Diammonium phosphate did not end here but it further
evolved towards a different approach in producing DAP by using a pre neutralizer before
pipe cross reactor
viii
Table of Contents
CHAPTER 1 .............................................................................................................................. 1
CHAPTER 2 ............................................................................................................................ 11
ix
CHAPTER 3 ............................................................................................................................ 22
CHAPTER 4 ............................................................................................................................ 28
CHAPTER 5 ............................................................................................................................ 37
CHAPTER 6 ............................................................................................................................ 43
xi
Designing ................................................................................................................................. 43
CHAPTER 7 ............................................................................................................................ 72
CHAPTER 8 ............................................................................................................................ 87
CHAPTER 9 ............................................................................................................................ 92
CHAPTER 10 .......................................................................................................................... 98
CHAPTER 1
Fertilizer is a material that contains one or more chemical elements necessary for proper
development and growth of plants. The important fertilizer are fertilizer animal, manures and
plant residue, these are also called Natural or Mineral Fertilizer. A synthetic fertilizer is a
material produced by industrial process with a specific purpose of being used as a fertilizer. A
fertilizer is essential in today’s agricultural system to replace the elements extracted from the
soil by the plants in the form of food [1].
Pakistan is an agriculture based country. Fertilizer sector contributes 25% to the GDP. Cropped
area of Pakistan has 54% of food grain crop. 87% of the fertilizer is used to enhance crop
production. 92% of the consumed fertilizer contains nitrogen. Nitrogenous fertilizers are
classified to organic and In-organic compounds as shown in figure 1. Amide fertilizers being
organic in nature are further classified to urea and calcium cyanimide.
The fertilizer industry in Pakistan has an oligopolistic structure. The product is differentiated
and there are almost nine firms in the industry. The current situation in the industry is one of
the excess demand. Currently domestic supply capacity is 5.8 mntpa (millions tons per annum)
and demand is 6.8 mntpa [2]. Fauji Fertilizers Bin Qasim is the only domestic producer of
Diammonium Phosphate (DAP) a fertilizer which is required in the planting of new crop.
Currently FFBL’s share of DAP market is 30% with 70% of the market being supplied with
imports[1].
2
3
Plants nutrients are usually categorized as being structural elements, primary nutrients,
secondary nutrients and micronutrients. A typical analysis for the dry matter from a healthy
plant in terms of these nutrients is shown in Table 1.1.
A detailed overview of plant need and demand of these three types of nutrients along with their
sources and importance is given below.
The elements nitrogen, phosphorus, and potassium are primary nutrients not only because
healthy plant growth requires them in relative abundance, but also because these are the
primary elements that most often must be furnished by fertilizers. None of these elements is a
principal component of the usual soil minerals. Elemental nitrogen is the primary component
of the atmosphere (79% by volume). To most plant however. This form of nitrogen is totally
inaccessible. Agricultural crop growth causes relatively rapid depletion of the primary nutrients
in the soil. Thus replenishment by fertilization becomes essential. The principal task of the
chemical fertilizer industry worldwide is to furnish agriculture with chemical forms of nitrogen
(N), phosphorus (P), and potassium (K) that when applied to the soil, can be readily assimilated
by crop plants. Ability to include secondary nutrients and micronutrients in the fertilizers when
needed is also a responsibility of the industry, but volume wise it is the production of N, P and
K fertilizers that defines the industry.
These secondary nutrients, calcium, magnesium and sulfur are also very important. These are
known as secondary because of the need of furnished through fertilizer application, because
these elements also are abundant components of soil minerals at most locations. These elements
also are incidental components of many fertilizers. Moreover the widespread agricultural
practice of liming by application of pulverized limestone or dolomite to the soil intended
chiefly for control of soil pH, incidentally adds calcium and magnesium. Many soils contain
sulfur pawing to atmospheric emissions from the industrial burning of coal and from volcanic
eruptions. Thus intentional fertilizations to furnish the secondary elements in majority cases
omitted. However there are expectations like there are large area in Continent Australia and the
South-eastern United States that are naturally deficient in sulfur and can be made more fertile
by this application of Sulphur containing fertilizers.
5
1.1.1.3 Micronutrients:
Most micronutrient elements are sufficiently present in native soils or impurities in non-
micronutrients fertilizers applied to soil. Thus fertilization to provide these micronutrients
elements specifically can often be omitted. Important exceptions arise in cases from repeated
cropping. In these special cases significant benefits are obtained by the application of small
amounts of micronutrient sources and on the Volumatic basis this is only a small part of the
world of fertilizer industry.
Such fertilizers which are assimilated directly by the plants are known as direct fertilizers.
Such substances which are introduced into the soil just to increase their mechanical, chemical
and biological properties are known as indirect fertilizers.
Such fertilizers contains all the important ingredients for the growth of plants in the combine
form so that extra fertilizers are not needed.
Fertilizers which contain only few elements such as ammonium phosphate or potassium nitrate
are called incomplete fertilizers.
6
Such fertilizers which contains many ingredients and which are get by mechanical mixing of
various fertilizers are known as mixed fertilizers.
Naturally present organic fertilizers include manure, worm casting, peat moss, seaweed and
sewage.
Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mined rock phosphate,
and limestone (which is a calcium source).
Numerous chemical compounds have been shown to be suitable as sources of primary nutrients
in fertilizers. A partial listing is given in Table 1.2. Because the route of these nutrients into the
plant is through root absorption from the soil solution, solubility of the compounds in the soil
solution is of prime importance. All of the Di-calcium Phosphate. Di-Calcium phosphate
nevertheless is suitably soluble in most soil solutions and is recognized as a highly acceptable
fertilizer component. Agronomic response to phosphorus in fertilizers can be suitably
predicated by laboratory measurement of solubility in certain neutral or alkaline citrate solution
reagents. Solubility in pure water therefore is not a necessity although a certain degree of water
solubility is recommended by most agronomists.
7
Phosphorous plays an important role in photosynthesis and some other vital processes. It
stimulates early growth and root formation promotes seed formation and contributes to the
general hardness of the plants. Without phosphorous seeds would be sterile.
The required concentration of phosphorous in the soil solution depends primarily on the crop
species being grown and the level of production desired. Australian researchers indicates that
concentration of 0.2 – 0.3 ppm is adequate for a verity of crops. Mr. Fox of the University of
Hawaii refers to the phosphorous in soil solution needed by the crops concentration of
phosphorous as the external phosphorous requirement of several crops. Maximum crops grain
yields may be obtained when solution concentration are as low as 0.01ppm if the yield potential
is low but yield potential is associated with a level of about 0.025ppm.
The requirement of wheat is on average slightly greater than for corn. Sorghum is believed to
have a requirement similar to that of corn, soybean has much higher requirement then corn.
Two types of phosphorous in soil are used: Organic soil phosphorous and inorganic soil
phosphorous. The main requirement is only concerned with inorganic phosphorous.
The phosphorous content of most virgin soil is very low. Furthermore the phosphorous content
of soil is in forms unavailable to plants. Also there are practically no natural routes of
phosphorous replenishment operating other than the natural recycling of plant material and
animal wastes. The growth of legumes in a crop rotation pattern, although effective for
supplying nitrogen, does nothing towards supplying phosphorous. Organic manures do furnish
some phosphorous but are much less effective than in supplying nitrogen, for these reasons
repeated cropping of land without fertilization can soon deplete the supply of phosphorous and
the land becomes barren.
One fertilization practice initiated in the early nineteenth century that was effective in
furnishing phosphorous was the application of ground bones to soil. Raw bones normally
contain 8-10 % phosphorous (20-25% P2O5) and are thus rich phosphorous sources.
