THERMODYNAMIC DEPHOSPHORIZATION DURING

STEEL MAKING
METALURYCALL THERMODYNAMIC

Abrar Muharman

3334131932

Presenter

M. Afrizal Danar Galang P.

3334130800

Presenter

Ismi Pungky Permatasari

3334131932

Reporter

Mursidil Kamil

3334131542

Reporter

Rafa Muadz

3334132038

Reporter

Rhea Werdaningsih

3334131716

Presenter

JURUSAN TEKNIK METALURGI - FAKULTAS TEKNIK

UNIVERSITAS SULTAN AGENG TIRTAYASA
CILEGON BANTEN
2015

CHAPTER I
INDTRODUCTION
1. Steelmaking
Steelmaking is the process for producing steel from iron and ferrous ores
and scrap. In steelmaking, impurities such as nitrogen, silicon, phosphorus,
sulfur and excess carbon are removed from the raw iron, and alloying elements
such as manganese, nickel, chromium and vanadium are added to produce
different grades of steel.
Steelmaking has existed for millennia, but it was not commercialized until
the 19th century. The ancient craft process of steelmaking was the crucible
process. In the 1850s and 1860s, the Bessemer process and the Siemens-Martin
process turned steelmaking into a heavy industry. Today there are two major
commercial processes for making steel, namely basic oxygen steelmaking,
which has liquid pig-iron from the blast furnace and scrap steel as the main
feed materials, and electric arc furnace (EAF) steelmaking, which uses scrap
steel or direct reduced iron (DRI) as the main feed materials.

Figure 1. basic oxygen steelmaking

Figure 2. electric arc furnace (EAF) steelmaking

Modern steelmaking processes can be broken into two categories: primary
and secondary steelmaking. Primary steelmaking involves converting liquid
iron from a blast furnace and steel scrap into steel via basic oxygen
steelmaking or melting scrap steel and direct reduced iron (DRI) in an electric
arc furnace. Secondary steelmaking involves refining of the crude steel before
casting and the various operations are normally carried out in ladles.

A. Primary Steelmaking
Basic oxygen steelmaking is a method of primary steelmaking in
which rich carbon molten pig iron is made into steel. Blowing oxygen
through molten pig iron lowers the carbon content of the alloy and changes
it into steel. Primary steelmaking consists of refining of hot metal or scrap
or hot metal to steel in converter or electric furnace. The objective is to
refine hot metal to the nearly desired chemistry.
Basic oxygen steelmaking (BOS, BOP, BOF, and OSM), also known
as Linz-Donawitz-Verfahren steelmaking or the oxygen converter process.
Basic oxygen steelmaking is a method of primary steelmaking in which rich
carbon molten pig iron is made into steel. Blowing oxygen through molten
pig iron lowers the carbon content of the alloy and changes it into low
carbon steel. The convenrter can be classified by three type :

a) Top blown steelmaking

In converter steelmaking pure oxygen is blown from top through a
water cooled lance fitted with multi hole nozzles. This technology of
refining of hot metal is called top blown steelmaking.
b) Combined top and bottom blowing
In some converters, oxygen is blown from top and bottom and
these processes are called top and bott om blowing, Duplex blowing or
hybrid blowing.
c) Bottom blowing
In some converters oxygen is blown through the bottom and the
process is bottom blown converter. This variant is not popular amongst
steelmakers.

Figure 3. Type of Converter

Oxygen is blown from top and the following reactions occour :

[Fe] + [O]

(FeO)

[C] + [O]

{CO}

[Si] + 2[O]

(SiO2)

[Mn] + [O]

(MnO)

2[P] + 5[O]

(P2O5)

[C] + (FeO)

{CO} + [Fe]

(Fe) + (MnO)

(FeO) + [Mn]

B. SECONDARY STEELMAKING
After the molten metal is tapped into a ladle from converter or EAF it
is often given one or more extra treatment depending upon the grade of steel
required. These further refining stages are collectively known as secondary
steel making and can include ladle stirring with argon, powder or wire
injection, vacuum degassing and ladle arc heating. Some high-grade steels
combine all of these treatments. These processes improve homogenisation
of temperature and composition, allow careful trimming to precise
compositions, remove harmful and unwanted gases such as hydrogen and
reduce elements such as sulphur to very low levels. Secondary steelmaking
in ladles has become an integral part of steelmaking. Ladles have additional
heating facility and are called Ladle furnaces (LF). The objective of
secondary steelmaking is to make the steel of desired chemistry and
cleanliness by performing the following treatments in ladle:
a) To stir the molten steel by purging inert gas through the bottom of the
ladle.
b) To inject slag forming powder either through a lance for further refining.
c) To produce clean steel either by removing inclusions or modify them by
suitable injecting materials.
d) To carry-out deoxidation and degassing.

