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Good morning everyone! I will be discussing the phosphorus industries.

And the title for my presentation


is URINE FOR A TREAT. So why URINE for a treat?!

So to know why Urine for a treat is the title for my presentation, let’s start the discussion with the brief
history of phosphorus. In 1669, Brandt discovered phosphorus by evaporating urine and heating the
residue until it emitted phosphorus vapor, which he collected by condensing it in water. He kept his
discovery a secret because he thought he discovered the Philosopher’s stone but He eventually sold to it
to Daniel Kraft, who in turn showed it to Boyle. Robert Boyle was fascinated and decided to study
phosphorus along with his assistant, Godfrey. When Boyle lost interest, Godfrey took over, and
established a successful commercial production of phosphorus and even exporting to Europe.
However, before the discovery of phosphorus in 1669, the use of phosphatic materials as fertilizers was
already in practice. Carthaginians in 200 B.C. utilized bird dung, the Incas of Peru valued guano to the
extent of making it a capital offense to harm birds, and American Indians employed fish and bones in
their agricultural methods. Until the mid-nineteenth century, bones and guano were the primary sources of
phosphorus.
a British patent by John B. Lawes marked the start of the acid phosphate industry, which later became the
foundation of the domestic fertilizer industry. Subsequently, phosphate ores were discovered in England,
initially applied directly to the soil but later treated with sulfuric acid for increased efficiency.
It started when phosphate ores were discovered in England and John B Lawes decided to treat it with
sulfuric acid to produce superphosphate which was the first commercial fertilizer.

The fundamental raw material for the phosphorus industry is the phosphate rock, existing in nature as
the mineral apatite. This mineral serves as the primary source for elemental phosphorus and other
phosphorus-derived materials. It is categorized into three grades based on it %P2O5 content: low-grade if
it contains 12-16% of P2O5, medium-grade if it contains 17-25%, and high-grade if it contains 26-35%
P2O5.
Global assessments indicate that the main regions holding the bulk of estimated natural phosphorus
reserves are Morocco and Western Sahara, constituting about 73%, with China at 4%, and Russia,
Jordan, and the US each at 2%.
Based on this assessment, we can already guess that when it comes to acquiring phosphate rock,
Philippines usually imports instead of mine phosphate rock

Phosphorus is usually categorized into two kinds; white/yellow phosphorus and red phosphorus.
Yellow/white phosphorus is a waxy solid and appears white in color but turns yellow upon exposure to
light. It has a garlic-like odor and is poisonous. It has a tetrahedral structure with a chemical composition
P4. it is highly reactive and immediately ignites upon contact with air that’s why it must be stored
underwater to prevent spontaneous ignition in air.
Red phosphorus shares a chemical composition of P4 and a tetrahedral structure with white or yellow
phosphorus; however, it undergoes polymerization. Unlike its waxy counterpart, red phosphorus
manifests as a hard crystalline material with a high degree of oxidation resistance and stability. It is red in
color and unlike yellow/white phosphorus, it is odorless and non-poisonous. It also has a lower reactivity,
and this is attributed to its polymeric nature.

In the global context, it was reported in de boer’s 2019 study that 85% of phosphates produced for the
market are processed into mineral P fertilizers. The phosphorus industry is closely linked with
fertilizer planning and production that it is growing concurrently with the nitrogen and potassium industry
due to its crucial role in fertilizer plants.
It is also important to note that in a fully developed phosphate industry, the typical practice involves
converting white or yellow phosphorus into red phosphorus and/or other necessary chemicals. It is
uncommon to find a phosphorus industry solely dedicated to the production of white or yellow
phosphorus.

There are two examples of Phosphorus Industries in the Philippines. The Philphos and AFC
The Philippine Phosphate Fertilizer Corporation is engaged in the manufacturing and distribution of
agricultural fertilizers. The company specializes in producing phosphatic fertilizers, which it markets
through wholesalers and retailers across the Philippines, Vietnam, Thailand, and Indonesia.
Atlas Fertilizer Corporation. the oldest and the pioneering fertilizer company in the Philippines to
successfully implement full-scale manufacturing of a comprehensive range of mixed fertilizer grades,
commonly referred to as compound inorganic fertilizer and popularly known among farmers as NP-NPK-
NK fertilizers. In this context, N represents Nitrogen, P signifies Phosphorus, and K denotes Potassium—
essential elements that plants need to meet their nutrient demands throughout various growth stages, from
maturity to harvest.
From what I said earlier, the lack of a domestic phosphate rock source in the Philippines necessitates
the importation of raw materials for fertilizer production. According to Volza's Global Export data,
The Philippine Phosphate Fertilizer Corporation (Philphos) held the highest market share in rock
phosphate imports, with 286 shipments.

