FACULTY OF ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

BY

Tahir swar tahir

SUPERVISOR

Mr.Ali Hosin Alibag

JUN / 2020
Contents
1.1 INTRODUCTION ................................................................................................................................. 2
1.2 Forms ................................................................................................................................................ 3
1.3 Inorganic commercial fertilizer .......................................................................................................... 3
1.3.1 Controlled-release types ................................................................................................................. 4
1.3.2 Application ..................................................................................................................................... 5
1.3.3 Problems with inorganic fertilizer ................................................................................................... 6
1.3.3.1 Water pollution........................................................................................................................ 6
1.3.3.2 Contamination with impurities ................................................................................................. 6
1.3.3.3 Fertilizer dependency............................................................................................................... 7
1.3.3.4 Soil acidification ....................................................................................................................... 8
1.3.3.5 Trace mineral depletion ........................................................................................................... 8
1.3.3.6 High energy consumption ........................................................................................................ 9
1.3.3.7 Contribution to climate change ................................................................................................ 9
1.3.3.8 Impacts on mycorrhizas ........................................................................................................... 9
1.3.3.9 Lack of long-term sustainability ................................................................................................ 9
1.4 Organic fertilizer .............................................................................................................................. 10
1.4.1 Comparison with inorganic fertilizer.......................................................................................... 10
1.4.1 Examples of organic fertilizer .................................................................................................... 11
CHAPTER TWO ...................................................................................................................................... 13
2.1 Explain the Methods of production of ammonium chloride.............................................................. 13
2.2 Properties ........................................................................................................................................ 13
2.3 Manufacture .................................................................................................................................... 13
2.3.1 Direct reaction ......................................................................................................................... 13
2.3.2 Duel salt process ....................................................................................................................... 14
2.4 Advantages ...................................................................................................................................... 14
2.5 Disadvantages ................................................................................................................................. 14
2.6 USES ................................................................................................................................................ 16
References ........................................................................................................................................ 16

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1.1 INTRODUCTION
Fertilizers are chemicals given to plants with the intention of promoting growth; they are usually
applied either via the soil or by foliar spraying.

Fertilizers typically provide, in varying proportions, the three major plant

nutrients (nitrogen, phosphorus, and potassium), the secondary plant
nutrients (calcium, sulfur, magnesium), and sometimes trace elements (or micronutrients) with a
role in plant nutrition: boron, manganese, iron, zinc,copper and molybdenum.

The three primary ingredients of fertilizers are listed on the fertilizer bags as
nitrogen, phosphate and potash as three numbers, indicating the ratios in that order. Thus a 5-10-
5 fertilizer would have 10 per cent phosphate in its ingredients.

Manure was once the dominant fertilizer, and is still used, but its role is greatly diminished.
Fertilizer can be created either from natural organic material such as manure or compost (see
also organic gardening), or artificially as through the Haber-Bosch process which
produces ammonia. This ammonia is used to produce nitric acid. A reaction product of ammonia
and nitric acid already gives Ammonium nitrate which is a fertilizer product. The nitric acid and
ammonia also can be used in the Odda Process to produce compound fertilizers such as 15-15-
15.

The Haber-Bosch process uses about one percent of the Earth's total energy supply in order to
provide half of the nitrogen needed in agriculture. Organic material has the advantage of adding
carbon compounds to the soil. A major source of soil fertility is the decomposing crop residue
from prior years, though this is not considered "fertilizer."

Justus von Liebig wrote in 1840 the law of the minimum required by the plant.

Over-use of fertilizer can lead to algal blooms in lakes and streams that receive run-off from crop
lands, and lead to long-term degradation of the soil; see in this
regard eutrophication and nutrients. For these reasons, it is recommended that knowledge of the
nutrient requirements of the soil vis-a-visthe crop precede applications of commercial fertilizer.

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In short, excess nutrient elements can cause local soil and off-site damage, as well as waste
money.