9
Decomposition of raw bones in soil is quite slow however limiting effectiveness. Also the
supply of bones is insignificant in regard to world need for phosphate fertilizer. In about 1830,
in England sulfuric acid pretreatment of bones was began as an effective method of increasing
the availability of the phosphorous to growing plants. About 10 years later, similar sulfuric acid
treatment of mineral phosphate ore was begun to produce the effective fertilizer product now
known as ordinary (or normal) super phosphate.
Essentially all fertilizer phosphate is derived from mineral phosphate. Deposits of mineral
phosphate are abundant and widely dispersed throughout the world. Nearly all of the mineable
deposits are minerals of the apatite group represented by the general formula Ca5 (F, Cl, OH,
0.5CO3) (PO4)3 as mined essentially the ores require beneficiation to reduce the content of clay
silica or other extraneous material. Beneficiation methods commonly used are washing and
floatation using various flotation agents. Beneficiated ores as supplied to fertilizers producers
rang in P2O5 content has been 32% but is decreasing as high grade ores become exhausted. The
phosphorous content of ores and concentrates is in the trade usually expressed as bone
phosphate of lime (% BPL) which is tricalcium phosphate Ca3 (PO4)3. Concentrate of 32%
P2O5 content has a grade of 69.9% BPL.
Realizing the importance of fertilizers for an agricultural country, the development of this
industry in Pakistan is considered. Until 1950 the use of chemical fertilizer in Pakistan was
unknown. The first imports were made in 1952, as a consequence of an acute food shortage.
The use of fertilizers increased slowly in enhancing the yield of crops.
The government of Pakistan has taken several significant steps to boost agricultural production
over the last five years. The domestic production of fertilizer during the first nine months (July-
March, 2010-11) of the current fiscal year was up by 4.5 percent. The import of fertilizer
increased by 133 percent; hence the total availability of fertilizer also increased by 25.3 percent.
Total off take of fertilizer surged by 23.8% due to a subsidy of Rs.500 per bag of Sulfate of
Potash (SOP)/ Marinate of potash (MOP) has been announced. Nitrogen off-take increased
by 15.4% while that of phosphate by 66.2%. Main reasons for increased off-take of fertilizers
were affordable price of DAP and higher support price of wheat. Average retail sale prices of
nitrogenous fertilizers increased while that of phosphate decreased considerably.
11
CHAPTER 2
Process Selection
2.1 Ammonia:
Ammonia is a chemical compound with the formula NH3. At 20oC and 1atm pressure ammonia
is a gas with a characteristic pungent smell. Its main use are in the production of fertilizers,
explosives and polymers. Ammonia can also be used directly as a fertilizers by forming a
solution with irrigation water, without additional chemical processing. This later use allows the
continuous growing nitrogen dependent crops such as maize without crop rotation. Ammonia
is well suited as a refrigeration units. Ammonia is also the basic raw material for most of the
military explosives, ash, nitric acid, Nylon, Plastic, Dyes, Rubbers and refrigeration and many
others [1].
Today the term Ammonia synthesis is increasingly used when referring to the total ammonia
production process. Synthesis conditions are no longer viewed in isolation. They are important
consideration in the total process but can be determined properly only in relation to the total
plant integration.
The complete process of industrial ammonia production can be subdivided into the following
sections: [1]
Following are the process which can be used for the ammonia synthesis.
The Kellogg process is along traditional lines, operating with steam/carbon ratio of about 3.3
and stoichiometric amount of process air and low methane slip from the secondary reformer.
The synthesis pressure depends on plant size and is between 140 and 180 bar. Temperatures of
the mixed feed entering the primary reformer and of the process air entering the secondary
reformer are raised to the maximum extent possible with today’s metallurgy. This allows
reformer firing to be reduced and, conversely, the reforming pressure to be increased to some
extent to save compression costs. An important contribution comes from Kellogg’s proprietary
cross-flow horizontal converter, which operates with catalyst of small particle size, low inlet
ammonia concentration, and high conversion. Low-energy carbon removal systems contribute
to the energy optimization. When possibilities to expert steam or power are limited, part of
secondary reformer waste heat is used, in addition to steam generation, for steam superheating,
a feature in common with other modern concepts. Proprietary items in addition to them
horizontal converter are the traditional Kellogg’s reformer, transfer lines and secondary
reformer arrangement, waste-heat boiler, and chiller in the refrigeration section [4].
There are various process use for ammonia production from decades but Kellogg’s process has
its own benefits which are discussed below. Kellogg’s process big advantage is that it can be
implemented in one of three ways:
Kellogg’s Process potential increases capacity and to provides a suitable retrofit design.
Synthesis loop that had separate feed streams for hydrogen and nitrogen allowed the Kellogg’s
process reactor to be run under a variety of stream rations.
Kellogg’s process reactor was a three bed radial flow converter with a unique proprietary
sealing system which avoided hotspots within the catalyst bed. The Kellogg’s process catalyst
was loaded in its oxidized state just as most catalyst are although it is only active in the reduced
state. Therefore fresh synthesis gas, which heated the catalyst bed to 637 K was used to for the
reduction process. The synthesis loop operated at the original design pressure of 2000 psia. A
continuous purge is required in this retrofit because the expanded plant contains more inert
than in the original synthesis loop. This is more efficient and highly flexible system has been
very easy to operate and has paved the way for grassroots facilities.
Grassroots designs are different from retrofit and expansion designs in that they use 3 and 4
bed intercooled reactors. The reaction for this is so that the iron catalyst can take advantage of
high ammonia reaction rates at low ammonia concentrations. As the reaction progresses,
however, the ammonia concentrations increase and the iron catalyst loses its effectiveness. The
Kellogg’s process catalyst is then used to produce high exit ammonia concentrations at low
pressures, since it can be used at high ammonia concentrations.
In Kellogg’s process the lower pressure synthesis loop, which leads to significant capital
savings, results from the use of a single case gas compressor with thinner walled and lighter
vessels, fittings and piping. This synthesis loop is also advantageous in that it uses energy more
efficiently by recovering heat at a much higher temperature, yielding a 40% decrease in energy
conversion relative to conventional designs. Since the synthesis loop is less complex than in
other plants, operator attention is expected to be less as well. In addition all of these benefits
bring with them an expectation of greater reliability.
Kellogg’s process implemented as either a retrofit, expansion, or grassroots design, has proven
to have significant benefits such as reduced capital costs and energy savings. Kellogg’s
ammonia synthesis configuration leads to an economically advantageous and flexible ammonia
plants [3].
14
Diammonium Phosphate (DAP) is a very important fertilizer that fulfills the need of phosphate
requirement in the soil. Following are the properties of DAP [5].
Diammonium phosphate (DAP) has become one of the most extensively used fertilizer
materials in comparison with other fertilizer salts.
Ammonia (NH3) and Phosphoric acid (H3PO4) are the main raw materials: both are taken from
different sources ammonia is produced from natural gas while phosphoric acid is produced
from treatment of phosphate rock [4].
It provides high concentration of plant food with favorable agro manic and physical properties
and it can be used for direct application. DAP is nonpoisonous, non-explosive and non-
inflammable. It is a prominent base material for dry mixing or blending to produce other grades.
It not only provides high concentration of plant food but it also compatible with mist mix
fertilizer material such as ammonium nitrate, ammonium sulfate, urea, potassium chloride and
maintains good physical properties. It provides economical method for fixing ammonia in solid
form (twice as much as monoammonium phosphate) and it provides increased water solubility
of products by contributing a high content of soluble P2O5. When used in producing wet mix
N-P-K grades can provide the following additional factors [7]:
These are the following process which are available for the manufacturing of DAP.
Diammonium phosphate (DAP) was produced from anyhow ammonia and electric furnace
phosphoric acid in a pilot plant using an atmospheric saturator process in the late 1940’s. This
process consists of aggregates of thin tubular crystals bounded by a film of fine crystal. The
product contained 5% of mono ammonium phosphate, but free of impurities.