Now, let’s go over the production of elemental phosphorus by electric furnace method. In the initial
reaction, calcium phosphate undergoes a reaction with carbon and silica, resulting in the formation of
yellow/white elemental phosphorus, calcium silicate, and carbon monoxide. Red phosphorus can be
obtained by subjecting yellow/white phosphorus to heat for a few hours.
The raw materials include crushed phosphate rock, coke as a reductant, and sand as flux.
The process begins with crushing fluorapatite or phosphate rock into grinders. The crushed phosphate
rock is then mixed with coke breeze and subjected to sintering and sizing. Based on the phosphate rock
analysis, the appropriate quantities of coke breeze and sand are added to the sintered material and the
resulting mixture is sent to an electric furnace for product conversion.
In the electric furnace, the overhead product contains P4 and CO vapors, along with some dust, while the
bottom product comprises slag, which is a valuable byproduct. This slag often contains ferrophosphorus,
which is recovered due to its potential use in road-bed gravel, soil liming, and glass manufacturing. The
electric furnace is maintained at a slight vacuum by fans in the downstream end to facilitate the
movement of furnace gases (P4, CO, and dust) towards the electrostatic precipitator. Here, dust is
removed, and the P4 and CO proceed to a condenser with water spraying.
In the condenser, the P4 is cooled, and the resulting liquid yellow phosphorus is collected as the
condenser's bottom product, stored under water for safety precautions. The non-condensed CO serves as
the overhead product and can be recycled for use as fuel or synthesis gas.
To obtain red phosphorus, yellow phosphorus is introduced into a covered batch converter, which
operates at a specific temperature, typically 250 degrees Celsius or higher, for a predetermined duration.
The converter is equipped with a total reflux condenser to prevent the escape of any P4 vapor. Following
the conversion from yellow to red phosphorus, the material undergoes solidification. The solidified
substance is cooled, chipped out, and subjected to washing with an aqueous sodium carbonate (Na2CO3)
solution, followed by a water wash to eliminate residual solution. The final product is then transferred to a
dryer, where stabilization is achieved with magnesium oxide dust.
Historically, white phosphorus has been utilized in military applications such as smoke screens and
incendiary devices, along with applications in the chemical industry for producing phosphoric acid, while
red phosphorus is found in the material on matchboxes used for striking safety matches. Red
phosphorus is also found

Next would be, the production of phosphoric acid by electric furnace method. Phosphate rock reacts
with carbon and silica to yield elemental phosphorus, calcium silicate, and carbon monoxide. Following
this, phosphorus and carbon monoxide react with oxygen to form phosphorus pentoxide and carbon
dioxide. Finally, phosphorus pentoxide undergoes further reaction with water to generate phosphoric acid.
Raw materials include phosphate rock, coke as reductant, and sand as flux.
The first three process; the sintering and sizing of phosphate rock, the production of elemental
phosphorus, and the separation of waste; is the same as the previous discussion about the production of
elemental phosphorus. Now, instead of your elemental phosphorus directly going into the condenser, it
will first undergo a combustion process to yield a P2O5 and carbon dioxide.
the product undergoes hydration with water to yield potent phosphoric acid, while the remaining vapor is
subjected to an electrostatic precipitator to eliminate carbon dioxide and procure the remaining
phosphoric acid. the resultant phosphoric acid undergoes a purification process dependent on the specific
impurities present. The application of sulfuric acid is employed for the precipitation of calcium values and
the recovery of phosphoric acid. In instances where arsenic is present, treatment with hydrogen sulfide is
deemed necessary. For phosphoric acid containing fluorides, purification is achieved through the
utilization of powdered silica.

production of phosphoric acid by wet process. Calcium phosphate reacts with strong sulfuric acid and
water to yield phosphoric acid and gypsum.
Raw materials include phosphate rock, strong sulfuric acid, and water. High grade phosphate rock is
recommended to avoid solubilization of mine rock impurities and around 93% - 98% sulfuric acid is
recommended to make the strongest phosphoric acid possible and to decrease evaporation costs.
Following a sequence of operations involving drying and crushing, the phosphate rock is systematically
introduced into the reactor alongside sulfuric acid and recycled phosphoric acid. To regulate the
exothermic nature of the reaction, precise control of the reactor's temperature is achieved through the
utilization of circulating cooling air. Subsequently, the resulting products—gypsum and phosphoric acid
—are conveyed to a traveling pan filter where the filtrate, phosphoric acid, is removed and evaporated in
a single effect evaporator to increase its concentration for more than 50 percent. It will then be stored for
further use. The slurry obtained in the filtration process is washed with hot water to remove residual
traces of phosphoric acid or other unreacted sulfuric acid. These acids will be recycled back into the
reactor. The remaining washed gypsum will be taken as a product and used for other processes.

The phosphoric acid obtained is then used in the production of a series of liquid or solid fertilizers.
The most important are single and triple superphosphates (SSP, TSP) and ammonium phosphates (MAP,
DAP), and superphosphoric acid.
Based on the diagram; Single Superphosphate is made by mixing natural phosphate rock with sulfuric
acid while triple superphosphate is made by mixing natural phosphate rock with phosphoric acid.
Mono- and di-ammonium phosphate, collectively known as ammoniated phosphates, are created by
introducing ammonia—whether in liquid or gaseous form—into weak phosphoric acid. This production
process results in MAP and DAP, recognized as the world's most widely used phosphorus fertilizer. These
fertilizers are composed of two constituents commonly found in the fertilizer industry
Superphosphoric acid is made by removing water from phosphoric acid, thereby increasing its
phosphoric acid concentration.

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