Desgasificado Al Vacío

Tema 4.
Desgasificado al vacío
PROCESOS SIDERÚRGICOS III
Fernando Contreras B.
4 June 2010
Procesos Siderúrgicos III – Desgasificado al vacío
TEMARIO
1.1 Introducción
1.2 Vacuum technologies
1.3 Reactions under vacuum
1.4 Generation of vacuum
Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 2

INTRODUCTION

INTRODUCCIÓN
- VD consists in the generation of very low pressure at the interface between

liquid steel & the atmosphere.
- As a consequence, the equilibrium for gas solubility changes allowing the
removal of the volatile elements dissolved in the steel.
-Initially, VD
was used to
decrease H
dissolved in
the steel.
Then VD
became
mandatory
to produce
ULC steels &
IF steels.
Low content
of C & N.

VACUUM TECHNOLOGIES

INTRODUCCIÓN – General classification

INTRODUCCIÓN – Stream degassers
- Degasification of the steel occurs on the stream during the transference

from one unit to another.
LLD:Ladle to ladle

LMD:Ladle to mould

TD: Furnace to ladle

VACUUM TECHNOLOGIES – Ladle degassers
- Occurs with the liquid steel inside the ladle. It has two main designs,
- With external recirculation:
Part of the liquid steel is sucked out of the ladle and forced into a second
vessel where the vacuum is applied and then returned to the original
ladle. Three types of recirculating degassers have been developed:
-DH: Dortmund Hoerder
-RH: Ruhrstahl Heraeus
-RH-OB (KTB) Kawasaki Top Blown
- Without external recirculation

-The full ladle (steel & slag) is permanently under vacuum. Three
technologies have been developed,
-VTD: Vacuum Tank Degasser, or TD
-VOD: Vacuum Oxygen Decarburization
-VAD: Vacuum Arc Degasser

VACUUM TECHNOLOGIES – DH Dortmund Hoerder

VACUUM TECHNOLOGIES – Ruhrstahl Heraeus

VACUUM TECHNOLOGIES – Ruhrstahl Heraeus -Kawasaki Top Blown (RH-KTB)

VACUUM TECHNOLOGIES –Vacuum degasser (VTD)

VACUUM TECHNOLOGIES –Vacuum Oxygen Decarburization (VOD)

VACUUM TECHNOLOGIES –Vacuum Arc Degassing (VAD)

VACUUM TECHNOLOGIES –Summary
- The vacuum technologies most used are RH & TD with the corresponding
version for oxygen blowing. Comparisons are shown next:

REACTIONS UNDER VACUUM

REACTIONS UNDER VACUUM –Decarburization & deoxidation
- Deoxidation is performed through C-O reactions.

- The equilibrium of the system is studied with the following reactions,
- Decreasing the pressure of the system, the equilibrium of the reaction

moves to the right side to generate CO(g).
- Due to the decrease of CO partial pressure, reaction between C & O
dissolved in the bath becomes more intense.
-Oxygen can be available in the bath as less stable oxide (FeO, MnO) or as
dissolved O which come from the oxidation stage in EAF.

REACTIONS UNDER VACUUM – Decarburation in Tank Degasser
- Without Ar stirring,
-The reaction is favored

only near bath surface
(the reduced pressure is
only effective on the
surface).
-The reaction rate is

limited by C & O
diffusion in the liquid
phase.

- With Ar stirring,
-The reaction rate

increases remarkably.
-C & O are brought to the
reaction surface more
rapidly.
-The argon bubbles
increase the available
reaction surface.
-The steel is permanently
recirculating from the
bottom to the surface.

- With Ar stirring,
-When the reaction

occurs under vacuum
with strong Ar
stirring, the diffusion
of [C] & [O] to the
place of reaction to
form {CO} is
enhanced.
-CO finally is
incorporated into the
Ar bubble & dragged
out of the system.
-Ar & CO gas are
dragged out through
the vacuum system.