The DAP was produced in a continuous single stage atmospheric saturator by continuously
feeding gaseous ammonia and strong electric furnace phosphoric acid (75-85% H3PO4), at an
ammonia-phosphate ratio 2:1 into a saturated solution of ammonium phosphate at about 60 to
70oC. DAP crystallized out of the solution and was recovered by settling, centrifuging, washing
and drying. The ammonia and phosphoric acid mole ration in the solution was maintained as
low as practical without precipitating mono ammonium phosphate. This mole ratio was about
1.6, which corresponded to a pH of 5.8 to 6.0. The DAP crystals precipitate from this solution
were wet with a film of relatively more acidic mother liquor, a portion of which was displaced
by water during washing and the reminder crystallized in the surface of the DAP crystal. The
pilot plant produced about 40 pound of DAP per hour per square foot saturator cross section.
When it is compared with other fertilizer salts the Diammonium phosphate (DAP) product was
comparatively stable resisted compatible physical characteristics and on exposure to 30oC and
relative humidity up to 80%, moisture absorption and ammonia loss were negligible [7].
16
Drawbacks:
Attempt to use wet process phosphoric acid for production of DAP by the atmosphere saturator
process were unsatisfactory because of the formation of precipitates that retarded filtration.
This process was started in the early 1950s when Tennessee Valley Authority (TVA) produced
Diammonium phosphate (DAP) on demonstration scale in a vacuum crystallizer. The process
which was earlier developed in pilot plant consisted of feeding gaseous ammonia and furnace
grade phosphoric acid into the vacuum crystallizer. This product was a coarse crystalline
material containing 21% nitrogen and 53% phosphorous pentoxide [8].
Drawbacks:
Attempt to use wet process phosphoric acid for production of DAP by the atmosphere saturator
process were unsatisfactory because of the formation of precipitates that retreated filtration.
Same results reported in vacuum crystallizer.
Gas driven off in the pyrolytic distillation of coal, called “coking” contain approximately 1%
by volume of ammonia. Therefore an absorption type scrubber was used to strip the ammonia
from the effluent gas before releasing the gas to atmosphere.
Two type of the ammonia saturator or scrubber were most commonly used the absorption pf
the ammonia. In the Koppers or single stage tube type saturator, the gas was dispersed into the
acid liquid phase by means of a submerged sparger ring or cracker pipes. Secondary cleanup
of ammonia from the gas was accomplished by sprays in the vessel above the tube [7].
17
In the second type of the saturator, designed by the Otto construction Company, the liquid level
was below the reaction zone of the vessel. The gas flowed upwards through the vertical
cylindrical vessel, counter-current to acid liquor sprays from a main bank of nozzles and from
auxiliaries nozzle located near the inlet and outlet [8].
Drawback:
The crystal formation and separation process were essentially the same for diammonium
phosphate (DAP) as for ammonium sulfate. However because of complication in settling
resulting from a difference in specific gravity between diammonium phosphate crystal and the
liquor at the operating pH and temperature, approximately twice as much settling tank area and
a non-turbulent feed were necessary for successful settling of DAP product crystal.
In the early 1960s TVA developed what is perhaps today the most widely accepted process for
production of granular diammonium phosphate. Although a number of the Dorr-Oliver blunger
type plants are still in operation, most recent new plants have been the (TVA) type having a
pre neutralizer for partial ammoniation of the phosphoric acid and completion of ammoniation
in a TVA patented rotary ammoniator granulator instead of a bulger. Granulation is controlled
by recycling product fines to the drum. Numerous refinements and variations have been made
in the process in subsequent plants, especially in the areas of dust control, ammonia recovery,
energy conversion, metering, controls, etc. [6, 7, 8].
The basic process involves partial pre neutralization of the acid in a pre-neutralizer (reaction
tank) followed by completion of ammoniation to diammonium phosphate in the rotary
ammoniators-granulator. Excess ammonia, which must be fed to ammoniator-granulator to
produce diammonium phosphate, is recovered by scrubbing the off gases with the acid to be
used in the process. The granular product is normally dried and in most plants cooled, and
screened, having the undersized and crushed oversized recycle to the granulator to control
granulation [7].
1) The heat of reaction of ammonia and phosphoric acid is used to evaporate water in the
neutralizer.
18
2) Advantage are taken of the maximum solubility of the ammonia/phosphoric acid mole
ratio of about 1.45 therefore, the pre neutralizer is operated at as near this point as is
practical to obtain the most concentrated slurry having satisfactory fluidity. This slurry
can either flow by gravity into a saw tooth weir pipe for distribution in the ammoniator-
granulator, or be pumped into a spared spray system located over the moving bed of
dry recycle inside the ammoniator-granulator. The latter procedure has proved most
satisfactory. It provides more consistent control and better slurry distribution.
Ammoniation of the slurry in the ammoniator granulator drum to a mole ratio of 2.0
lowers the solubility and cause crystallization of the diammonium phosphate. This
decreases the amount of the liquid phase present, thereby lowering the recycle
requirement [8].
Some of the plants originally equipped with blungers have been modified to use TVA-type
rotary ammoniator instead of blunger. Plants built in the United States in the recent years use
the TVA-type rotary ammoniator-granulator [6].
The best process for DAP production is the TVA granulation process. The advantages of the
process with individual equipment are described below [7]:
There are two main raw material needed for the production of Diammonium Phosphate.
This section gives a brief account of the preparation of the raw materials required for the
production of Diammonium phosphate from their naturally occurring sources.
Phosphate rock is a non-detrital sedimentary rock which contains high amounts of phosphate
bearing minerals. The phosphate content of Phosporite is at least 15-20%. Which is a large
enrichment over the typical sedimentary rock content of less than 0.2%. The phosphate is
present as fluorapatite Ca3 (PO4)3F (CFA) typically in cryptocrystalline masses (grain sizes <
1µm) referred to as cellophane. It is also present as hydroxyapatite Ca5 (PO4)3OH, which is
often dissolved from vertebrate bones and teeth, whereas fluorapatite can originate from
hydrothermal veins. Other sources also include chemically dissolved phosphate minerals from
igneous and metamorphic rock. Phosphorite deposits often occur in extensive layers, which
cumulatively cover tons of thousands of square kilometers of the Earth’s crust.
Phosphate rock is typically found an average of 25 feet beneath the ground’s surface. The
phosphate matrix is a mixture of pebbles, sand and clay. The sandy layer of soil covering this
matrix is removed by electrically operated draglines. A dragline is powerful machine that digs
phosphate rock around the clock. The draglines equipped with large buckets then dig the matrix
and deposit the materials into a shallow containment area called a well. Here high pressure
water guns controlled by operators in a portable pit car, liquefy the materials into a watery
mixture called slurry. The material is then transported through pipeline to a beneficiation plant.
20
The washer is the first step in separating phosphate from the clay and sand. Here large clay
balls are mechanically disintegrated in equipment called log washers. The materials then moves
through a series of vibrating screens (+16 meshes) where it is cleansed of clay and the pebble
sized phosphate is recovered as a finished product. The pebble is moved to dewatering tanks
and the inventory pile by conveyors. The sand and the fine particles of phosphate called
concentrate are retained for flotation processing. The clay that has been separated from the
matrix is pumped through pipelines to storage ponds (clay setting ponds), where the clay slowly
settles to the bottom.
At the flotation plant reagents are mixed with the concentrate. This process separates the two
components. The sand is transported by pipelines to the mine for use in land reclamation. The
phosphate concentrate is sent to dewatering tanks and then to the inventory pile.
