The
ladle degassing refining method is the main method of refining outside the
furnace (also known as secondary steelmaking). Out-of-furnace refining is the
process of transferring the molten steel smelted in a roughing furnace
(electric furnace and converter) to another high-temperature vessel (mainly a
ladle) for refining: Refining is a process of using different metallurgical
treatment methods and devices outside the furnace according to the type of
steel to be smelted.
One
method is classified as:
(1)
Ladle processing type, such as ladle argon blowing, ladle powder spraying and
vacuum cycle degassing (RH);
(2)
Ladle refining type, such as vacuum oxygen decarburization (VOD), argon oxygen
decarburization (AOD), ladle refining (LF, ASEA-CKF, VAD, etc.). Only by
understanding the basic structure and technology of these devices can we
understand the construction of refractory materials and the lining materials
used in these devices. There are 6 common ladle refining devices as follows.
RH device
The RH method is a suction-type vacuum degassing refining method, also known as a circulating method vacuum degassing device, as shown in Figure 1. This method was developed in 1985 by Rheinstahl and Heraeus companies in Germany. The method and device are suitable for vacuum processing of large containers, and are widely used in the production of special steel, ordinary steel and stainless steel.
The
main functions of this method are:
(1)
Degassing functions such as dehydrogenation, deoxygenation and denitrification;
(2)
Vacuum decarburization function;
(3)
The composition and temperature are homogenized by stirring, and the function
of floating and separating non-metallic inclusions is realized. The device is
composed of a vacuum degassing chamber, Ar gas blowing device, immersion pipe,
exhaust system and alloy silo. Two immersion pipes are arranged under the
vacuum degassing chamber, and high-speed Ar gas is blown into one immersion
pipe (rising pipe). According to the principle of the air pump, the molten
steel in the ladle is brought into the lower part of the vacuum degassing
chamber, and then from the other immersion pipe The (downcomer) returns to the
ladle to realize the circulation degassing. The circulation speed is controlled
by the amount of Ar gas blown in. The high-speed argon blowing and the flow of
molten steel in the ladle will definitely aggravate the damage of the tank
lining refractories.
The
RH furnace works under vacuum and high temperature. It is divided into three
replaceable parts: upper, middle and lower parts. The service life of the
refractory material in the lower part is shorter, and the service life of the
riser pipe is the shortest. The lining material of RH furnace is usually made
of high-quality magnesia chrome bricks or alkaline rammed overall lining, and
the masonry is divided into different parts.
AOD device
AOD is the English abbreviation for Argon Oxygen Decarburization. This device is a stainless steel refining device developed by Union Carbid Company in 1967. In October of the same year, the world's first AOD furnace was built in Jocelyn Stainless Steel Company in the United States. Due to the low equipment cost and few operational problems of this device, it quickly gained popularity in the world. 75% of the world's stainless steel is refined by AOD. The schematic diagram of A0D device is shown in Figure 2.
The
appearance is similar to the converter, but in fact it is still a refining
steel ladle. The main function is to blow the molten steel in the primary
smelting furnace (such as electric arc furnace), blow argon and oxygen in the
A0D to further decarburize the molten steel, and then refine it through
reduction and desulfurization to complete the purpose of adjusting the
composition. There are 2~4 double casing tuyere on the side wall of the molten
pool near the bottom of the furnace. The (O₂+Ar) mixed
gas is blown into the molten steel from the inner pipe, and Ar gas is blown
into the protective tuyere from the gap between the inner pipe and the outer
pipe. . The generated CO gas is diluted with Ar gas and its partial pressure is
reduced, and decarburization is performed while suppressing the oxidation loss
of Cr. Before AOD decarburization, the carbon content of molten steel is
1%~2.5%, and the temperature is about 1550°C. Change the Ar/O₂ ratio in
order to efficiently gradually decarburize from the high-carbon zone to the
low-carbon zone while suppressing the oxidation of Cr. When the carbon content
is reduced to the set carbon content, stop blowing oxygen and use Ar gas for
stirring.
