Journal of Chongqing University (English Edition) [ISSN 1671-8224]

Vol. 13 No. 1
March 2014

doi:10.11835/j.issn.1671-8224.2014.01.02
To cite this article: XIONG Shuang, ZENG Hui, CAO Yang, WANG Qing-xiang. Change and control of nitrogen in molten steel production process [J]. J Chongqing Univ: Eng
Ed [ISSN 1671-8224], 2014, 13(1): 11-16.

Change and control of nitrogen in molten steel production process

XIONG Shuang , ZENG Hui, CAO Yang, WANG Qing-xiang
Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education, Wuhan University of Science and Technology,
Wuhan 430081, P. R. China

Received 8 January 2014; received in revised form 17 February 2014

Abstract: The change and control of nitrogen content in molten steel was investigated through the production process of LDBAr-LF-RH-CC. Results show that nitrogen content reduces gradually in converter-steelmaking stage, rises rapidly from the end
of converter process to the end of argon station process, continues to increase in ladle furnace process, and decreases slightly in
RH refining stage. Since nitrogen is removed mainly by BOF steelmaking and vacuum refining operations, nitrogen in molten
steel should be removed as much as possible in these two operations. However, nitrogen uptake should be minimized in other
operations of molten steel production process.
Keywords: molten steel; production process; nitrogen content; change; control
CLC number: TF76

Document code: A

Introduction a

Although nitrogen content in steel is very little, it has

considerable effects on the mechanical performance

Nitrogen in steel exists in the form of nitride and it

of steel

[4]

. It not only reduces the mechanical

affects the quality of steel in two aspects. On one

performance of steel, but also becomes an important

hand, it can improve the hot rolling performance,

cause of defects such as crack, skin blowhole, and

ductility and high temperature process ability of the

central porosity [5-6].

steel by the refined grain precipitated from VN in the

The pipeline steel, which is used to transport oil

non-quenched and tempered steel that contains

and natural gas, is growing rapidly at present. As oil

vanadium

[1-3]

. Obviously, this produces good social

and natural gas resources are mostly located in remote

and economic benefits. On the other hand, as the

and harsh areas, the delivery pressure in pipeline is

interstitial impurity such as C and N can diffuse easily

high, the medium is both complex and corrosive, and

in Fe atomic lattice at low temperature, the cold

pipelines are generally assembled and girth welded in

forging performance of steel can be reduced.

the field. All above require the pipeline steel to be

strong and tough, but also to have good performance
to resist fatigue, fracture and corrosion. Both of them

Corresponding author, XIONG Shuang ():

put forward strict requirements on the nitrogen

773968119@qq.com.

11

S. Xiong, et al.
Change and control of nitrogen

content in these steel, thus on the denitrification and

steel. There are two methods to reduce partial pressure

nitrogen

of nitrogen at present: one is to reduce the system

control

during

steelmaking

process.

Consequently, it is necessary to research the change

of nitrogen content and its causes, which can provide

pressure, such as VD and RH process

other is dilution, such as AOD process

theoretical basis for improving nitrogen desorption

measures

and

the

control

of

nitrogen

during

steelmaking progress.

[11]

[9-10]

, and the

Molten steel also contains O, S, Si, Cr, Ni, Mn, C,

Mo and other elements, and the combined influence
among elements cannot be ignored

[12]

. Elements such

as Cr, Mn, and Mo are not conducive to the

2

Nitrogen absorption and desorption theory of

denitrification as they reduce the activity of nitrogen.

molten steel

Elements such as C, Si, and N can improve the activity

of the nitrogen, so they are conducive to the

Nitrogen has certain solubility in each state of steel.

Gaseous nitrogen and dissolved nitrogen in molten
steel abide by the following chemical equilibrium [7-8]:
1/2N2 [N].

(1)

The solubility of nitrogen in molten steel conforms

to the law of square root, namely

%N ( K N

PN 2 ) / f N ,

denitrification. O, S and some other elements are

special, however. On one hand, they can improve
nitrogen activity, which is conducive to denitrification;
on the other hand, they can increase the gas-liquid
interfacial diffusion resistance of nitrogen as surface
active

denitrification
3

(2)

substance,

which

is

not

conducive

to

[13]

Production tests and results

The production tests of change and control of

nitrogen content during steel production process for

where KN is the equilibrium constant of nitrogen

the pipeline steel grade X70 have been conducted in

dissolution reaction in Eq. (1), PN 2 is the partial

a steelmaking plant which has top and bottom

pressure of nitrogen in the gas phase, and f N is the

combined blown converters with a capacity of 250 t.

activity coefficient of nitrogen in molten steel.