This process involves the electric furnaces melting of the ore using coke and silica to produce
elemental phosphorous, which is then converted to phosphoric acid by first oxidizing (burning)
to it to produce P2O5 and then absorbing P2O5 in water. This process results in a food grade
acid of high purity that has been proven to be too expensive for general fertilizer use. The
4P + 5O2 2P2O5
This process involves an initial step in which the ore is solubilized in sulfuric acid, because of
this requirement for this acid it is obvious that sulfur is a raw material of considerable
importance to the fertilizer industry. The acid rock reaction results in formation of phosphoric
acid and precipitates of calcium sulfate. The second principle step in the wet process is filtration
to separate the phosphoric acid from the precipitated calcium sulfate. Wet process phosphoric
acid is much less pure than electric furnace acid, but for most fertilization production the
impurities such as iron aluminum and magnesium are not objectionable and actually contribute
to improve physical condition of the finished fertilizer. Impurities also furnish some
micronutrient fertilizer elements. The chemistry of phosphoric acid manufacture and
purification is highly complex, largely because of the presence of impurities in the rock. The
main chemical reactions in the acidulation of phosphate rock using sulfuric acid to produce
acid.
22
CHAPTER 3
A flow diagram of the process Tennessee Valley Authority (TVA) process for the production
of granular DAP being used in this plant is displayed in process diagram. Any referrals made
to the flow sheet in the following passages of process description would refer to this diagram.
The following passages give a detailed description of the flow sheet.
The manufacture of DAP starts with the provision of raw materials of the desired grade. For a
quality product of the raw materials should be free from any impurities which in reality is not
100% possible. Details of the grade of raw materials being used for DAP production are given
below.
3.1.1 Ammonia:
Ammonia being used is anhydrous, 99.5% pure and having a nitrogen content 82.4%.
Phosphoric acid being used is merchant grade having 52% P2O5 content and containing 12-
17% impurities.
H2O = 13.187%
Inert = 15.043%
23
With a single reaction tank, the anhydrous ammonia is normally feed at from 2-4 location
around the circumference in the lower portion of the tank. Either liquid or vaporized ammonia
is used in as much as heat and additional equipment is normally required to vaporize the
ammonia. The phosphoric acid is normally fed from source as 54% P2O5 content. This varies
in this range depending on the source of rock used in making the wet process phosphoric acid,
which in turn varies the impurities entering with the acid. The mole ratio of ammonia to
phosphoric acid is normally held between 1.4 and 1.45. This will normally give the maximum
solubility for the slurry. The temperature of the slurry is normally maintained at about 115.5 oC.
For operating control the mole ratio is determined by periodically checking the pH of slurry
samples. At a mole ratio of 1.45 some free ammonia is lost in the steam from the pre
neutralizer. Therefore, the exhaust from the pre neutralizer is scrubbed with acid. One scrubber
is generally used for the pre neutralizer and ammoniator-granulator.
The slurry containing between 16 and 20% water is normally pumped to a spray header in the
ammoniator-granulator. In the early systems the pre neutralizer tank was located above the
ammoniator-granulator, which permitted gravity flow of the slurry to the ammoniator-
granulator [8].
24
In a pipe cross reactor process, chemical heat of reaction between ammonia and phosphoric
acid results in the production of a hot mixture of low moisture melt and steam. This melt is
used to cause granulation, having an emission temperature between 115.5 to 137.7oC, instead
of steam and water as used in the conventional process. The pipe cross reactor is a reaction
tube mounted so that the acids, ammonia and water are added in a section just outside the feed
of the rotary ammoniator-granulator and having the reaction tube extending into the
ammoniator-granulator for discharge onto a moving bed of dry material [7].
Ammonia and water are mixed before entering through a smaller tube at the feed end of the
reactor. This tube extends beyond the section where the acids are added and mixed before
reacting with the ammonia. Phosphoric acids is introduced through lines installed
perpendicular to the reactor tube. The water introduces a smoother reaction between the
ammonia and acid. By the reacting these materials inside a confined area, much of the chemical
heat of reaction is retained to vaporize most of the water entering with the ammonia and acid,
this water is removed in the exhaust gases from the granulator. The temperature of the melt is
well above its normal melting point when it is discharged. Pressure from the reaction provides
good distribution of the near anhydrous melt as it leaves discharge section of the pipe reactor.
The basic advantage of the pipe cross is that a higher percentage of the heat of reaction of
ammonia with acid can be used to evaporate water entering with raw material and still provide
a proper fluid state to build product size granules when the material is discharged on to a bed
of moving fine recycling material without problem in distributing and transferring the low
moisture melt from the reactor [8].
Less recycle is required rather than the blunger type this reduces the requirements for
subsequent operations such as drying, cooling, sizing and recycles handling with considerable
increases in the cost of energy in recent years this becomes an important consideration [6].
The partially reacted product mono ammonium phosphate from the pipe reactor is directly
sprayed into the ammoniator granulator through the slotted discharge of the pipe reactor. As
the pipe reactor is placed inside the ammoniator granulator thus no pumping equipment is
required. The ammoniator granulator is an inclined rotating drum in which the slurry from the
reactor is sprayed on a bed of ammonium phosphate solids and recycled under-sized Dap
granules from the screens. The partially reacted reactor product is produced to completion by
further ammoniation to diammonium phosphate in the ammoniator granulator by using
additional anhydrous ammonia which is sparged from beneath the bed by using a sparger.
Overall NH3:H3PO4 mole ratio is brought to 2. This granulator drastically decreases ammonium
phosphate solubility and this promotes solidification and releases further heat of reaction which
volatilizes additional moisture. Beside the formation of granules from the reactor slurry the
undersized granules from the screens are coated by the slurry which also contributes to granule
formation and growth. The recycle rate of undersized product to the granulator in process is
1.5 kg per kg of product. Variation of this recycle rate is principle control over granulation
efficiency in the drum. Some quality of sulfuric acid is also added to the granulator to adjust
the grade of the DAP of the DAP by reacting more readily with ammonia than phosphoric acid
thus reducing the percentage of P2O5 in the final product. The motion of the granulator causes
the rolling slurry and solids to turn into granules and the angle of the granulator and its angular
speed is critical to product flow rate and most importantly in maintaining the size range of the
granules. The Diammonium phosphate granules from the ammoniator granulator are at a
temperature of 98oC and contain a moisture content of about 3.5%. The product from the
granulator needs drying which is sent to dryer.
In both the pipe cross reactor and rotary ammoniator granulator the absorption of feed ammonia
is incomplete thus acid scrubbing of the effluent vapors from these units is an important feature
of the process. The effluent vapors from the granulator also contain water vapors evaporated
in the reactor and the granulator. The ammonia vapors are absorbed and neutralized in the
scrubber by diluted phosphoric acid having a P2O5 concentration of 35% which is achieved by
diluting feed phosphoric acid having P2O5 concentration of 52% through water as seen in the
flow sheet. The partially ammoniated phosphoric acid is then recycled back to the pipe cross
26
reactor and thus becomes one of the two phosphoric acid streams as mentioned earlier and also
visible from the flow sheet. The water vapors are expelled as off gases.
The granular diammonium phosphate from the granulator is sent to the rotary cooler where
they are cooled by contacting them counter currently with ambient air at a temperature of 35oC.
Through this cooling operation some moisture is also lost rendering the cooled product to have
a moisture content of 2%.
The Diammonium phosphate granules are then sent to the screens where they are screened for
size. The undersized granules are recycled back to the granulator where they are coated with
the reactor slurry to increase their size. While the oversized granules are sent to the crusher
where they are crushed and again sent back for screening. The desired sized granular
ammonium phosphate is sent to the packaging and storage section.
