09

Phosphorous Problem

AkMB Rashid
Professor, Department of MME
BUET, Dhaka

Today’s Topics
 Behaviour of phosphorous in metal and slag
 Oxidation of phosphorous
 Effect of temperature
 Effect of metal and slag composition
 Conditions of dephosphorisation
 Conditions for simultaneous removal of carbon and phosphorous
 Rephosphorisation
 Introduction
• Phosphorus can be dissolved in iron in substantial quantities.

• Dissolution of phosphorus proceeds with evolution of a certain quantity of heat:

1/2{P2} = [P]; DG° = - 140,200 - 9.62 T

• Phosphorus is usually regarded as a harmful impurity in steel

1. widens the “pasty zone” and narrows the g-region  cause segregation
2. produces structural inhomogeneities  impairs the plastic properties of steel

Sources of P in iron: Classification of iron (based on P level):

• Pig iron • Class A iron (P < 0.15%)
• Scrap and ferro-alloys • Class B iron (P up to 0.20%)
• Class C iron (P up to 0.30%)
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Behaviour of Phosphorous in Metal and Slag

• At the steelmaking temperatures, the stable state of phosphorus is gaseous {P2}
and oxide of phosphorus, P2O5 is also a gas.

• Phosphorus has a very high solubility in liquid iron as well.

• Considerable interactions between iron and phosphorus exists in liquid alloys

leading to strong deviations from ideality.

• Dissolution of P from its gaseous state:

1/2{P} = [P]1wt% ; DG° = -122,170 – 19.25 T J/mol

Influence of other alloying elements on 𝑒𝑃𝑂 = -0.62

activity of phosphorus in iron solutions 𝑒𝑃𝑆 = +0.041
(determined using Wagner’s approximation) 𝑒𝑃𝑆𝑖 = +0.094

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 3CaO + P2O5 = Ca3(PO4)2 ; DH298
𝑜
= -677,840 J/mol

• Large negative heats of formation reflect the strength of the attraction

between the 𝑃𝑂43− anions and the cations of the basic oxides

• This indicates that the activity coefficient of P2O5 in basic slags is extremely
small, reaching as low as 10–18 in lime-rich slags.

• Basic slags thus make an excellent sink for phosphorus in steelmaking.

• Although Henrian behaviour is generally assumed for phosphorus both

in slag and metal, the relation between activities of P in metal and slag
solution is not linear.

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Oxidation of Phosphorus

• Phosphorus removal from hot metal is regarded as the most important

refining reaction.

• It can be effectively carried out only in primary steelmaking operations to

achieve phosphorus contents of around 0.025 to 0.030 wt.% in steel.

• With increasing demand for ultra-low phosphorus steel (wt.% P < 0.005) for
some special grades (like steel used in automobiles), removal of phosphorus
has become of even greater significance.

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 • Phosphorus has atomic number 15 and it can give up all 5 electrons from its
outermost shell to become P5+ or accept 3 electrons to become P3− to attain
stable configuration.

• This means that phosphorus can be removed both under oxidizing as well as
reducing conditions.

• But removal of phosphorus under reducing conditions is not practical since

its removal is highly hazardous.

• Thus, P removal is practised mostly under oxidizing conditions.

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Oxidation of Phosphorus

2[P]1wt% + 5[O]1wt% = (P2O5); DG° = -740,375 + 535.365T J/mol

𝑎𝑃2𝑂5 • At T > 1382 K, ΔG° becomes positive,
𝐾𝑃 =
ℎ𝑃 2 ℎ 𝑂 5 which results in decomposition of P2O5
to P and O.
−∆𝐺 𝑜 38668
log 𝐾𝑃 = = − 27.96 • Thus, removal of P requires that 𝑎𝑃2 𝑂5
2.303 RT 𝑇
must be reduced.

𝑂 = 𝑎𝐹𝑒𝑂 𝑂 𝑠𝑎𝑡

𝑁𝑃2𝑂5 𝐾𝑃 𝑎𝐹𝑒𝑂 5 [𝑂]5𝑠𝑎𝑡  To have a higher index of phosphorisation,

=
𝑃2 𝛾𝑃2𝑂5 𝛾𝑃2𝑂5 must be low in the slag

Index of phosphorisation

8/23
 𝑎𝑃2 𝑂5 −∆𝐺 𝑜 38668
𝐾𝑃 = log 𝐾𝑃 = = − 27.96
ℎ𝑃 2 ℎ𝑂 5
2.303 RT 𝑇

Assuming [hP] = [P] and [hO] = [O], at 1600 °C and at equilibrium

𝑎𝑃2𝑂5
𝐾𝑃 = = 4.0x10−8
𝑃2 𝑂 5

Assuming wt% P = 0.01 and wt% O = 0.08% in a steel at turndown,

𝑎𝑃2𝑂5 = 1.57x10–17

If wt% P2O5 = 2.0 wt%, then 𝑁𝑃2𝑂5 = 0.01 and 𝛾𝑃2𝑂5 = 1.31x10–15

 Such a low value of 𝛾𝑃2𝑂5 is possible only in a highly basic slag

since P2O5 is an acidic oxide.

