PUPUK FOSFOR

(PHOSPHORUS FERTILIZER)
Terminology:

• Water soluble (larut air) P = pupuk P diekstrak dengan air

• Citrate soluble P = sisa water soluble pupuk P diekstrak
dengan 1 N ammonium citrate
• Available P = water soluble P + citrate soluble P
• Citrate insoluble = pupuk P yang tidak terekstrak dengan
water + citrate.
• Total P = water soluble + citrate soluble + citrate insoluble
• Fertilizer P content is expressed as P2O5 instead of elemental P.
The conversion between % P and % P2O5 is :

• % P= % P2O5 x 0,43
• P2O5 = %P x 2,29
 Source of P Fertilizer
• Rock phosphate (RP) is the primary raw materials for P
fertilizer. Phosphorite, phosphate rock or rock phosphate is a
non-detrital sedimentary rock which contains high amounts
of phosphate bearing minerals such as fluorapatite Ca5(PO4)3F
(CFA) and hydroxyapatite Ca5(PO4)3OH or Ca10(PO4)6(OH)2.
Limestones and mudstones are common phosphate bearing
rocks.
• The major RP deposits are found in the US, Morocco, China
and Russia, representing nearly 70 % of total world
production. RP minerals are apatites [Ca10(PO4)6(X)2], where X
is either F-, OH- or Cl-. Flourapatite [Ca10(PO4)6(F)2], is the most
common RP. RP contains numerous impurities of CO3, Na and
Mg.
1. Rock Phosphate

The most reactive RPs are those containing francolite, a CO3-F

apatite. Afetr several processing and purification steps, RP contains
numerous minor constituents such as CO3, Na, and Mg and variable
amounts of heavy metal impurities including Cd which might be
harmful to human health. Sedimentary RPs are highest in Cd with
level up to 300 mg/kg of P2O5, of which ~ 60 to 80 % can be retained
in P fertilizers. The EU restric Cd to 20 mg/kg of P2O5.

None of the P is water soluble, although the citrate solubility varies

from 5 to 17 % of total P
2. Phosphoric Acid (H3PO4)

Phosphoric Acid (H3PO4), or green or wet-process acid, contains 17-24

% P, and is produced by reacting RP with H2SO4. The reaction also
produces gypsum (CaSO4.2H2O) that can be used as a S and Ca
fertilizer, an amandment for sodic soils, and for other industrial
purposes. H3PO4 can also be made by heating RP in electric furnace
to produce elemental P that is reacted with O2 and H2O to form
H3PO4. H3PO4produced by burning is termed white or furnace acid
and is produced mostly for nonagricultural uses.

Agricultural-grade green acid is used to acidulate RP to make Ca and

NH4 phosphates. It can also be injected in soil or irrigation water,
particularly in alkaline and calcareous area.
• Wet-process phosphoric acid:
[Ca10F2(PO4)2]6 + 10H2SO4 +20H2O10CaSO42H2O + HF +6H3PO4

• Furnace-process phosphoric acid:

1593oC
[Ca3(PO4)2 + 3SiO2 + 5C -------> 3(CaO.SiO2) + P2 + 5CO

Liquid elemental phosphorus (P4) mixed with air and burned

to phosphorus pentoxide (P2O5).
P2O5 + 3H2O  3H3PO4
3. Calcium Phosphate

Ca phosphate fertilizers – single superphosphate,

triplesuperphosphate, and enriched superphosphate – were
once the most important P sources. Unlike H3PO4 and NH4+
phosphate, superphosphate have no aprociable effect on soil pH.

• Single superphosphate (SSP) is the oldest commercially

produced synthetic fertilizer and the most common among
the group of superphosphates. The prefix “super” probably
refers to its superiority over crushed animal bones when it
was first produced in the 1840s.
• Single superphosphate (SSP) is manufactured by reacting
H2SO4 with RP:

[Ca3(PO4)2]3.CaF2] + 7H2SO4  3Ca(H2PO4)2 + 7CaSO4 + 2HF

Rock Phosphate sulfuric acid monocalcium gypsum hydrofluoric
phosphate acid

SSP contains 7 tp 9,5 % P (16 to 22 % P2O5) and is 90 % water

soluble. SSP is an excellent source of P and S (12 % S). A
representative sample of ordinary or normal superphosphate
also contains traces of Mg, Fe, Al, Cu, Mn, Zn and Cl.
• TSP contains 17-23 % of P (44-52% of P2O5) and is produced by
treating RP with H3PO4 :

[Ca3(PO4)2]3.CaF2] + 12H3PO4 + 9H2O  9Ca(H2PO4)2 + CaF2

• Triple superphosphate (TSP) was manufactured to increase

the P content of SSP, although TSP contains < 1 % S. Its high
content of is an advantage because transportation, storage
and handling costs make up a large fraction of total fertilizer
cost.
• Pupuk SP 36 (SNI 02-3769-2005)