27
28
CHAPTER 4
Material Balance:
Material Balance for the Production of 1500 Tons per Day of Diammonium Phosphate
Screen
2
PRODUCT
Product
Reaction:
According to stoichiometry
NH3 : H3PO4
1.45 : 1
At this ratio the 90% of the phosphoric acid is consumed in the Pre neutralizer
Hence
Moles of NH3 leave the Pre Neutralizer = 562.67 - 349.245 = 213.425 Kmol/hr
Amount NH3 leave the Pre Neutralizer = 213.425 x 17.031 = 3634.84 Kg/hr
Assumption
Ammonia leaves the Pipe cross reactor = 3634.84 - 627.8427 = 3011.99 Kg/hr
Reaction:
Total Amount of NH3 required in Pre neutralizer = 562.67 x 17.031= 9582.83 Kg/hr
CHAPTER 5
Energy Balance
Heat In:
= 119218.75 KJ/hr
Heat Out
= 558505.67 KJ/hr
Heat out with H2O evaporated = 424.08 x 1.9 (393.15-298.15 ) =76546.44 KJ/hr
Heat In
Heat In From PCR to Granulation Excluding Heat of Content with H2O Evaporated=
10324553.07 KJ/hr
= 906055.14 KJ/hr
Heat out
Heat consumed to take NH3 from 238.65 to 298.15K = 10242.62x2.302 (298.15 - 238.65)
= 1402918.6KJ/hr
Heat out with moisture goes to Dryer =6798.4x4.17 (363.15 - 298.15) = 1842706.32KJ/hr
Hot Out
CHAPTER 6
Designing
m = 12.15 kg/sec
= 0.014796 Ns/m2
= 72.15 mm = 0.07215 m
Area = π/4 D2
= π/4 (0.07215)2
= 4.086 × 10-3 m2
44
Dynamic Head:
𝑙 ⍴𝑣 2
∆𝑃𝑓 = 8𝑓( )( )
𝑑 2
Velocity = u = flow rate / area
= 0.014796 / 4.086×10-3
= 3.62 m/s
= (1579×0.07215×3.62) / 0.00769
= 53629
= 5 × 104
Relative Roughness:
= 0.046 / 72.15
Total: = 338
= 24.385 m
= 25 + 24.385
= 49.385m = 49.5 m
So, we get
= 8(0.0025)×(49.5/0.07215)×1579×(3.622/2)
= 141960 N/m2 or Pa
46
Static Head:
Suppose: Δz = 10 m
= 217680 N/m2
∆𝑃 ∆𝑃𝑓
𝑔∆𝑧 + − −𝑊 =0
⍴ ⍴
So,
Pump Efficiency:
From Graph:
Efficiency of pump = 57 %
Pump Power:
Power = (W × m) / efficiency
≈ 3.1 Kwatt
Pump Head:
= 33.2 m
47
Pump RPM:
From Graph:
𝑃 𝑃𝑓 𝑃𝑣
𝑁𝑃𝑆𝐻(𝑎) = +𝐻− −
⍴∗𝑔 ⍴∗𝑔 ⍴∗𝑔
Where
P = Atmospheric Pressure
Pf = Dynamic Head
Pv = Vapor Pressure
NPSHa = (101325/9.81*1579)+10-(141960/9.81*1579)-(933.26/9.81*1579)
= 7.336 m
48
Reaction Involved:
Reaction Kinetics:
Volume of Reactor:
𝑉 CAo.𝑋A
Residence Time = t= = [16]
𝑉𝑜 −𝑟A
VoCAo.𝑋A
V=
−𝑟A
0.15489×16.1122×0.9
V=
1.169
L=1.6 D
𝜋𝐷²𝐿
Volume of reactor = V = 4
𝜋𝐷²1.6𝐷
1.86 =
4
𝑉 𝑉
Residence time = 𝜏 = = = 12.5 sec
𝑉𝑜 0.15489
Di = 0.4D
Di = Impeller Diameter
D = Diameter ofTank
Di = 0.4×1.15
Di = 0.46 m
𝑃
Power Number = Np = KReFr =
𝐷⁵𝑁ᵌ𝜌
𝐷𝑖²𝑁𝜌
Reynold Number = Re =
𝜇𝑧
𝐷𝑖𝑁²
Froude Number = Fr =
𝑔
P = Power of Shaft, W,
Di = agitator Diameter, m,
ƿ = Blade Pitch
ƿ
=1
𝐷𝑖
Ƿ = 0.46m
0.46²×16.666×1178.75
Re =
4.9215
Re = 845
51
0.46×16.666²
Fr =
9.81
Fr = 13
P = 0.19×16.663×0.465×1178.75
P = 21348.4 W
52
REACTION:
NH3 : H3PO4
1.45 : 1 [12]
Phosphoric acid is our limiting reactant.so calculation based on the phosphoric acid.
= .01611 Kmol/m3
𝐾 = 𝐴𝑒𝐸𝑎/𝑅𝑇
𝐸𝑎
𝑙𝑛𝐾 = + 𝑙𝑛𝐴
𝑅𝑇
Assume the granulation of MAP fertilizer has the same factors for the pipe cross reactor.[18]
Ea=44.2 kJ/mol
Arrhenius equation.
𝐸𝑎
𝑙𝑛𝐾 = + 𝑙𝑛𝐴
𝑅𝑇
lnK = 0.86
K = 2.41 sec-1
54
Rate of reaction = K Ca
V=0.492 m3
V= 492000cm3
Residence time:
t = V/Vo
t = (0.492) / .01289
t = 38 sec
L = 36D
55
Volume of Reactor:
= 3.14/4(36D3)
0.492 = 3.14/4 x 36 D3
Further calculation:
D = 0.2591 m = 25 cm
L = 9.32 m = 932 cm
Area=length x Diameter
Length = .5 D
Length = 12.5cm
Diameter= .25D
Diameter= 6.25 cm
Area = 78 cm2
Design Steps:
Air Properties:
mv = 5098.8 Kg/hr
mg = 499.8ton/day
Diameter of Dryer:
G = 4500 lb/ft2.hr
S = 40ft2
Ua = 0.5G.67 / D
Ua = 13.8Btu/hr.ft3.°F
RPM:
Actual temperature 90 ˚C
A=Q/v
A = 0.5Dc x 0.2Dc
Particle size: Not less than 90% of the material shall pass through 4 mm IS sieve and
be retained on 1 mm IS sieve. Not more than 5% shall be below 1 mm size.
As we have to deal with tiny particles and these are expensive and we can't waste this
product as it could also be a cause of pollution so we will chose the Design below:
Where:
d2 = mean diameter of the particle separated in the proposed design at the same
separating efficiency.
= 54113.07935 m/hr
= 54113.07935/3600 m/sec
= 15m/sec
63
= 1.999 m
De = 0.995 m
= 0.2 x 0.995
= 0.199 m
= 0.5 x 0.995
= 0.4975 m
= 2.5 x 0.995
= 2.4875 m
= 1.5 x 0.995
= 1.4925 m
= 0.5 x 0.995
= 0.4975 m
64
= 0.5 x 0.9990
= 0.4995m
= 0.975 x 0.995
= 0.373 m
= 10
= 2143.126 m3/hr
= 6705.1 - 0.9721
= 6704.1279 kg/m3
Scaling Factor:
= 2.095
= 0.194 m2
= 12.43 m2
= 0.099 m2
Pressure Drop:
Φ = fc.As / A1
Φ = fc.As / A1
Φ = 0.63
2.0𝐷𝑐
𝑟𝑡 𝐷𝑐− 2
=
𝑟𝑒 0.5𝐷𝑐
= 1.8
u1 = (2143.126/3600) x (1/0.99)
66
= 6 m/s
u2 = (2143.126/3600) x (1/0.194)
= 3.06 m/s
= 43670.3Kg/hr
= 27.66 m3/ hr
= 31.11 m3/ hr
Assuming:
L/D ratio =2
L = 2D
31.11 = (πD2/6) x 2D
D = 3.10 m
L = 6.2 m
Where,
Di = Internal diameter
Pi = Internal pressure
f = Design stress
= 95785.2 N/m2
68
= 0.9386 atm
= 0.0952 N/mm2
f = 150 N/mm2
Thickness = Pi x Di/2f - Pi
= 1 mm
Corrosion allowance = 2 mm
So
Thickness (l) = 3 mm
Domed Head:
Knuckle radius = RK = 6% of RC
= 0.186 m
Assuming no joints J= 1
Stress Concentration:
= 0.25x [3 + 4.08]
= 1.77
69
Now
= 1.8 mm = 2 mm
By putting values,
Thickness = 1 mm
So an ellipsoidal head is most economical, hence we will take thickness as wall 3mm [5].