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• The different basic oxides have different ability to lower 𝛾𝑃2𝑂5 .

42000
log 𝛾𝑃2𝑂5 = −1.12 22𝑁𝐶𝑎𝑂 + 15𝑁𝑀𝑔𝑂 + 13𝑁𝑀𝑛𝑂 + 12𝑁𝐹𝑒𝑂 − 2𝑁𝑆𝑖𝑂2 − + 23.58
𝑇
 CaO is the most powerful dephosphorizer of all basic oxides.

• Na2O and BaO are more powerful than CaO

• but they cannot be used in steelmaking
because of their tendency to attack and
corrode the refractory lining of the furnace.

• The approximate dephosphorization

power for some cations in slag :

Ca2+ Mg2+ Mn2+ Fe2+

30,000 : 1000 : 3 : 1
Effect of metal oxide on activity coefficient of P2O5
 Effect of Temperature
(a) Oxidation of P with oxygen of the gaseous phase:
4/5[P] + {O2} = 2/5(P2O5); DG° = -618,836 + 175.0 T J/mol;

(b) Oxidation of P with oxygen dissolved in the metal:

4/5[P] + 2[O] = 2/5(P2O5); DG° = -384,953 + 170.24 T J/mol;

(c) Oxidation of P with oxygen present in iron oxides of the slag:

4/5[P] + 2(FeO) = 2/5(P2O5) + 2[Fe]; DG° = -142,944 + 65.48 T J/mol

• oxidation of dissolved phosphorus [P] is associated with heat evolution

 In some processes based on the conversion of high-phosphorus pig iron
(such as the basic Bessemer process), phosphorus is the main ‘fuel’

• a decrease in temperature favours oxidation of phosphorus

11/23

Effect of Metal Composition

• The process of phosphorus removal is impeded when the metal has a

high concentration of easily oxidizable impurities (such as Si, Mn or C)

• These elements interact with iron oxides and thus diminish the oxygen
content of the slag.

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 Effect of Slag Composition

• A higher oxygen content and a high activity of iron oxides of the slag
promotes phosphorus oxidation

• To remove phosphorus from metal and retain it in slag, the activity of P2O5
in the slag must be decreased.

• This can be achieved by forming a basic slag by adding lime (or limestone).

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• CaO, reacts with P2O5 to form stable

compounds of (4CaO.P2O5) or (3CaO.P2O5).

2[P] + 5(FeO) + 4(CaO) = (4CaO.P2O5) + 5[Fe]

2[P] + 5(FeO) + 3(CaO) = (3CaO.P2O5) + 5[Fe]

• The extent of dephosphorization is often

characterized by the index (4CaO.P2O5)/[P]2.
• Simpler ratios such as (P2O5)/[P]2, (P2O5)/[P],
or (P)/[P] are also used.

 Dephosphorization increases with increase in (FeO)

content of slag and becomes maximum in between
15-16% FeO.
 For (FeO) > 15-16%, dephosphorization decreases.
Dependence of (P2O5)/[P] ratio on FeO
 The above behaviour can be observed at all content of slag at different CaO/SiO2 ratios
basicities of slag. in laboratory experiments at 1685 °C
 Why this dual behaviour of FeO ?

• FeO is the source of oxygen for oxidation of P.

• So, for a given basicity of slag, (FeO) increases the oxidizing power of the slag.

• Beyond the optimum value of FeO in slag, FeO replaces CaO and may either
combine with CaO or with P2O5.

• Thus, higher is the wt% FeO, lower will be the wt% CaO, and this will adversely
affect the dephosphorization ability of the slag.

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• The maximum dephosphorization ratio increases

with the increase in the slag basicity.

• Higher basicity requires higher amount of CaO

dissolved in slag.

• Any undissolved CaO will not be effective for

dephosphorization.

• As the optimum value of FeO is more or less

independent of slag basicity, control of FeO in slag
is important for efficient dephosphorization.

Dependence of (P2O5)/[P] ratio on FeO

content of slag at different CaO/SiO2 ratios
in laboratory experiments at 1685 °C
 Conditions for Dephosphorization
2[P] + 5(FeO) + 3(CaO) = (3CaO.P2O5)

𝑎3𝐶𝑎𝑂.𝑃2𝑂5 𝑎3𝐶𝑎𝑂.𝑃2𝑂5 𝑃 5 3
𝐾= ≈ = 𝐾 𝑎𝐹𝑒𝑂 𝑎𝐶𝑎𝑂
[ℎ𝑃 ]2 𝑎𝐹𝑒𝑂 5 𝑎𝐶𝑎𝑂 3 [ℎ𝑃 ]2 𝑃

The conditions for an efficient dephosphorization are:

• aCaO in slag should be high.