During the beginning of oxygen blowing and oxidative decarburization, the oxidizability of the slag increased, and the temperature rose above 1700°C. In the reduction period, add ferrosilicon or aluminum to reduce the chromium in the slag and increase the alloy yield. Although the alkalinity of the slag is very low during this period, high alkalinity slag is required during the final lime desulfurization period. During the entire refining process, the slag changes from acidic to alkaline, and the atmosphere changes from oxidizing atmosphere to reducing atmosphere. In addition to intermittent operation, the furnace lining temperature is high and fluctuates greatly. AOD furnace lining generally uses magnesia-chrome bricks, which are gradually replaced by magnesia-calcium bricks.
There
are two main types of refractories used in AOD furnaces, one is
magnesia-chromium refractories, and the other is dolomite refractories. At
present, there is a trend towards dolomite refractories. Dolomite bricks or
magnesia-aluminum-carbon bricks are mostly used for tapping; the furnace body
and bottom are made of fired dolomite bricks or resin combined dolomite bricks;
the upper part is made of fired dolomite bricks or resin combined dolomite
bricks; the slag line is used for firing Mainly magnesia-forming dolomite
bricks; the tuyere adopts zirconium-containing sintered magnesian dolomite
bricks; bulk materials are mainly dolomite-based ramming materials or
cement-combined magnesia-based ramming materials.
VOD device
VOD
is the abbreviation of vacuum oxygen decarburization, also known as vacuum
oxygen decarburization. In this type of external refining equipment (see Figure
3), the ladle containing the molten steel in the converter or electric furnace
is placed in a vacuum chamber, and argon is blown from the bottom of the
ventilating brick to stir, and at the same time, vacuum is degassed, and then
oxygen is blown to the molten steel from the top to decarbonize And join the
ferroalloy. This method of producing low-carbon stainless steel with less
hydrogen, oxygen and non-metallic inclusions is a technology developed by
Witten in West Germany in collaboration with Standard-Messo in 1965, so it is
also called the Witten method.
The
high temperature of oxygen blowing (above 1700°C), slag intrusion and vacuum
conditions have caused VOD ladle lining refractories to withstand harsh service
conditions. The slag line and the molten pool wall adopt recombined
magnesia-chrome bricks and direct-combined magnesia-chrome bricks respectively.
In order to eliminate the harm of hexavalent chromium to human health, magnesia
chrome bricks are being gradually replaced by ultra-high temperature fired
directly bonded magnesia dolomite bricks. Recently, low-carbon magnesia-carbon
bricks, low-carbon magnesia dolomite bricks or aluminum-magnesium preforms have
been developed and applied.
VOD
furnace refractory configuration of several steel mills:
Use unit |
Bottom |
Slag line |
The rest |
|
Slag
line |
Slag
line |
|||
Steel 1 |
High aluminum |
Direct magnesia chrome brick and recombined
magnesia chrome brick |
High aluminum bricks |
|
Steel 2 |
Fired oil-impregnated dolomite brick |
Resin bonded dolomite brick |
Burning oil immersion directly combined with
dolomite bricks |
High aluminum bricks |
Japan |
Aluminum magnesium castable |
Semi-recombined magnesia chrome brick |
Directly combined with magnesia chrome brick |
|
High temperature fired magnesia dolomite
brick |
Ordinary fired dolomite brick |
|||
Europe |
Magnesia chrome brick and dolomite brick |
Ordinary Dolomite Brick |
Ordinary Dolomite Brick |
LF device
LF device is also called ladle refining furnace. This method was developed by Japan in 1971. The reduction refining process of the electric arc furnace is transferred to the ladle refining device with heating refining function, and the influence of the melting oxidation refining process of the electric arc furnace on the reduction refining process is minimized to ensure the reduction refining effect of the device.