1.2 Forms
Fertilizers come in various forms. The most typical form is solid fertilizer in granulated or
powdered forms. The next most common form is liquid fertilizer; some advantages of liquid
fertilizer are its immediate effect and wide coverage.

There are also slow-release fertilizers (various forms including fertilizer spikes, tabs, etc.) which
reduce the problem of "burning" the plants due to excess nitrogen. Polymer coating of fertilizer
ingredients gives tablets and spikes a 'true time-release' or 'staged nutrient release' (SNR) of
fertilizer nutrients.

More recently, organic fertilizer is on the rise as people are resorting to environmental
friendly (or 'green') products. Although organic fertilizers usually contain a lower concentration
of nutrients, this lower concentration avoids complication of nitrogen burn harming the plants. In
addition, organic fertilizers such as compost and worm castings break down slowly into complex
organic structures (humus) which build the soil's structure and moisture- and nutrient-retaining
capabilities.

1.3 Inorganic commercial fertilizer

Fertilizers are broadly divided into organic fertilizers (composed of organic plant or animal
matter), or inorganic or commercial fertilizers. Plants can only absorb their
required nutrients if they are present in easily dissolved
chemical compounds. Both organic and inorganic
fertilizers provide the same needed chemical
compounds. Organic fertilizers provided other macro
and micro plant nutrients and are released as the organic
matter decays—this may take months or years. Organic
fertilizers nearly always have much lower concentrations of plant nutrients and have the usual
problems of economical collection, treatment, transportation and distribution.

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Inorganic fertilizers nearly always are readily dissolved and unless added have few other macro
and micro plant nutrients. Nearly all nitrogen that plants use is in the form of NH3 or
NO3 compounds. The usable phosphorus compounds are usually in the form of phosphoric acid
(H3PO4) and the potassium (K) is typically in the form of potassium chloride (KCl). In organic
fertilizers nitrogen, phosphorus and potassium compounds are released from the complex organic
compounds as the animal or plant matter decays. In commercial fertilizers the same required
compounds are available in easily dissolved compounds that require no decay—they can be used
almost immediately after water is applied. Inorganic fertilizers are usually much more
concentrated with up to 64% (18-46-0) of their weight being a given plant nutrient, compared to
organic fertilizers that only provide 0.4% or less of their weight as a given plant nutrient.[11]

Nitrogen fertilizers are often made using the Haber-Bosch process (invented about 1915) which
uses natural gas (CH4+) for the hydrogen and nitrogen gas (N2) from the air at an elevated
temperature and pressure in the presence of a catalyst to form ammonia (NH3) as the end
product. This ammonia is used as a feedstock for other nitrogen fertilizers, such as anhydrous
ammonium nitrate (NH4NO3) and urea(CO(NH2)2). These concentrated products may be diluted
with water to form a concentrated liquid fertilizer (e.g. UAN). Deposits of sodium nitrate
(NaNO3) (saltpeter) are also found the Atacama desert in Chileand was one of the original (1830)
nitrogen rich inorganic fertilizers used. It is still mined for fertilizer.

1.3.1 Controlled-release types

Urea and formaldehyde, reacted together to produce sparingly soluble polymers of various
molecular weights, is one of the oldest controlled-nitrogen-release technologies, having been
first produced in 1936 and commercialized in 1955. The early product had 60 percent of the total
nitrogen cold-water-insoluble, and the unreacted (quick release) less than 15%. Methylene ureas
were commercialized in the 1960s and 1970s, having 25 and 60% of the nitrogen cold-water-
insoluble, and unreacted urea nitrogen in the range of 15 to 30%. Isobutylidene diurea, unlike the
methylurea polymers, is a single crystalline solid of relatively uniform properties, with about
90% of the nitrogen water-insoluble.