70
Mass = 133476 Kg
= 72.54 m3
= 81.6 m3
Assume; L/D =2
L = 2D
81.6 = πD2/6 x 2D
D = 4.25 m
L = 8.5 m
= 150567.2 Kg/m.sec2
= 150.567 KN/m2
= 1.485 atm
= 0.15 N/mm2
= 2 mm
71
Corrosion allowance = 2 mm
Thickness = 4 mm
Domed head:
Stress concentration:
CS = 1/4[3 + (RC/RK)1/2]
= 0.25[3 + (4.17/0.25)1/2]
= 1.77
= 14.2 mm = 14 mm
= 2 mm
Ellipsoidal head is economical than head with 4mm wall of the tank.
72
CHAPTER 7
As the field of process control has matured over the last 30 years, it has become one of the core
areas in chemical engineering. One of the important themes that we emphasize here is the need
to understand the process-its operation, constrains, design, and objectives. The way the plant
is design has a large impact on how it should be controlled and what level of control
performance can be obtained. (1)
Thus the operating pressures, temperatures, concentration of chemical, and so on, should
always be within allowable limits process may be controlled more precisely to give more
uniform and higher quality products by the application of automatic control, often leading to
higher profits. Additionally, processes which respond too rapidly to be controlled by human
operators can be controlled automatically. Automatic control is beneficial in certain remote,
hazardous, or routine operations.
As it is very obvious that process profit is usually the most important advantage to be obtained
by applying automatic control, the quality of control and its cost should be compared with the
economic return expected and the process technical objectives. The economic return includes
reduced operating costs, maintenance cost, product cost and overall cost.
Objectives
Safety:
Smooth production
Quality:
Economics:
To operate at the lowest production cost, in a typical chemical processing plant these objectives
are achieved by a combination of automatic control, manual monitoring and laboratory
analysis.
In almost every control configuration, we can distinguish the following hardware elements.
It represents the material equipment together with physical or chemical operation that
occurs. In this discussion, the process is fermentation.
Such instruments are used to measure the disturbance, the controlled output variables, or
the necessary secondary output variables and are the main sources of information about
what is going on in the process.
The measuring means depend upon the types of variable, which is to be measured, and
these variables must be recorded also. Following are some typical sensors, which are used
for different variables measurements [14].
• Pressure sensors
74
• Temperature sensors
• Flow rate sensors
• Level sensors
For measuring the temperature, also used for severe purpose some radiation detectors may
also be used.
Gas chromatograph:
It is used for measuring the composition of the steam. A good device for the measurement
depends upon the environment in which it is to be used. Like a thermometer, it is not a good
measuring device, as its signal is not rapidly transmitted. So signal transmission is very
important in selecting the measuring device. So the measuring device must be rugged and
reliable for an industrial environment.
Transducers
Many measurements cannot be used for control until they are converted to physical
quantities such as electric voltage and current a pneumatic signal. For example, stream
gauges are metallic conductors whose resistance changes when mechanical strain is
imposed on it. Thus they can be used to convert a mechanical signal to electric one.
Transmission lines
These are used to carry measurements signal from measuring device to the controller. In
the past, mostly transmission lines were pneumatic nature that they are using the
compressed air or liquid to transmit the signal but with the automation of industry and
advent of electronic controllers, electric lines have over-ruled the pneumatic operations,
75
many times the measurements coming from a device are very weak and these must be
amplified to get the things right. So it is very often to find amplifies in the transmission
lines to the controller. For example the output of a thermocouple is only a few milli-volts
so they must be amplified to few volts to get the controller.
7.2 Controller:
This is hardware element that has “intelligence”. It receives the information from the
measuring device and decides what action must be carried out. The older controllers were
controller limited intelligence, could perform very limited and simple operations and could
implement very simple control laws. The use of digital computers in this field has increased
the use of complication control laws.
The final control element: this is the hardware element that implements the decision taken
by the controller. For example, if the controller decides that flow rate of the outlets stream
should be increased or decreased in order to keep the level of the liquid in a tank then the
final control element which is a control value in this case implements the decision by
slightly opening or closing the value.
Modes of control
There are various modes in which the process can be controlled. The different Modes
depend upon the types of controllers and the action it takes to control any process variable.
Actually the controller action is dependent on the output signal of the transmitter (sensor
with transducer) used to control the process. Different controllers react in different manner
to control this off-set between the controlled variable and the set point.
On the prescribed basis, following are the different types of control actions.
• On-off control
• Proportional control
• Integral control
• Rate or derivative control
• Composite control
Also there are combined control actions of different types of controllers. Actually in
different operations, it is very rare that only one of the above control actions is found but a
76
composite control action is the more often practice. Following are typical composite control
modes, which are usually used.
Characteristics of controller
• Pneumatic controllers
• Electronic controllers
• Hydraulic controllers
While dealing with the gases, the controller and the final control element may be
pneumatically operated due to the following reasons,
1. The pneumatic controller is very rugged and almost free of maintenance. The
pneumatic equipment is simple.
2. Pneumatic controller appears to be safer in a potentially explosive atmosphere
which is often present in the industry.
3. Transmissions distances are short pneumatic and electronic transmissions system
are generally equal up to about 200 to 300 feet. Above this distance electronic
system beings to offer savings.
Actually in industry, only P, PI, and PID control modes are the usual practice. The selection
of most appropriate type of controller for any particular environment is a very systematic
procedure. There are many ways and means that how a particular type of system may be
controlled through which type of controller. Usually type of controller is selected using
only quantitative considerations stemming from the analysis of the system and ending at
the properties of that particular controller and the control objective. Proportional, integral
and derivative control modes also affect the response of the system. Following is the
summarized criterion to select the appropriate controller for any process depending upon
the detailed study of the controller and control variable along with process severity.
77
Simple P-controller can be used if we can achieve acceptable off-set with not too high
values of gain. So for gas pressure and liquid level control, usually a simple proportional
controller may be used.
A steady-state error always remains for proportional controller so in systems where this off-set
is to be minimizes, a PI-controller is incorporated. So in flow control applications, usually PI-
controller is found.
3. Used a PID-controller to increase the speed of the closed loop response and
retain robustness:
The anticipatory characteristic of the derivative control enables to use somewhat higher values
of proportional gains so that off-set is minimized with lesser deviations and good response of
the system. Also it adds the stability to the system. So this type of control is used for sluggish
multiline short best controller is selected on following basis;
I. Severity of process
II. Accuracy required
III. Cost
For instrumentation and control of different sections and equipment’s of plants, following
control loop are most often used.
A method of control in which a measured value of a process variable is compared with the
desired value of the process variable and any necessary action is taken. Feedback Control is
considered as the basic control loop system. Its disadvantage lies in its operational procedure,
for example if a certain quantity is entering in a process, then a monitor will be there at the
process to note its value. Any changes from the set point will be sent to the final control element
through the controller so that to adjust the incoming quantity according to desired value (set
point). But in fact change has already occurred and only corrective action can be taken while
using feedback-control system.
This is a control method designed to prevent errors from occurring in a process variable. This
control system is better than feedback control because it anticipates the change in the process
variable before it enters the process takes the preventive action. While in feedback enter system
action is taken after the change has occurred.