2. Effect of Phosphorus on The Properties of Carbon Steels

Steel containing phosphorous has some adverse as well as good effects.
Phosphorous has great influence towards the solid solution strengthening of
ferrite. The comportment of a modest quantity of phosphorous can increase the
yield and ultimate strength of mild steel. It also increases the deep drawability
and hardness of steel. Referable to the above advantages such steels are used
for cold forming operation. Phosphorous in steel can also increase corrosion
resistance. On the other hand the harmful effects of phosphorous in steel
include various types ofembrittlement, which reduce the resilience and
malleability. High phosphorous steel melt has low melting point, which
produces crack during continuous casting.
a) Cold shortness in steel
The brittle behavior of steel containing phosphorous, at a
temperature less than recrystallization temperature is called cold shortness.
It is a condition of wrought iron, steel, or other metal, in which the metal,
on account of its brittleness, cannot be worked when cold without fracture
or cracking

at the edges. Phosphorous decreases ductility and hence

increase the tendency of the steel to produce crack during cold working.
b) ductility
When Phosphorous, Manganese or Silicon is added to steel, the
tensile strength of steel increases and elongation decreases. This
relationship is shown in Figure 4 balance between cold formability and
hardness must be maintained to produce high strength formable steel. As
Phosphorous level increases, ductility of steel decreases severely due to
the embrittlement. As expected, the strengthening effect of phosphorus is
accompanied by a concomitant decrease in ductility. For example, Figure 4
shows the relationship between the decrease in elongation and increase in
tensile strength resulting from P, Mn and Si. Thus, phosphorus (and other
strengthening elements) decreases formability so that a balance between
strength and formability must be considered in designing high strength
formable steels.

Figure 4: Decrease in ductility (percent total elongation) with tensile strength for
P, Si and Mn.

c) Strenght
Phosphorus is one of the most potent solid solution strengtheners
of ferrite. Hence, small additions of phosphorus are used to inexpensively
increase the strength of low carbon sheet steel. Figure 5 compares the
change in lower yield strength of carbon steel as a function of alloy
addition for several common elements. Figure 5 show the change in lower
yield point as a function of alloy addition. From the Figure 5 we can
conclude that, small amount of phosphorous can increase yield point by a
large amount. Only Carbon and Nitrogen have a higher strengthening
effect than phosphorous. This is because, phosphorous is substitutional
solute in ferrite, where as Carbon and Nitrogen enter the crystal lattice as
an interstitial solute.

Figure 5. Effect phosphorus of the steel strenght

3. Dephosporization (Phosphorus Removal)

Steel is a mixture of iron and carbon. The content of carbon (C) affect
the hardness of the steel, and the required maximum carbon content in steel is
2%, in addition, the steel contains elements other mixtures called alloys, such
as manganese (Mn), silicon (Si), sulfur (S), Chromium (cr), Vanadium (Vn),
molybdenum (Mo), tungsten (Wo), and phosphorus (P).
In all cases, the oxidation of dissolved phosphorus is associated with
heat evolution. Especially much heat is liberated when it is oxidased by
gasesous oxygen. In some process based on the conversion of high-phosphorus
pig iron (such as basic Bassemer process), phosphorus is the main fuel the
element that produces on oxidation the required heat of metal heating.
Desfosforisasi process is performed on LD converter or other refining
furnace, by adding oxygen and reagents to binding phosphorus thus forming
slag. Regaen which can be used in the form of CaO. The phosphorus reaction
with the lime can be describe :
2[P] + 8(FeO) (3FeO.P2O5) + 5[Fe]
(3FeO.P2O5) + 3(CaO) (3CaO.P2O5) + 3(FeO)
2[P] + 5(FeO) + 3(CaO) (3CaO.P2O5) + 5[Fe]

4. Sources Of Phosphorous Input.

Phosphorous comes in to steelmaking furnace from:
a) Hot Metal
All the phosphorous present in blast furnace burden goes to hot
metal, since deohosphorization is not possible in blast furnace due to
reducing atmosphere.
b) Sponge iron
Sponge iron may contain upto 1.0% phosphorous.
c) Recycled BOF Slag
d) Coke

5. Requirement of Low phosphorus Steels

a) To have improved mechanical properties like temper embrittlement, low
temperature ductility.
b) To have better corrosion resistance and deep drawing properties.
c) To reduce hydrogen induced cracking and stress corrosion cracking.
d) To reduce chances of cracking during bending.
e) For the equipment in chemical industry.
f) For reprocessing equipment of the nuclear industry.
g) To prevent segregation during continuous casting.