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In the 1960s, the National Fertilizer Development Center began developing Sulfur-coated urea;
sulfur was used as the principle coating material because of its low cost and its value as a
secondary nutrient.[17]Usually there is another wax or polymer which seals the sulfur; the slow
release properties depend on the degradation of the secondary sealant by soil microbes as well as
mechanical imperfections (cracks, etc.) in the sulfur. They typically provide 6 to 16 weeks of
delayed release in turf applications. When a hard polymer is used as the secondary coating, the
properties are a cross between diffusion-controlled particles and traditional sulfur-coated.

Other coated products use thermoplastics (and sometimes ethylene-vinyl acetate and surfactants,
etc.) to produce diffusion-controlled release of urea or soluble inorganic fertilizers. "Reactive
Layer Coating" can produce thinner, hence cheaper, membrane coatings by applying reactive
monomers simultaneously to the soluble particles. "Multicote" is a process applying layers of
low-cost fatty acid salts with a paraffin topcoat.

1.3.2 Application
Synthetic fertilizers are commonly used for growing all crops, with application rates depending
on the soil fertility, usually as measured by a soil test and according to the particular crop.
Legumes, for example, fix nitrogen from the atmosphere and generally do not require nitrogen
fertilizer.

Studies have shown that application of nitrogen fertilizer on off-season cover crops can increase
the biomass (and subsequent green manure value) of these crops, while having a beneficial effect
on soil nitrogen levels for the main crop planted during the summer season. [19]

Nutrients in soil can be thrown out of balance with high concentrations of fertilizers. The
interconnectedness and complexity of this soil ‘food web’ means any appraisal of soil function
must necessarily take into account interactions with the living communities that exist within the
soil. Stability of the system is reduced by the use of nitrogen-containing fertilizers, which
cause soil acidification.

Applying excessive amounts of fertilizer has negative environmental effects, and wastes the
growers' time and money. To avoid over-application, the nutrient status of crops should be
assessed. Nutrient deficiency can be detected by visually assessing the physical symptoms of the
crop. Nitrogen deficiency, for example has a distinctive presentation in some species. However,

5
quantitative tests are more reliable for detecting nutrient deficiency before it has significantly
affected the crop. Both soil tests and Plant Tissue Tests are used in agriculture to fine-tune
nutrient management to the crops needs.

1.3.3 Problems with inorganic fertilizer

1.3.3.1 Water pollution

The nutrients, especially nitrates, in fertilizers can cause problems for natural habitats and for
human health if they are washed off soil into watercourses or leached through soil into
groundwater. In Europe these problems are being addressed by the European Union's Nitrates
Directive.[21] Within Britain farmers are encouraged to manage their land more sustainably in
'catchment-sensitive farming'

1.3.3.2 Contamination with impurities

Common agricultural grade phosphate fertilizers usually contain impurities such as fluorides,
cadmium and uranium, although concentrations of the latter two heavy metals are dependent on
the source of the phosphate and the production process. These potentially harmful impurities can
be removed; however, this significantly increases cost. Highly pure fertilizers are widely
available and perhaps best known as the highly water soluble fertilizers containing blue dyes
used around households. These highly water soluble fertilizers are used in the plant nursery
business and are available in larger packages at
significantly less cost than retail quantities.
There are also some inexpensive retail
granular garden fertilizers made with high
purity ingredients. Oregon and Washington in
U. S. have fertilizer registration programs with
on-line databases listing chemical analyses of
fertilizers. The most widely used inorganic
fertilizer is super-phosphate and its double and triple strengthed derivatives double super and
triple super. Super phosphate was first developed by Lawes at the Rothamstead Agricultural
Research Institute in England in the early 19th Century. [25] Lawes added sulfuric acid to

6
conventional rock phosphate containing the mineral apatite, a calcium fluoro-phosphate. The
resulting water soluble phosphorus was able to significantly improve yields on a variety of crops
at the Rothamstead Centre and the Superphosphate industry was born. Unfortunately over
decades of subsequent usage - it became clear that the solubilisation of fluorine also occurred in
the process and this had the same effect as the other halogen sterilants(chlorine, bromine, iodine)
over time - soil sterilization.