-Decarburization can be studied

using the [C]-[O] equilibrium
graph for different partial
pressure of {CO}.
- Equation relates the operative
parameters:
Pco= partial pressure of CO
[O]= ppm dissolved in the steel
(eq)
[C]= %C in eq.
T= temperature
- When decarburation starts in
point a (at 1 atm) and the TD
operates at 0.2 atm, the final
%[C]-ppm O will correspond to
point b.

REACTIONS UNDER VACUUM – Decarburation in Tank Degasser (kinetics)
-The kinetics of decarburization

follows the relationship:
-Where kc is a constant & depend on, a) specific flow rate of stirring

b) degassing time (t)

REACTIONS UNDER VACUUM – Decarburization Chemistry
-We can rearrenge the mass action law equation to,
[O]=Pco/[C]Kco
-If the pressure above the steel is reduced to 0.1 atm, Pco will also drop
to 0.1 atm and the equilibrium [C].[O] product will decrease
accordingly.
-C & O will be removed in the ratio 12:16 as determined by their
respective atomic masses.
-The injection of additional oxygen into the steel can be used to
produce very low C steels (e g., <0.001%).

REACTIONS UNDER VACUUM – Degassification (Hydrogen Equilibrium)
-The reactions for dissolution are:
-The sources of H2 are:

-Water which come from humidity.
-Air or any humid material in contact with the steel

REACTIONS UNDER VACUUM – Degassification (Hydrogen equlibrium)
-The basic eq reaction is [H]=1/2 {H2}g. The eq constant is:
-The H concentration at Eq is proportional to the pressure square root.

-The dissolution of H (also N) in pure iron obeys Sievert’s Law:
gas atomic concentration = Eq constant x partial pressure
of gas

REACTIONS UNDER VACUUM – Degassification (Hydrogen kinetics)
-Considering that in modern VD the operating pressure is around 10

mbar and appliying the following formula.
[H] f=final H content

[H] i=initiall H content
t =VD process time
KH = H removal
constant, min-1
-To accelerate the

reaction kinetics, it is
necessary to stirr the
bath with Ar. H removal
constant depends on the
working pressure and
stirring flow.
REACTIONS UNDER VACUUM – Degassification (Hydrogen kinetics)
-If no Ar stirring is promoted, following occurs, 2[H] = {H2}
-The reaction will only take place at

bath surface.
-The reaction rate is limited by H
diffusion in the liquid phase.
-Is Ar stirring is promoted, following occurs,
-H is brought to the reaction surface

more rapidly.
- The Ar bubbles increase the
available reaction surface.
-The Ar bubbles drag the H out of
the steel

REACTIONS UNDER VACUUM – Degassification (Hydrogen removal)
-[H] dissolved in the steel reacts to form H2 gas molecule which is

absorbed by the Ar bubble and dragged out of the liquid steel.

REACTIONS UNDER VACUUM – Degassification (Nitrogen equlibrium)
-The basic eq reaction is [N]=1/2 {N2}g.

-N concentration at Eq is proportional to the square root of its partial
pressure (Sievert’s Law). The Eq constant is defined as follows,
-Like H, Nitrogen removal also occurs due to the decrease of its partial
pressure in the gaseous phase but differs in some particular aspects:-
- Velocity is limited by the pressure of surface active elements like
[O] & [S]
- Surface active elements block the sites for N2 passage to the
interface.
REACTIONS UNDER VACUUM – Degassification (Nitrogen kinetics)
-A simplified formula for N removal velocity is:
[N]f= final N content

[N]i= initial N content
T= VD process time
KN= N removal constant
considering O & S equal
to zero (min-1)
-KN depends on the operative pressure and on the stirring intensity.

- N removal is more difficult than H’s since N diffusivity in liquid steel is lower.
Hence, Ar stirring has to be more intense.
-N removal is retarded also by elements such as Al & Ti which have a high
affinity for Nitrides.

-If no Ar stirring is promoted, following occurs, 2[N] = {N2}
-Reaction occurs at bath surface which

is reduced by presence of S & O.
-Reaction rate is limited by N diffusion
which is slower as N diffusivity is lower
(larger atom).
-Is Ar stirring is promoted, following occurs,
-The gaseous phase is generated by Ar

bubble.
- Increases the area of the interphase
gas liquid.
-Available surface for N removal.