The production process is LD-BAr-LF-RH-CC.

It can be seen from Eq. (2) that the solubility of

127 heats have been tested from February 15 to

nitrogen in molten steel is affected by temperature,

March 27, 2011. Molten steel samples of each heat

partial pressure of nitrogen, and composition of molten

was taken at the late period of converter blowing

steel.

process by the sublance, at the endpoint of converter

As the dissolution of nitrogen in molten steel is an

process, at the end of Ar station, at the end of LF

endothermic reaction, the solubility of nitrogen

process, at the end of RH process, and in tundish.

increases when the temperature rises. Therefore, the

The nitrogen content of all molten steel samples has

temperature of molten steel needs to be lowered to

been determined according to the convention of

reduce the nitrogen content.

production field by routine. The 127 heats of pipeline

The solubility of nitrogen in molten steel declines

steel grade X70 have been sampled at each sampling

with the decrease of nitrogens partial pressure, and

point along the process of LD-BAr-LF-RH-CC.

vice versa. Therefore, we should reduce the partial

The nitrogen content results of the samples are listed

pressure of nitrogen for the denitrification of molten

in Table 1.

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J. Chongqing Univ. Eng. Ed. [ISSN 1671-8224], 2014, 13(1): 11-16

S. Xiong, et al.
Change and control of nitrogen

Table 1 Average nitrogen content ([N]) at each sampling

conditions in converter, the carbon oxygen reaction

point during the production process of the pipeline steel grade

reacts fiercely and the nitrogen content of molten steel

X70

decreases by the denitrification of CO bubbles.

Sampling point
Converter sublance
Converter endpoint
Ar station endpoint
LF endpoint
RH endpoint
Tundish

[N]/(mg/L)
21.5
17.8
57.4
83.3
62.9
60.4

Molten steel absorbs a significant amount of

nitrogen from steel tapping to argon station process.
This is because molten steel contacts with air
aggressively and absorbs a lot of nitrogen during steel
tapping process and the following argon blowing
process, which is designed to enhance the reactions
between molten steel and slag, carburant, alloying

Change and analysis of nitrogen content during

agent, etc. If the tapping hole is not round, or scattered

steel production process

flowing occurs, or argon blows too violently, nitrogen

absorption of molten steel will be more severe. In

Based on Table 1, statistical results of nitrogen

addition, most of the oxygen in molten steel is removed

content changing in the 127 heats pipeline steel grade

by slag and alloying agent during tapping steel, the

X70 during the process of LD-BAr-LF-RH-CC are

carbon oxygen reaction stagnates and CO bubbles

as shown in Fig. 1.

reduce instantly by a large margin. As a result, the

nitrogen content of the molten steel increases.
Carburant and high nitrogen alloys such as MnFe can
also increase nitrogen content of molten steel.
Therefore, the nitrogen content of alloy needs to be
monitored and alloys with low nitrogen content should
be used in low nitrogen steel smelting.
The main reason of nitrogen absorption in LF
process is that nitrogen in the air goes into molten steel
by being ionized into nitrogen ions in the arc region, as
the surface of the molten steel in arc area becomes bare
due to the breakdown of slag layer by arc. In addition,
a certain amount of ferroalloys or carbon powder are

Fig. 1 Statistical curve of nitrogen content changing in the

pipeline steel grade X70 during production process

As can be seen in Fig. 1, nitrogen content of molten

steel reduces gradually in the converter process, rises

added into molten steel in LF refining for composition

adjustment. To strengthen the reaction, a large amount
of argon is used for stirring. These can also cause
additional exposure of molten steel to the atmosphere,
resulting in nitrogen absorption.

rapidly from steel tapping to argon station process,

Fig. 1 shows that nitrogen in molten steel can be

continues to increase in ladle furnace process, and

removed to a certain degree in the RH vacuum

decreases in RH refining process.