1.3.3.3 Fertilizer dependency

Effectively farmers unknowingly became

100% dependent on 'bought in' water
soluble, inorganic fertilizers since the
sterilization of soil microflora including its
mycorrhiza, reduced the availability of
other natural and trace minerals within the
soil. This to some extent explains the
resurgence of interest in organic and
particularly 'biodynamic' farming systems since these systems replace the essential soil
organisms so essential to converting soil minerals into plant available (but rarely water soluble)
nutrients.[27] They do this by a variety of processes including chelation where by essential
minerals become plant available - as measured by weak citric acid extraction techniques. Hence
the citric acid solubility of phosphate rocks has emerged as a measure of plant availability and
enabled so-called 'reactive' phosphate rocks to be used as fertilizer minerals. These should not be
confused with high fluorine apatite rocks in which the fluoride content performs a similar
function to its role in hardening teeth enamel, i.e. immobilizing phosphorus. This explains the
oceanic origins of many of these high fluorine rocks (Christmas Island, Ocean Island) since the
fluorine absorbed from the sea has prevented what were originally massive deposits of bird
guano - from being leached from the coral based limestone rocks on which they were originally
deposited.

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1.3.3.4 Soil acidification

Also regular use of acidulated fertilizers generally contribute to the accumulation of soil acidity
in soils which progressively increases aluminum availability and hence toxicity. The use of such
acidulated fertilizers in the tropical and semi-tropical regions of Indonesia and Malaysia has
contributed to soil degradation on a large scale
from aluminum toxicity, which can only be
countered by applications of limestone or
preferably magnesian dolomite, which neutralises
acid soil pH and also provides essential
magnesium.

1.3.3.5 Trace mineral depletion

Many inorganic fertilizers, particularly those based on superphosphate, may not replace trace
mineral elements in the soil which become gradually depleted by crops. This depletion has been
linked to studies which have shown a marked fall (up to 75%) in the quantities of such minerals
present in fruit and vegetables.[28] Explanations for this include the early encouragement of so-
called "luxury consumption" of trace elements as a result of their acidulation and subsequent
dissolution in soil water, by free sulphuric acid sourced from superphosphate. This mechanism
has also been identified as a possible causal agent for take-up of the heavy metal cadmium from
superphosphate based fertilizers. In Western Australia deficiencies of zinc, copper, manganese,
iron and molybdenum were identified as limiting the growth of broad-acre crops and pastures in
the 1940s and 1950s.[29] Such nutrients are described as 'rate limiting' nutrients. Soils in Western
Australia are very old, highly weathered and deficient in many of the major nutrients and trace
elements.[29] Since this time these trace elements are routinely added to inorganic fertilizers used
in agriculture in this state.[29]

Many soils around the world are deficient in zinc, leading to deficiency in plants and humans

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1.3.3.6 High energy consumption

In the USA in 2004, 317 billion cubic feet of natural gas was consumed in the
industrial production of ammonia, less than 1.5% of total U.S. annual consumption of natural
gas.[34] A 2002 report suggested that the production of ammonia consumes about 5% of global
natural gas consumption, which is somewhat under 2% of world energy production. [

Ammonia is overwhelmingly produced from natural gas, but other energy sources, together with
a hydrogen source such as water (via water splitting or electrolysis), can be used for the
production of nitrogen compounds suitable for fertilizers. The cost of natural gas makes up about
90% of the cost of producing ammonia. The increase in price of natural gases over the past
decade, along with other factors such as increasing demand, have contributed to an increase in
fertilizer price.

1.3.3.7 Contribution to climate change

Nitrogen fertilizer can be converted by soil bacteria to nitrous oxide, a greenhouse gas.