REACTIONS UNDER VACUUM – Defulfurization under vacuum
- It is controlled by the reaction:
- During vacuum treatment the reaction is strongly favored because

operated at:
-High temperature
-Strong Ar bubbling
-High degree of deoxidation
-Increase of specific slag/steel area
-For desulfurization under vacuum near equilibrium conditions can be

reached.
REACTIONS UNDER VACUUM – Defulfurization under vacuum
- A equation has been developed in terms of amount of slag required to

achieve a specific S concentration as follows:
- Eq considers equilibrium conditions and terms mean next,

Wm = weight of steel
Ls= sulfur distribution ration given by (%S)/[%S].
%So & %S aim = Initial & aim S concentration.
- The Ls value depends on the S capacity of the slag and is

related to:
-Under good conditions, value of Ls=500 are assemble in
practice.
Example
GENERATION OF VACUUM

GENERATION OF VACUUM – Vacuum treatment
In general the specification of a Vacuum System considers,

-Volume of the vessel to be evacuated.
-Flow of Ar to be injected in the vessel.
-Last operative pressure to be attained.
-Pumping capacity at the operative pressure.
-Time to reach the operative pressure.
Three types of equipment are generally used,

-Liquid ring pumps.
-Mechanical pumps.
-Steam ejectors.

GENERATION OF VACUUM – Liquid ring punps
PROS,
-High suction capacity.
-Not affected by liquid or dust
entrained in the process gas
stream
-High reliability due to simple
design
-Low maintenance required
CONS,
-Cannot achieve a pressure
below 150 mbar (when water is
used for the production of the
liquid ring)

GENERATION OF VACUUM – Mechanical Pump (Roost type)
PROS,
-Steam is not required therefore
some energy can be saved.
CONS,
-Must treat relarively cold and
absolutely dust-free fluids only.
Therefore a heat exchanger and
bag filter must procede the
pumps.
-Cost exceeds that of the steam
jet pump system.

GENERATION OF VACUUM – Steam Ejectors (Jet pumps)
PROS,
-High suction capacity.
-Not affected by liquid or dust entrained in the process gas steam.
-High reliability due to the absence of moving parts.
-Practically no maintenance required.
CONS,
-Requires a steam generator.

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Tema 4.

PROCESOS SIDERÚRGICOS III

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 2

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 3

- VD consists in the generation of very low pressure at the interface between

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 4

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 5

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 6

- Degasification of the steel occurs on the stream during the transference

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 7

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 8

TD: Furnace to ladle

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- Without external recirculation

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 10

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 11

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 12

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 13

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 14

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 15

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REACTIONS UNDER VACUUM

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 18

- Deoxidation is performed through C-O reactions.

- Decreasing the pressure of the system, the equilibrium of the reaction

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 19

-The reaction is favored

-The reaction rate is

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 20

-The reaction rate

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 21

-When the reaction

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 22

-Decarburization can be studied

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 23

-The kinetics of decarburization

-Where kc is a constant & depend on, a) specific flow rate of stirring

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 24

-We can rearrenge the mass action law equation to,

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 25

-The reactions for dissolution are:

-The sources of H2 are:

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 26

-The basic eq reaction is [H]=1/2 {H2}g. The eq constant is:

-The H concentration at Eq is proportional to the pressure square root.

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 27

-Considering that in modern VD the operating pressure is around 10

[H] f=final H content

-To accelerate the

-If no Ar stirring is promoted, following occurs, 2[H] = {H2}

-The reaction will only take place at

-Is Ar stirring is promoted, following occurs,

-H is brought to the reaction surface

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 29

-[H] dissolved in the steel reacts to form H2 gas molecule which is

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 30

-The basic eq reaction is [N]=1/2 {N2}g.

-A simplified formula for N removal velocity is:

[N]f= final N content

-KN depends on the operative pressure and on the stirring intensity.

Desgasificado al vacío Instructor: Fernando Contreras 4 June 2010 32