2. Ration control
A control loop in which, the controlling element maintains a predetermined ratio of one
variable to another. Usually this control loop is attached to such as system where two different
streams. Enter a vessel for reaction that may be of any kind. To maintain the stoichiometric
quantities of different streams this loop is used so that to ensure proper process going on in the
process vessel.
This type of control loop is normally used for a huge vessel where, reading of a single variable
may be different at different locations. This type of control loop ensures safe operation because
it employs all the readings of different locations simultaneously, and compares them with the
set point, if any of those readings is deviating from the set point then the controller sends
appropriate signal to final control elements.
79
In this loop controller is per set with different values corresponding to different action to be
taken at different conditions. The advantage of this loop is to maintain the proper conditions
and avoid abnormalities at very differential level.
This is a control in which two or more control loops are arranges so that the output of, one
controlling element adjust the set point of another controlling element. This control loop is
used where proper and quick controls difficult by simple feed forward or feed backward
control. Normally first loop is a feedback control loop. We have selected a cascade control loop
for our heat exchanger in order to get quick on proper control [14].
80
As the ratio of ammonia fed to the pipe reactor to that fed to granulator is 1.9 : 1, so ratio
controller will be applied on the NH3 stream coming from storage.
81
As the ratio of H3PO4 fed to the reactor and to that of scrubber is 1.7 : 1, so ratio controller will
also do the job here, as follows. [14].
82
The flow of liquid NH3 and H3PO4 to the pipe reactor is controlled by a ratio controller. The
pipelines for these materials are also equipped with flow indicator. The flow valve is controlled
by a controller which maintains the desired ratio of 1.45 : 1 (NH3 : H3PO4) to provide the
conditions of maximum solubility. [14].
83
The ratio controller is applied to maintain the ratio of 1:1 of slurry:NH3 sparges. [14].
84
The pipe reactor is equipped with a temperature transmitter and pressure transmitter mounted
on the panel. The cold slurry coming from the scrubber controls the temperature in pipe reactor
i.e. 150°C. A flow valve controls the flows of scrubber slurry from tank. The pressure indicator
is used to record any significant change in pressure in the pipe reactor. As an increase in
temperature will give rise to an increase in pressure. Thus pressure will in turn reduce the flow
of NH3 and H3PO4 which reduce the temperature and pressure.
85
The temperature in the granulator is maintained at 95°C in the granulator by the following
instrumentation [14].
86
87
CHAPTER 8
Cost Estimation
Where:
1 $ = 104.83 PKR
= 1081364 (3.15)
= 3406296 $
= 3406296 (1.40)
89
= 4768815$
= 238440 $
= 238440 + 4768815
= 5007255 $
Fixed Cost:
= 0.05 x 4768815
Variable Cost:
= 0.10 x 238440
Raw Material:
1. Ammonia (NH3) Cost = Flow Rate x Operating time x Cost per ton
= 475 x 347 x 545
= 89829625 $ per year
2. Phosphoric Acid Cost = Flow Rate x Operating time x Cost per ton
Utilities Cost:
1. Total Electricity Cost = 0.037 $ per KWh
91
= 359437769 + 906073
= 360343842 / 520500
= 0.692 $ per Kg
1$ = 104.83 PKR
= PKR 2900
92
CHAPTER 9
Selecting an appropriate site for the plant is a critical factor in determining its profitability and
success. Several factors must be taken into account when selecting a site for the plant. These
factors are as follows:
• Societal consideration
• Raw material availability
• Property cost
• Taxation
• Labor availability
• Energy availability and cost
• Transportation accessibility
• Environmental permit
• Living conditions
The most primary factor in determining the suitability of a region for the eraction of plant is
the social and cultural trends of the area. Many societies do not easily accept industrial
development. They might consider it a threat to their peaceful environment some societies
resist the presence of people from other regions because they feel that their Cultural norms
might be endangered due to the presence of people from other cultures. In some areas where
agriculture is the main source of livelihood, people might not be easily convinced to sell their
lands.
93
The raw material must be easily available. The plant must be locational near the industries that
produced ammonia and phosphoric acid. If the phosphoric acid and ammonia is also produced
with in the same industry, then it should be located where phosphate rock and natural gas is
present at a lower cost of extraction or purchase.
The cost of land is important in determining the overall investment for the plant. Plant must
generally be located away from residential areas because the land price is generally high there.
Industrial areas or remote areas near the raw materials are preferable locations.
9.1.4 Taxation:
The tax rates vary from region to region. Different tad patterns must be studied before taking
the final step of deciding the region because it is a lifelong commitment with the authorities.
Unstable political conditions may also be a discourage factor as new government might revise
the tax rates. Industrial zones and tax free zones are more preferable areas to set up any
industry.
Labor force is considered to be the “wheels” of an industry. It is important for the plant to be
located in such an area where the availability of both skilled and unskilled labor of the industry.
It is preferable to set up the industry in the vicinity of another similar industry it adds to the
ease of finding skilled labor and also might cut down the extra expense that might be incurred
in training the unskilled.
The electricity and gas facilities should be available and at a reasonable cost. These facilities
are generally available at discounted rate in the industrial zones. If the plant must be located in
94
some place where electricity is not available then alternative power production options must
be carefully looked upon before taking the final decision.
95
For a competent product price, the industry must be located near highways or ports as it is
easier to get raw-materials and products transported in and out of the industry. The location
must also be close to the market in order to save transportation expenses and time.
An environmental based line is usually required to establish how the plant would affect the
surroundings. Air quality issues can be the deciding factor in sitting. As air permits often take
the most time to obtain. Water pollution also needs to be addressed. Federal, state and regional
regulations are often in conflict with each other. Hiring a consultant to steer a way through this
compels myrid of regulations can be useful. What the environmental discharges are and how
best to mitigate their effects by providing a plant that this design to minimize the impact are
key issues.
The facilities and environment that could be offered in the industry might be a factor to attract
skilled personnel and members of higher management to come to remote locations. So while
selecting the location it is important to take into considerations the ability of the region to
support such environment and facilities, like schools, clubs, etc. these things are a vital for the
growth of the industry.
The environmental problems that different countries have to face vary with their stage of
development, the structure of their economies and their environmental plies.
The standards imposed by industrial economies may set reasonable along term goals but
developing countries like Pakistan rarely have the means to adopt them immediately. Instead
each country must determine its own priorities. However the main body of this chapter deals
with the regulatory control established by the environmental laws.
96
Major Effluent from the pant using phosphoric acid and ammonia as a raw material from the
production of DAP may include.
• Fluoride
• Ammonia
• DAP dust
• Water
Fluoride emission is a major concern of both the Industry and the environmental protection
agencies use to the nature of the chemistry involved in the preparation of phosphoric acid and
the DAP fertilizer. Although not classified as endangering public health, fluoride emissions
have been designed as well as fare related pollutant. The evolution of fluoride from the
manufacture of mono ammonium phosphate (MAO) and Diammonium phosphate (DAP) is
dependent upon the fluoride of phosphoric acid.
In the case of MAP and DAP operation the major sources of fluoride and ammonia emission
are the reactors and the granulators. Since fluoride emissions are considered to be welfare
rather than health related.
Environmental laws allow applying less stringent requirements for the existing regulated
facility. Considerable flexibility resists in weighing factors such as economic conditions,
physical constraints, technical feasibility and environmental impact on the surrounding
community. Flexibility allowed for granular DAP plant is 0.060 lbs of fluoride/ton of P2O5.
Since 1979 there have been no significant improvements in fluoride removal efficiencies by
scrubbing or the demonstration of emerging technologies for fluoride control. In order to
determine the type of equipment most suitable for fluoride control, the nature of emissions
must be first examined.