1.3.3.8 Impacts on mycorrhizas

High levels of fertilizer may cause the breakdown of the symbiotic relationships between plant
roots and mycorrhizal fungi.[

1.3.3.9 Lack of long-term sustainability

Inorganic fertilizers are now produced in ways which theoretically cannot be continued
indefinitely by definition as the resources used in their production are non-renewable. Potassium
and phosphorus come from mines (or saline lakes such as the Dead Sea) and such resources are
limited. However, more effective fertilizer utilization practices may decrease present usage from
mines. Improved knowledge of crop production practices can potentially decrease fertilizer usage

9
of P and K without reducing the critical need to improve and increase crop yields. Atmospheric
(unfixed) nitrogen is effectively unlimited (forming over 70% of the atmospheric gases), but this
is not in a form useful to plants. To make nitrogen accessible to plants requires nitrogen
fixation (conversion of atmospheric nitrogen to a plant-accessible form).

Artificial nitrogen fertilizers are typically synthesized using fossil fuels such as natural gas and
coal, which are limited resources. In lieu of converting natural gas to syngas for use in the Haber
process, it is also possible to convert renewable biomass to syngas (or wood gas) to supply the
necessary energy for the process, though the amount of land and resources (ironically often
including fertilizer) necessary for such a project may be prohibitive.

1.4 Organic fertilizer

Organic fertilizers include naturally occurring organic materials, (e.g. chicken
litter, manure, worm castings, compost, seaweed, guano, bone meal) or naturally occurring
mineral deposits (e.g. saltpeter). Poultry litter and cattle manure often create environmental and
disposal problems, making their use as fertilizer beneficial. Bones can be processed into
phosphate-rich bone meal; however, most are simply buried in landfills.

Even if all bones, human, animal and plant wastes were recovered to the extent practical and
used for fertilizer, mineral fertilizers and synthetic nitrogen would still be required to make for
losses to leaching, to the atmosphere, runoff and the losses impractical to recover

1.4.1 Comparison with inorganic fertilizer

Organic fertilizer nutrient content, solubility, and nutrient release rates are typically all lower
than inorganic fertilizers.[50][51] One study[which?] found that over a 140-day period, after
7 leachings:

 Organic fertilizers had released between 25% and 60% of their nitrogen content
 Controlled release fertilizers (CRFs) had a relatively constant rate of release
 Soluble fertilizer released most of its nitrogen content at the first leaching

10
In general, the nutrients in organic fertilizer are both more dilute and also much less readily
available to plants. According to the University of California's integrated pest management
program, all organic fertilizers are classified as 'slow-release' fertilizers, and therefore cannot
cause nitrogen burn.[52]

Organic fertilizers from composts and other sources can be quite variable from one batch to the
next.[53] Without batch testing, amounts of applied nutrient cannot be precisely known.
Nevertheless, one or more studies have shown they are at least as effective as chemical fertilizers
over longer periods of use.

1.4.1 Examples of organic fertilizer

Chicken litter, which consists of chicken manure mixed with sawdust, is an organic fertilizer that
has been shown to better condition soil for harvest than synthesized fertilizer. Researchers at
the Agricultural Research Service (ARS) studied the effects of using chicken litter, an organic
fertilizer, versus synthetic fertilizers on cotton fields, and found that fields fertilized with chicken
litter had a 12% increase in cotton yields over fields fertilized with synthetic fertilizer. In
addition to higher yields, researchers valued commercially sold chicken litter at a $17/ton
premium (to a total valuation of $78/ton) over the traditional valuations of $61/ton due to value
added as a soil conditioner.[55]

Other ARS studies have found that algae used to capture nitrogen and phosphorus runoff from
agricultural fields can not only prevent water contamination of these nutrients, but also can be
used as an organic fertilizer. ARS scientists originally developed the "algal turf scrubber" to
reduce nutrient runoff and increase quality of water flowing into streams, rivers, and lakes. They
found that this nutrient-rich algae, once dried, can be applied to cucumber and corn seedlings and
result in growth comparable to that seen using synthetic fertilizers. [56]