The
LF device (see Figure 4) has a simple structure, basically adding a top cover
that can insert 3 graphite electrodes in the molten steel casting ladle (the
electrode is used for three-phase AC heating). Through the breathable brick
installed at the bottom of the ladle, inert gas (such as Ar gas) can be blown
into the molten steel, and the molten steel can be heated and stirred under the
reducing slag, which is excellent in deoxidation, desulfurization and reduction
of non-metal effect. Some LF furnaces are used in conjunction with VD (vacuum
degas s ing).
The
refractory materials commonly used in LF furnace are divided into slag line
part, furnace wall, furnace cover and bag bottom. The slag line is more
severely damaged under the erosion of high-alkalinity slag, and magnesia-carbon
bricks with good thermal shock properties are often used; LF furnace fireplace
slag penetration is more serious, and it is easy to cause structural peeling.
The traditional selection of high alumina bricks can no longer meet the needs
The use of carbon and MgO-added materials is used to overcome, and the refined
package lining has also been developed from the finalized to the indeterminate
direction; the furnace cover is basically castable; the furnace bottom is made
of cast large bricks or dry ramming. Beaten up.
ASEA-SKF device
A ladle refining equipment jointly developed by ASEA and SKF is shown in Figure 5.
The
equipment mainly includes arc heating device, vacuum degassing device,
electromagnetic induction stirring device, special ladle with non-magnetic
steel plate, alloy and other auxiliary raw material input device and ladle
mobile trolley capable of tilting and removing slag. The outstanding feature of
this equipment: remove the ladle vacuum degassing cover and replace it with the
electrode heating cover, it will perform arc heating and refining like an
electric furnace. The device is a device with multiple functions, which can
ensure the safety of molten steel degassing, the deoxidizer and alloy added into
the tank are evenly distributed, the temperature of molten steel can be
adjusted, and the refining of molten steel in the steelmaking furnace can be
partially transferred to this device. To shorten the refining time of the
steelmaking furnace. This method is also called arc heating electromagnetic
stirring refining method or electromagnetic stirring vacuum degassing method.
The
service conditions of ASEA-SKF ladle refractory lining are much harsher than
ordinary ladle. The temperature of molten steel in the tank is increased by
50~100℃,
and the residence time of molten steel in the tank is almost doubled. The slag
resistance of refractory materials in an oxidizing atmosphere is reduced by
half when the temperature is increased by 30-50°C. Under vacuum conditions,
molten slag penetrates into the brick along the pores of the binder and
destroys its structure. When the temperature of molten steel increases from
1650°C to 1700°C, the corrosion of all refractory materials (except fused-cast
bricks) increases by 1.5 to 2 times.
ASEA-SKF
ladle is in the use condition of severe temperature fluctuation, Radex-DB605
containing complex spinel combined with magnesia chrome brick (MgO57.3%, Al ₂0₃7.7%, Cr ₂O₃ 20.2%, Fe₂0₃ 12.7%, SiO₂0 .6%, bulk
density of 3.3g/cm³, apparent porosity of
13.5%, compressive strength of 35~45MPa, load softening temperature higher than
1750℃,
4h expansion at 1550℃ after heating by 0.1%, water cooling at 1300℃, weight loss
of 20% The thermal shock resistance of 10 times) has been recommended by most
countries for ASEA-SKF ladle working linings with severe temperature
fluctuations. (Some countries have tried this brick in the ASEA-SKF 150t ladle
slag line, and the service life is only 8 times). The slag line closest to the
electrode is best to be cast magnesia chrome brick. In recent years, these
magnesia chrome bricks have been gradually replaced by directly bonded magnesia
dolomite bricks or magnesia carbon bricks.