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9.1.12 Ammonia:
Ammonia is a colorless, alkaline gas, is lighter than air and possesses a unique pungent order.
The flue gasses from the reactor and granulator contain unreacted ammonia. This is recovered
from the flue vapors in the scrubber by absorbing in phosphoric acid. Despite these protective
measures some of it escapes into the environment. Ammonia can also leak through pipes and
equipment and could be hazardous to the health of the workers, as it is rapidly carried to long
distances by air. Any detectable release of ammonia can be absorbed by spraying water over
the leakage site in order to prevent an accident while the problem is being worked on.
In the DAP plant the DAP dust procedure from the cooler and screening and crushing
equipment can be of serious concern. These particles can cause respiratory and other health
related problem. The control of particulate sources from screening crushing can be handled by
bad houses, while those from cooler can be handled by cyclone separators.
Environmental control in the phosphatic fertilizer industry is more complex than just scrubbing
air and gaseous emissions. The scrubber water, used to efficiently clean the air being discharge
via the stacks, must now meet the standards of discharge promulgated under the clean water
act.
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CHAPTER 10
HAZOP ANALYSIS
10.1 Introduction:
The objective of HAZOP study is to provide safety, health and care to all the man power
working in the plant and to provide maintenance and safety to the plant by reducing risk of the
accident.
1. Face shield and gloves should be worn because every time there is a danger of coming
in contact with a corrosive liquid.
2. Be prepared for any condition that would prove hazardous to personnel or equipment
should be kept.
3. High-pressure leaks should be reported immediately.
4. If any chemical spill occurs, clean the area of any source of ignition and wash down the
area slowly with water to minimize vaporization.
5. Operators should be aware of location of emergency and safety equipment.
6. Operators should be aware of all the toxic, corrosive and flammable materials used in
the process.
7. Firefighting equipment should not be tampered with.
8. Access to ladders, escapes, safety showers, eyewash stations and air mask stations must
be kept clear. Waste material and refuses must be kept in proper locations where they
will not cause fire.
9. If any safety equipment is not working properly, it should be reported and set right.
10. No smoking is allowed in the plant or its vicinity.
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Any acceptable design must contain the minimization of building and equipment hazards such
as corrosion, fire explosion and hazards caused due to fumes and poisonous materials. Special
care should be given to the disposal of waste material. Elimination of process leakage and
spillage hazards due to corrosion and other factors should be paid extra attention.
Lights:
Proper light arrangements should be made to facilitate the movement and working of personnel
and minimizing the risk of tripping over pipes.
Electrical and mechanical hazards should be minimized. Every machine should be equipped
with proper safety guards. Poor and faulty wiring, overloaded circuits and improperly loaded
circuits should not be used.
Chemical Hazards:
Special care should be given to avoid any exposure to sulfuric acid and phosphoric acid. Most
reliable manuals for safety are chemical safety data sheet compiled by manufacturing chemist’s
association. These manuals discuss the safe handling of most hazardous chemicals while also
providing drawing, data tables and graphs.
Personnel Safety:
Special equipment such as safety goggles, gloves and ear muffs should be provided to the
personnel so they can enhance their performance in a safe and healthy environment.
100
In TVA granular process it is acid base reaction. So safety should be kept in mind. High
pressure and temperature streams are major concern for the safety purposes. Special procedures
are used to avoid contact with sulfuric acid and phosphoric acid.
➢ Sulfuric acid cause rapid damage to human beings which cause serious consequences.
Fumes of sulfuric acid cause serious damage to the respiratory system.
➢ Liquid or spray mist may produce tissue damage particularly on mucous membranes of
eyes. Skin contact may produce burns. Severe over exposure causes death
.Inflammation of eyes is characterized by redness.
➢ Phosphoric acid in case of skin contact or eye contact is very hazardous. Liquid or spray
mist may produce tissue damage particularly on mucous membranes of eye. Mouth and
respiratory tract. Severe over exposure can result in death.
➢ In case of eye contact immediately flush eyes with the plenty of water for at least for
15 minutes.in case of skin contact flush skin with plenty of water for at least 15 minutes.
Wash with soap or antibacterial cream.
➢ Ammonia is a flammable gas. If it is heated it May explode.it is very toxic if it is inhaled
and also very toxic for aquatic life.
➢ Do not expose to eyes use and store only outdoors or in well ventilated place. Eliminate
all ignition sources it is safe to do .wear protective gloves and protective clothing to
handle it properly.
➢ If it is inhaled take victim to the uncontaminated breathing atmosphere .keep victim
warm and rested.in case of physical contact flush affected area for the plenty of water
for 15 minutes.
➢ Protective Equipment should be used during the following procedures.
• Manufacture or formation of product.
• Repair and maintenance of contaminated equipment.
• Cleanup of leaks.
• Any situation resulting in hazardous exposure.
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Table: Material safety information for chemicals and materials used in process.
Health hazard Irritation to skin and Irritation to skin and Severely corrosive to
eyes. Very toxic when eyes very toxic when eyes, skin and lungs.
fumes inhaled. fumes inhaled.
Exposure Eye and skin contact, Eye and skin contact, Eye and skin contact,
inhalation, ingestion. inhalation, ingestion. inhalation, ingestion.
First Aid Exposed area Flush Expose skin area Exposed area kept
with water for 15 Wash with water. warm and inhalation
minutes. Inhalation: Inhalation: Get to victim will kept under
Seek medical fresh air. Ingestion: supervision for 48
attention Drink water. hours
Study Node:
Process Parameters:
• Flow
Process Parameter:
• Reaction
Process Parameter:
• Temperature
Study Node:
• Reactor wall
Process Parameter:
• Pressure
Study Node:
• Scrubber
Process parameter:
• Temperature
Storage vessel is used for the storage of phosphoric acid and sulfuric acid.
Study Node:
• Vessel
Process Parameter:
• Pressure
Study Node:
• Granulator
Process Parameter:
References:
1. http://www.pakinvestorsguide.com/index.php?topic=151.45;wap2
2. Kenneth J. Jardine, V.V.A., Method for producing fertilizer grade DAP having an
increased nitrogen concentration from recycle. Jun 5, 2001.
3. Byron R. Parker, B.W.C., Diammonium phosphate produced with a high-pressure
pipe reactor. Jul 19, 1988.
4. Max Appl, Dannstadt-Schauernheim, Federal Republic of Germany, Ammonia
5. Ammonia Synthesis Catalysts: Innovation and Practice, Huazhang Liu
6. Chemical Engineering Design Coulson and Richardson Vol # 06
7. Method for producing fertilizer grade DAP having an increased nitrogen
concentration from recycle, Kenneth J. Jardine, Vaughn V. Astley,Jun 5, 2001
8. Catalytic Ammonia Synthesis : Fundamentals and Practice
9. William D. Fairchild, Process for producing granular diammonium phosphate
10. Byron R. Parker, Barry W. Curtis, Diammonium phosphate produced with a high-
pressure pipe reactor, Jul 19, 1988
11. Plant Design and Economics for chemical engineers, 5th Edition by Max S peter
and Klaus.D.Timmerhause.
12. Introduction to chemical engineering thermodynamics,6th edition by J.M.Smith
13. Fertilizer Manual by UNIDO Fertilizer Manual published in DEC, 1979
14. Fertilizer manual by neilson.
15. Fertilizer Encyclopedia by Vasant Gowariker
16. Chemical Process Control, by GEORGE STEPHANOPOULOS
17. Elements of Chemical Reaction Engineering, 4th Edition, by H.SCOTT.FOGLER
18. Chemical Reaction Engineering by Octave Leven Spiel, 3rd Edition
19. Fertilizer ammonium phosphate by jhon L.chadwick Manlo park California.94025
20. US4619684Production of diammonium phosphate by pressure reactor by tense
valley authority.