This means slag should have free dissolved lime.
A highly basic, lime-rich slag is required.
The slag should contain a lowest possible amount of undissolved free lime.

• aFeO in slag should be high i.e., slag should be oxidizing.

For efficient dephosphorization the FeO content of slag should be in between 15 to 16%.

• Low temperature favours high K

17/23

Principal conditions essential for dephosphorization :

1. formation of an oxidizing furnace atmosphere and oxidizing slag

with a high activity of iron oxides in it (the slag must have a (FeO)  15 wt%);
2. high basicity of the slag (high in CaO and low in SiO2) and
high activity of CaO in it;
3. quick formation of ferruginous-limy slag;
4. a relatively low temperature
(especially at moderate and high concentrations of carbon);
5. low activity (concentration) of phosphorus in the slag.

18/23
In practice, these conditions are provided by the following techniques:

(a) addition of iron oxides to the melt (in the form of iron ore or scale);

(b) addition of CaO (lumpy or powdered lime or limestone);

(c) blowing the bath with oxygen (or air);

(d) removing most phosphorus at an early stage of the heat when the temperature
of the metal is still not high;

(e) forming an active free-running slag as early as possible,

which can be achieved by bath stirring, adding certain fluidizers to the slag, etc.
Sometimes, the fluid final slag from the previous heat, containing high CaO and FeO and
little phosphorus, is left in the furnace;

(f) slag renewal (i.e. by slagging-off and the formation of new slag free from P).

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Conditions for Simultaneous Removal of C and P

𝑝𝐶𝑂 1305 Henrian activity is

𝐶 + 𝑂 = 𝐶𝑂 ; 𝐾𝐶 = = + 1.979 assumed equal to
𝐶 𝑂 𝑇 (wt %)
𝑁𝑃2𝑂5 𝛾𝑃2𝑂5 38668
2 𝑃 + 5 𝑂 = 𝑃2 𝑂5 ; 𝐾𝑃 = = − 27.96
[𝑃]2 [𝑂]5 𝑇

 Both reactions require oxidising conditions,

but the P reaction requires a slag, which is basic in nature in addition to oxygen.

• Thus, if C and P are to be removed simultaneously,

an important requirement is the availability of slag which acts as a sink for (P2O5).

• Thermodynamically, a slag is required in which activity coefficient of P2O5

is very low.

• The question is how low activity of P2O5 should be?

20/23
 𝑝𝐶𝑂 1305
𝐾𝐶 = = + 1.979 Consider molten metal contains 2% C
𝐶 𝑂 𝑇
and 0.15% P and the mole fraction of P2O5
𝑁𝑃2 𝑂5 𝛾𝑃2 𝑂5 38668
𝐾𝑃 = = − 27.96 in slag is 0.1.
[𝑃]2 [𝑂]5 𝑇

T (K) 𝛾𝑃2 𝑂5
𝐾𝑃 [𝑃]2 1673 1.60 x 10–21
𝛾𝑃2𝑂5 = 5
𝐾𝐶 [𝐶]5 𝑁𝑃2𝑂5 1773 1.32 x 10–22
1873 1.42 x 10–23
(using pCO = 1 atm)

• Both decarburisation and dephosphorization are possible simultaneously

in presence of slag in which 𝛾𝑃2𝑂5 has extremely low value.

• At low temperature, 𝛾𝑃2𝑂5 in slag is lower. Thus, low temperature is favourable.

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Rephosphorization

• At the end of a heat

 if the metal temperature is too high, and

 deoxidants are added to the metal

(part of them can pass to slag (but not to metal) and lower the activity of oxygen
in metal and that of iron oxides in slag)

phosphorus that has been oxidized and passed to slag can be reduced again
and returned to the metal (rephosphorization).

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• In the final melt, slag basicity gradually decreases as
 slag interacts with the ladle lining (which consists of SiO2 and Al2O3)
 SiO2 content increases due to the addition of FeSi as deoxidant

• All these factors (high temperature and the decrease in a(FeO) and CaO/SiO2)
form favourable conditions for the reverse passage of phosphorus to the metal.

• As a result, the last portions of steel poured from the ladle during teeming may
turn out to contain noticeably more phosphorus than the first ones.

Preventive measures against rephosphorisation

• Add CaO at the later stage to increase slag basicity
• Tap steel containing much lower P level than the required value

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