treatment process. This can be explained by Eq. (2). As

Denitrification in converter process mainly relies on

2[N] N2, the reaction will generate in the direction of

CO bubbles that generated from carbon oxygen

the nitrogen gas when the nitrogen pressure in RH

reaction. Due to good thermodynamic and kinetic

vacuum chamber is less than the equilibrium pressure

J. Chongqing Univ. Eng. Ed. [ISSN 1671-8224], 2014, 13(1): 11-16

13

S. Xiong, et al.
Change and control of nitrogen

of [N] in the molten steel, and [N] will escape from

submerged arc heating and to prevent nitrogen

molten steel in the form of nitrogen gas. Finally,

absorption caused by the surface of molten steel

nitrogen content decreases.

exposed

[14]

; seal ladle and smoke hood to keep

reducing atmosphere in the furnace and reduce the

5

Control of nitrogen in the steel production

contact between molten steel and the air; and use low

process

nitrogen alloys for the alloying treatment whenever

possible.

The control of nitrogen content must be done

Measures for optimizing denitrification during RH

throughout hot metal pretreatment, converter smelting,

process are as follows: increase the vacuum level and

refining

casting.

extend the vacuum refining time; use carbon oxygen

Theoretically, they both have certain denitrification

reaction under the vacuum conditions and increase the

ability during hot metal pretreatment, converter

lifting gas flow to improve the denitrification rate

smelting and RH vacuum refining process, but

put the main nitrogen control measures in the converter

denitrification should be mainly accomplished in

steelmaking process for smelting low or ultra-low-

converter

the

nitrogen steel; and control the vacuum conditions

denitrification efficiency and process optimization. The

during RH refining process to reduce nitrogen

main task of later processes, such as steel tapping,

absorption.

treatment

smelting

and

continuous

process

in

terms

of

refining and continuous casting, is to prevent or reduce

nitrogen absorption.

Technical

measures

for

preventing

[15]

nitrogen

absorption in continuous casting are as follows: seal

Measures to improve denitrification efficiency in

the gap between ladle bottom nozzle and long nozzle

converter process are as follows: raise the lance

by argon blowing to prevent the air seeping into when

position properly when converter smelting starts;

molten steel in the ladle comes into tundish [16]; seal the

increase the (FeO) content of slag to ensure that bulk

tundish and use the operation of large amount slag

materials in the furnace melt fully as soon as possible

when molten steel is in the tundish; and seal the gap

and cover the surface of molten steel evenly to avoid

between slide plate and submerged nozzle by argon

direct contacting between molten steel and the air; use

blowing when molten steel comes into the mold from

whole argon mode for bottom blowing converter to

tundish.

avoid nitrogen content rising caused by nitrogen supply

at the initial stage of bottom blowing; increase hot

Conclusion

metal ratio appropriately to reduce nitrogen brought by

steel scrap; increase the amount of slag appropriately to

1) The nitrogen content in molten steel reduces in

avoid the slag getting dry and keep the thickness of

converter smelting stage, increases rapidly from steel

slag layer enough to reduce the nitrogen absorption

tapping to argon station, continues to increase in ladle

during blowing process; improve terminal hit rate to

furnace process, and decreases slightly in RH refining

reduce point blow; keep positive pressure in furnace to

stage.

reduce nitrogen absorption; and keep steel tapping hole

round to prevent steel scattered flowing.

2) Denitrification in converter process mainly relies

on CO bubbles generated from carbon oxygen reaction.

Measures for controlling the nitrogen absorption in

Due to good thermodynamic and kinetic conditions in

LF process are as follows: make foaming slag with

converter, the carbon oxygen reaction reacts fiercely

appropriate thickness during refining process to ensure

and the nitrogen content of molten steel decreases by

14

J. Chongqing Univ. Eng. Ed. [ISSN 1671-8224], 2014, 13(1): 11-16

S. Xiong, et al.
Change and control of nitrogen

the denitrification of CO bubbles.

steels with high strength and ductility [J]. Metal

3) Molten steel absorbs a significant amount of

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Science and Heat Treatment, 2005, 47(11): 9-13.

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Yuji I, Rikio N. Effect of thermo-mechanical treatment

This is because molten steel contacts with air

on mechanical properties of high-nitrogen containing

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Cr

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International, 1996, 36(7): 855-861.

process, which is designed to enhance the reactions

[6]

Mn-Ni

austenitic

stainless

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Frechard S, Redjaimia A, Lach E, et al. Mechanical

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Huang XH. The ferrous metallurgy principle [M]. 3rd

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