 Spesifikasi : Kadar P2O5 total minimal 36%, Kadar P2O5 larut

Asam Sitrat minimal 34%, Kadar P2O5 larut dalam air minimal
30% dan Kadar air maksimal 5%
 Kadar Asam Bebas sebagai H3PO4 maksimal 6%,
 Sifat : tidak higroskopis, mudah larut dalam air, bentuk
butiran, warna abu-abu,
 Kemasan : dalam kantong bercap Kerbau Emas dengan isi 50
kg
4. Ammonium phosphate

Ammonium phosphates are produced by reacting wet-process

H3PO4 with NH3. Monoammonium phosphate (MAP) contains 11-13
% N and 21-24 % P (48 to 55 % P2O5) however the common grade is
(N-P2O5-K2O) = (11-52-0). DAP contains 18-21 % N and 20-23 % P
(46-53 % P2O5), the most common grade is (N-P2O5-K2O) = (18-46-0).

NH3 + H3PO4  NH4H2PO4

Ammonia orthophosphoric acid monoammonium phosphate (MAP)

2 NH3 + H3PO4  (NH4)2HPO4

Ammonia orthophosphoric acid diammonium phosphate (DAP)

3 NH3 + H4P2O7  (NH4)3HPO4

Ammonia pyrophosphoric acid triammonium pyrophosphate
MAP and DAP are granular, water-soluble fertilizers with the
advantage of high nutrient content, which minimizing shipping,
handling, and storage costs. They can be used for formulating solid
fertilizer by bluk blending or in manufacturing suspension fertilizers.
MAP and DAP are also for direct application as starter fertilizers. Row
or seed placement of DAP can cause seedling injury and inhibit root
growth through NH3 produced according to:

(NH4)2HPO4  2NH4+ + HPO42- (pH 8,5)

NH4+ + OH-  NH3 + H2O

These problem are especially common in calcareous or high-pH soils.

Adequate separation of seed and DAP is usually required to eliminate
seedling damage.
Initial soil reaction pH with DAP is about 8,5, which favor NH 3
production, whereas the soil reaction pH with MAP is 3,5.
5. Ammonium polyphosphate
Ammonium polyphosphate (APP) is manufactured by reacting
pyrophosphoric acid H4P2O7 with NH3. Pyrophosphoric acid is
produced from dehydration of wet-process acid. Polyphosphate is
a term used to describe two or more orthophosphate ions
(H2PO4-) combined together with the loss of one H2O molecule
per two H2PO4-. APP is a liquid containing 10 to 15 % N and 15 to
16 P (34 to 37 % P2O5) with about 75 and 25 % of the P present as
polyphosphate and orthophosphate, respectively.

A granular fertilizer, urea-ammonium phosphate (UAP) is

produced by reacting urea with APP. The fertilizer grade is 28-28-
0. UAP can be easily blended with other granular fertilizer.
6. Potassium phosphate

Potassium phosphate product include KH2PO4 and K2HPO4. They

are water soluble and commonly used in the horticulture
industry. Their high P and K content makes them attractive
materials for requiring both P and K. In addition, they are suited
for solanaceuos crops and leafy vegetables that are sensitive to
high level of Cl- associated with KCl. Their low salt index reduces
injury to germinating seeds and to young seedlings when they
are placed in or close to seed row.
7. Bone Phosphate

Bone phosphate is white to grayish material ground to powder

that is light in weight per volume. It is sometimes referred to as
steamed bone meal. Green bones are boiled and steamed at
high pressure for the purpose of removing fats. The removed
fatty materials is used for the manufacture of gelatin and glue.
Bones are then ground for easy handling and distribution.
Steamed bone meal contains 1 – 2 % of N and 22-30 % of P2O5
(10-13 % P). It is similar chemically to Ca3(PO4)2 and is commonly
reffered to as BPL, bone phosphate of lime.
8. Basic slag

Basic slag is an excellent source of P and lime. It contans Mg, Fe,

Mn, and B. Slag is heavy, dark brown powder ground so that 70 %
will pass through a 100 mesh (0,1 mm) sieve and 100 % through a
10 mesh (2 mm) sieve. It is produced by the open-hearth method
in the production of pig iron (crude iron). Phosphorus is removed
from iron ore because its presence weakens the cast of iron
produced. Iron ore and lime are heated in an open heater. It
contains 8 – 12 % of P2O5 , 3-5 % of Ca, and 6-8 % of CaSiO3. Some
chemists consider it a silicate and a phosphate of lime
(CaO)5.P2O5.SiO2]
 Rock Triple Basic Slag Bone
Phosphate Superphos Phosphate
phate