Typical
properties of recombined (semi-recombined) magnesia-chrome bricks at home and
abroad
performance
|
MgO/%
|
Cr2O3/%
|
CaO/%
|
SiO2/%
|
Al2O3/%
|
Fe2O3/%
|
Apparent
porosity /%
|
Bulk
density /g.cm-3
|
Compressive
strength /MPa
|
Load
softening temperature /℃
|
Linear
expansion rate /%
|
|
Grade
|
800℃
|
1400℃
|
||||||||||
QBDMGe12
|
75
|
15
|
1.3
|
1.5
|
3
|
4
|
16
|
3.18
|
50
|
1700
|
0.7
|
1.4
|
QBDMGe18
|
68
|
19
|
1.3
|
1.5
|
4
|
5.5
|
15
|
3.23
|
60
|
1750
|
0.7
|
1.4
|
QBDMGe20
|
65
|
20.5
|
1.3
|
1.7
|
4.2
|
7
|
15
|
3.26
|
60
|
1750
|
0.7
|
1.4
|
QBDMGe20
|
65
|
20.5
|
1.2
|
1.4
|
4
|
6.5
|
14
|
3.28
|
65
|
1750
|
0.7
|
1.4
|
QBDMGe22
|
63
|
22.5
|
1.2
|
1.4
|
4.5
|
7.5
|
14
|
3.23
|
65
|
1750
|
0.7
|
1.4
|
QBDMGe28
|
53
|
28
|
1.2
|
1.4
|
4
|
10
|
14
|
3.35
|
65
|
1750
|
0.7
|
1.4
|
Radex-DB60
|
62
|
21.5
|
0.5
|
1
|
6
|
9
|
18
|
3.2
|
|
1750
|
|
|
Radex-BCF-F-11
|
57
|
26
|
0.6
|
1.2
|
5.7
|
9
|
<16
|
3.3
|
|
1750
|
|
|
ANKROM52
|
75.2
|
11.5
|
1.2
|
1.3
|
6.4
|
4.2
|
17
|
3.38
|
90
|
1750
|
0.95
|
1.47
|
ANKROM56
|
60
|
18.5
|
1.3
|
0.5
|
6
|
13.5
|
12
|
3.28
|
90
|
1750
|
0.95
|
1.47
|
RS-5
|
70
|
20
|
|
<1
|
4
|
5
|
13.5
|
3.28
|
|
|
0.95
|
|
VAD device
VAD is the abbreviation for vacuum arc degassing. The vacuum arc degassing device is a device of the ladle degassing refining method (see Figure 6).
VAD
is a technology developed in 1968 by Finkl of the United States in
collaboration with Standard-Messo of West Germany. It is a method of producing
low-carbon stainless steel with less hydrogen, oxygen and non-metallic
inclusions. The device performs special refining in a ladle that receives
molten steel from a converter or electric furnace.
This method is very similar to ASEA-SKF, with the following two differences:
(1)
Its stirring is carried out with Ar gas like VOD;
(2)
It can be heated under vacuum (150~300Torr). Pack the steel that accepts molten
steel in the converter or electric furnace into a vacuum chamber, and conduct
electric arc heating while exhausting. In order to avoid the risk of discharge
below 100 Torr, the arc heating is stopped when the pressure of the vacuum
chamber is reduced to 200 Torr. When the exhaust is below 1 Torr, blow Ar gas
and stir for 6 to 10 minutes, then increase the pressure to 100 to 200 Torr for
arc heating, and blow Ar gas for 30 to 45 minutes for deoxygenation treatment.
(1Torr=133.3224Pa) The above are the six common refining devices outside the
furnace. In order to protect the metal structure of the cladding from the high
temperature of molten steel and molten slag, and to ensure the residence time
of molten steel in the ladle, the inner lining The choice of refractory
materials is also particularly important. At present, because the inner lining
of the ladle is damaged by molten steel and molten slag, erosion, high
temperature, etc., its service life is not very satisfactory. Both the
refractory industry and the steel industry are troubled by it, and the inner
lining of the ladle is damaged. Afterwards, major repairs or replacements are
required. These all take time. The unit consumption of domestic refractory
materials is still very high. The increase in refractory loss not only
increases the cost of steelmaking, but also affects the quality of steel.
Coupled with this year's national carbon neutrality and carbon peaking plan for
the steel industry, all have a great test for the refractory industry,
requiring technicians from various units to develop more energy-saving,
consumption-reducing and long-lived refractories.
LMM GROUP One stop service for steel industry, Refractory material ladle furnace
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