CHAPTER II
THERMOYNAMIC ASPECT
Although the boiling point of phosphorous is very low a considerable amount of
it still dissolved in liquid iron because of its strong interaction parameter with iron. The
iron and phosphorous lines on the Ellingham diagram are so closed to each other that
the entire phosphorous in the burden gets reduced along with iron in an iron blast
furnace. This might have posed a serious problem in the oxidation of phosphorous but for
the fact that the two lines are widely separated during steel making by decreasing the
activity of PO using a strong and excess basic flux. The standard and non-standard
lines on the Ellingham diagram are shown in Figure 6. The steelmaking slag may contain
upto 25% PO but even then the activity of PO in slag remains extremely low. For
effective removal of phosphorous basic steelmaking process have to employ slags of
high basicities. If the basicity falls, phosphorous may revert back to the metal phase. In
acid steel making process since the slag is nearly saturated with silica, phosphorous can
not be eliminated at all.
The oxide Ellingham diagram of interest in refining basic pig iron. Decreasing
the activity of the product oxide results in rotation of the line in clockwise direction. By
employing highly basic slags, the iron and phosphorous lines are thus widely separated.
The shaded area in Figure 6 indicates the basic steel making condition

Figure 6. Ellingham diagrams for P2O5

The content of phosphorus is carried over from the primary steel on steel
making arround 0.025 to 0.030 wt% in steel. At temperatures of steel making, the
stabil state of phosphorus is gaseous P2. P2O5 is also gas. Phosphorus has a very high
solubility in liquid iron. The Equilibrium Phosphorus

[ ]
[ ]
refernce : ebook of iron mking and steel making by adhira ghosth

For reaction
[ ]

[ ]

[ ]

(
[

)
}
] [ ]

at temperature 1600oC (1873 K) and at equilibrium

assuming

(
[

)
] [

[ ]

where
(

Assuming wt%P and wt% O in steel at tundown to be 0,01 % and 0,08 % with the
mole fraction of P2O5 in slag is about 0,01.
{

(
[

)
] [

] [
(

]
)

This indeed a very low value. Such a low

value is possible only in a

higly basic slag since P2O5 is an acidic oxide. P2O5 on slag activation coefficient
according to the equation of Turkdagon and Pearson.

It may be noted from the above equation that CaO is the most powerful
dephosriser, in fact Na2O, BaO are more than powerful than CaO, but they cannot
be used im steelmaking owing to their tendency to attack the lining of the furnace.
The approximate dephosphorisation power ratio for some slag has been estimed
as:

From equation of

will shows that for highly basic, limey slag it is

possible to obtain sufficiently low

for effective dephosporisation.

Phosphorus partition equilibrium between slag and metal is very important, Turkdogan
suggests an rellation partition coefficient of phosphorus (Lp), the reaction :

where
[

This equation intends to provide the capacity to absorb phosphorus from the
slag in terms of basic oxides.

CHAPTER III
CONCLUSION
Dephosporization is the methode of phosphorus removal by using
injection some oxygen and the addition of lime, the products is slag. The reaction
of dephosphorization :
2[P] + 8(FeO) (3FeO.P2O5) + 5[Fe]
(3FeO.P2O5) + 3(CaO) (3CaO.P2O5) + 3(FeO)
2[P] + 5(FeO) + 3(CaO) (3CaO.P2O5) + 5[Fe]
Removal of phosphorous takes place by oxidation. The product,
phosphorous pentoxide is being held by basic constituents, like CaO, present in
the slag. In steel making processes basicity of the slag is maintained by addition
of calcined lime. The reaction may be given by,
[P] + 5/2[O] + 3/2(O-) = (PO4)

Requirement of Low phosphorus Steels

a. To have improved mechanical properties like temper embrittlement, low
temperature ductility.
b. To have better corrosion resistance and deep drawing properties.
c. To reduce hydrogen induced cracking and stress corrosion cracking.
d. To reduce chances of cracking during bending.
e. For the equipment in chemical industry.
f. For reprocessing equipment of the nuclear industry.
g. To prevent segregation during continuous casting.

REFENECE
Ahindra Ghosh and Amit Chatterjee: Ironmaking and Steelmaking Theory and
Practice, Prentice-Hall of India Private Limited, 2008.
A.Ghosh, Secondary Steel Making Principle & Applications, CRC Press 2001.
R.G.Ward: Physical Chemistry of iron & steel making, ELBS and Edward
Arnold, 1962