JP4847400B2 - Manufacturing method of heat insulating material, alumina-spinel refractory heat insulating material, kiln furnace, heat insulating material construction method, and heat insulating material recycling method - Google Patents

Description

  The present invention is resistant to erosion to molten steel, molten metal, basic slag, etc., and has a low thermal conductivity alumina-spinel refractory heat insulating material and heat insulating material manufacturing method, kiln furnace container, heat insulating material construction method, and The present invention relates to a method for recycling the heat insulating material.

The fire-resistant and heat-insulating brick is a brick that has both fire resistance that can withstand high temperatures and heat insulation that blocks heat and does not escape to the outside, and is widely used as an energy-saving brick directly on the hot surface or on the back of the fire-resistant brick.
However, in general, fireproof heat-insulating bricks have high porosity, so they are inferior in corrosion resistance and are basically made of SiO ₂ -Al ₂ O ₃ (mullite), which is resistant to molten metal and molten basic slag. Corrosion resistance was insufficient. For this reason, it is rarely used in furnaces that handle hot metal / molten steel such as kneading wheels, converters, hot metal / molten steel pans, degassing furnaces, and tundishes.

  Moreover, since the conventional heat insulating material is low in strength, it is easily broken by the compressive stress accompanying the thermal expansion of the refractory brick. In addition, repeated heating and cooling have various problems that pulverization is considered to be caused by linear shrinkage. Therefore, in order to insulate the furnace that handles hot metal and molten steel, the early development of high-strength fire-resistant insulation, especially fire-resistant and heat-insulated panels, is difficult to be eroded by molten metal and molten steel and molten slag. There was a strong demand from the handling industry.

  Therefore, as a method for producing an alumina-spinel refractory insulating brick with low thermal conductivity and strong resistance to thermal shock, after mixing magnesia clinker powder, sintered alumina powder, and bonded clay in a predetermined ratio, a pore forming material Has been proposed, a method for producing a heat-resistant and heat-insulating brick in which water is added and then molded and subjected to a dry firing finish (for example, see Patent Document 1).

JP-A-53-39308

However, in the manufacturing method disclosed in Patent Document 1, since refractory clay is used as a binder, the heat insulating brick obtained contains a large amount of SiO ₂ , and as described above, The problem of the occurrence of pulverization due to insufficient corrosion resistance and reheating shrinkage still remained.

  In the present invention, in order to solve such problems, a method for producing a heat insulating material having high heat insulation performance even at high strength, high corrosion resistance and low reheat shrinkage, and its heat insulating material, kiln furnace container, heat insulating material It aims at providing the construction method and the recycling method of a heat insulating material.

The gist of the present invention is as follows.
(1) 4 to 17 parts by mass of magnesia clinker powder having a purity of 95% by mass or more and a maximum particle size of 100 μm or less; 70 to 82 parts by mass of alumina powder having a purity of 99% by mass or more and a maximum particle size of 310 μm or less; and mixed with 20 parts by weight, 4-16 parts by weight of MgO, _Al 2 _{O 3} and 80 to 93 parts by weight, in the range of 2 to 4 parts by weight of CaO, and, MgO: mass of _Al 2 _{O 3} After setting the ratio to 1: 5-25,
A method for producing a heat insulating material, comprising adding a pore forming material and performing a heat treatment.
(2) In addition to the pore forming material, hydrogen peroxide solution or hydrogen peroxide solution and a foaming agent are added, and the apparent porosity is continuously or stepwise in the vertical direction from the casting surface by casting. (1) The method for manufacturing a heat insulating material according to (1), wherein the heat treatment is performed after the change.

(3) 4 to 16 parts by mass of MgO, 80 to 93 parts by mass of Al ₂ O _{3 and 2} to 4 parts by mass of CaO, SiO ₂ is not contained except for inevitable impurities, and MgO: Al ₂ The mass ratio of O ₃ is 1: 5 to 25, the apparent porosity is 50% by volume or more, the thermal conductivity at 350 ° C. is 0.7 W / (m · K) or less, and the compressive strength is 5 MPa or more and 1500 ° C. An alumina-spinel refractory heat insulating material having a reheat shrinkage of -0.05% or more.
(4) The alumina-spinel refractory heat insulating material according to (3), wherein the apparent porosity changes continuously or stepwise.

(5) A furnace vessel characterized in that the heat insulating material according to (3) or (4) molded into a brick shape or a panel shape is attached to at least a part.
(6) The heat insulating material is fixed to the iron skin of the kiln vessel with a bolt through a fixing hole provided in the heat insulating material, and the bolt head is covered with a refractory castable or mortar. The kiln container as described in (5) characterized by these.

(7) A heat insulating material construction method for attaching the heat insulating material according to (3) or (4) to at least a part of a kiln container,
The heat insulating material is molded into a brick shape or a panel shape,
A fixing hole is provided in the heat insulating material, and the heat insulating material is fixed to the iron skin of the furnace vessel with a bolt through the hole.
A method for constructing a heat insulating material, wherein the bolt head is covered with a fireproof castable or mortar.
(8) A method for recycling a heat insulating material, wherein the waste material of the heat insulating material used hot in the kiln vessel described in (5) or (6) is utilized as a refractory raw material.

  According to the present invention, a heat insulating material having high corrosion resistance and high strength can be manufactured. Therefore, since the heat insulating material of the present invention can be applied as a permanent or semi-permanent tension of the kiln container by sticking to a part or the entire surface of the kiln container, the heat radiation from the iron skin of the kiln container is prevented. In addition to being suppressed and energy saving can be realized, the lining of the present invention is applied when the wear material is worn, thereby preventing leakage and leakage of steel.