Examples

 Compost
 Rock phosphate
 Bone meal
 Manure
 Alfalfa

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 Wood chips
 Raw Langbeinite
 Cover crops
 Unprocessed natural potassium sulfate
 Rock powder
 Ash[59]
 Blood meal
 Fish meal
 Fish emulsion

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 CHAPTER TWO
MANUFACTURE

2.1 Explain the Methods of production of ammonium chloride

Ammonium chloride (NH4Cl) is white crystalline salt highly soluble in water. Solutions of
ammonium chloride are mildly acidic. Ammonium chloride is used as fertilizer. As a fertilizer,
ammonium chloride has an advantage in that it contains 26% nitrogen, which is higher than that
found in ammonium sulfate (20.5%).

2.2 Properties

 Molecular weight : 53.491gm/mole  Odour : Odourless

 Appearance : White solid,  Melting point : 3380C(decomposes)
hygroscopic  Solubility : Solubility in water,
 Density : 1.527gm/ml alcohol

2.3 Manufacture
Ammonium chloride is manufactured by two processes

1. Direct reaction 2. Duel salt process

NH3+ HCl NH4Cl NH3 + H2O + CO2 NH4HCO3
NH4HCO3 + NaCl NaHCO3 + NH4Cl

2.3.1 Direct reaction

Gaseous ammonia is bubbled into 30 %hydrochloric acid solution in a reactor. The reaction is
controlled by addition of water. The resulting solutions are then reacted with ammonia. The
slurry from the saturator is centrifuged and the crystals are washed with water and dried with
warm air in a manner to that used in ammonium sulfate.

13
2.3.2 Duel salt process

The most widely used process for producing ammonium chloride is the salting out process for
soda ash manufacture or modified Solvay's process. In the process, 30% solution of ammonia is
treated with carbon dioxide in a carbonating tower to form ammonium carbonate. The
ammonium bicarbonate as it is formed reacts with sodium chloride to give sodium bicarbonate
and ammonium chloride. The bicarbonate is separated by filtration, washed and calcined to
produce sodium carbonate.

Handling and storage

Crystalline ammonium chloride is free flowing and non-abrasive and does not have any problem
in handling and storage. As it is susceptible to caking at high humidity and has slightly acidic
reaction, ammonium chloride has to be bagged in HDPE or jute bags lined with polyethylene
film.

2.4 Advantages
 Its low cost, as it is often directly available as a by-product from important industries
such as the Solvay soda industry and potassium sulfate industry

 The fact that it combats certain plant diseases and prevents others

2.5 Disadvantages
 Incompatibility of Cl- ions with the physiology of many plants

 The corrosive action which it exhibits owing to the high degree of hydrolysis that it
undergoes

 Difficult to store as it has tendency to cake.

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15
 2.6 USES
 Used as fertilizer.
 Used to produce low temperatures in cooling baths. Ammonium chloride solutions with
ammonia are used as buffer solution.
 It is an ingredient in fireworks, safety matches and contact explosives.
 Used in a ~5% aqueous solution to work on oil wells with clay swelling problems.
 It is also used as electrolyte in zinc carbon batteries.
 Uses in hair shampoo, in the glue that bonds plywood, and in cleaning products. In hair
shampoo, it is used as a thickening agent in ammonium based surfactant systems, such as
ammonium lauryl sulfate.
 Used in the textile and leather industry in dyeing, tanning, textile printing and to luster
cotton
 It is used as food additive.

References

[1 ] Rao, N. S. Biofertilizers in Agriculture & Forestry. IBH, 1993.

[2] Stocchi, E. Industrial Chemistry. Ellis Horwood, 1990.

[3] Lowrison, George. Fertilizer Technology. John Wiley and Sons, 1989

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