In addition, since the heat-insulating material of the present invention has a small reheating shrinkage rate, even if heating and cooling of the molten metal container is repeated, the occurrence of powdering and cracking, which are considered to be caused by linear shrinkage, can be suppressed, and the life can be extended. .
On the other hand, the permanent tension material and the semi-permanent tension material have not been recycled so far. However, the heat insulating material of the present invention has received a sufficient heat history so that there is no change in volume, and the alumina-spinel quality. Therefore, it can be recycled as a high fire-resistant aggregate.

As described above, the conventional method for producing a heat insulating material has a problem such as insufficient corrosion resistance due to containing a large amount of SiO ₂ in the obtained heat insulating brick. Focusing on not containing SiO ₂ as much as possible, by using alumina cement instead of refractory clay, high strength and high corrosion resistance can be secured, and reheating shrinkage at high temperatures can be suppressed. I found out that it was possible.

Specifically, the following two points were improved by using alumina cement instead of refractory clay.
The first point, without having to deliberately blending SiO ₂ component as a binder, equivalent to general refractory bricks, or more improvement in corrosion resistance is achieved in, was also improved strength at hot.
The second point is that it is possible to suppress reheating shrinkage at high temperatures by utilizing the expandability generated by the reaction of the CaO component in the alumina cement. Due to the expansion reaction at the high temperature, the joint is not opened when the actual furnace is used, so that there is an effect of preventing the hot water from the joint.
Hereinafter, the configuration of the present invention will be described in detail.

In the production of the alumina-spinel refractory heat insulating material of the present invention, 4 to 17 parts by mass of magnesia clinker powder having a purity of 95% by mass or more and a maximum particle size of 100 μm or less, and alumina powder having a purity of 99% by mass or more and a maximum particle size of 310 μm or less 70 to 82 parts by mass and 10 to 20 parts by mass of alumina cement are added and mixed.
Here, the chemical composition after mixing is 4 to 16 parts by mass of MgO, 80 to 93 parts by mass of Al ₂ O ₃ , ₂ to 4 parts by mass of CaO, and MgO: Al ₂ O ₃ It mix | blends so that mass ratio may be set to 1: 5-25.
For example, 10 to 20 L of pore forming material is added to and mixed with 100 kg of the above mixed raw material, kneaded after adding predetermined water, cast-molded, demolded, dried, or dried and then tunnel kiln Then, for example, a heat treatment such as firing at about 1500 ° C. is performed.
As the pore forming material, flammable materials such as sawdust and polystyrene that disappear upon firing, or hollow refractory particles such as pearlite are preferable.

The upper limit values of the maximum particle size of the magnesia clinker powder and alumina powder are specified as described above. When the particles exceeding the specified maximum particle size are used, the maximum particle size becomes too coarse and the formation of spinel This is because, since the reaction is greatly delayed, prolonged firing is required, which is not economical, and the correlation between the specific gravity of the bulk and the compressive strength is lower than that of a general refractory product.
Here, the correlation between the bulk density and compression strength is generally high for general refractory products. Therefore, by grasping the bulk density, it should be used as an index of compression strength. Can do. However, as described above, if the maximum particle size becomes too coarse, the correlation between the bulk density and the compressive strength decreases, and the bulk density cannot be used as an index of the compressive strength, which is inconvenient in production management. .
Therefore, by defining the upper limit of the maximum particle size as described above, the spinel formation reaction can be carried out in a short time in the heat treatment step, and the correlation between the bulk density and the compressive strength after the heat treatment is increased. It can be stabilized.

Further, since the particle diameters of the magnesia clinker powder and the alumina powder are not particularly problematic even if they are small, the lower limit value is not particularly defined, and is preferably set appropriately in consideration of the pulverization cost and the like.
Furthermore, the purities of the magnesia clinker powder and the alumina powder are respectively defined as described above. When the purity of the magnesia clinker is less than 95% by mass, SiO ₂ , Fe ₂ O _{3 and the} like are mixed on the production method and starting materials. It becomes a factor that lowers fire resistance.
On the other hand, if the alumina powder has a purity of less than 99% by mass, the alkali component is mixed and abnormal expansion occurs due to the spinelization reaction during the heat treatment.

  The raw materials were blended in 4-17 parts by mass of magnesia clinker powder, 70-82 parts by mass of alumina powder, and 10-20 parts by mass of alumina cement because magnesia reacted with alumina during heat treatment to produce spinel. This is because no free magnesia is left unreacted with alumina.

Next, about the chemical composition after mixing each raw material, MgO was made into 4-16 mass parts, when MgO is less than 4 mass parts, corrosion resistance is inferior, and when it exceeds 16 mass parts, it is unreacted at the time of heat processing. This is because MgO remains and lacks digestion problems and volume stability during repeated heat treatment.
The reason why 80 to 93 parts by mass of Al ₂ O ₃ is set based on the mixing ratio with MgO for the above-mentioned reason including the alumina component in the alumina cement.
The reason why the CaO content is 2 to 4 parts by mass is that if the CaO component in the alumina cement is less than 2 parts by mass, the strength development is weak and crack breakage occurs, and if it exceeds 4 parts by mass, oversintering occurs during use and the corrosion resistance is increased. Is due to deterioration.

Furthermore, as a result of investigating the relationship between the mass ratio of MgO and Al ₂ O ₃ and the corrosion resistance of molten steel, the corrosion resistance was good when the mass ratio of MgO: Al ₂ O ₃ was 1: 5 to 25.
Furthermore, when the mass ratio of MgO: Al ₂ O ₃ is in the range of 1: 5 to 13, the corrosion resistance is the highest, no cracks are generated or deformed, and sintering is favorable, which is preferable.
In particular, when the mass ratio of MgO: Al ₂ O ₃ is in the range of 1: 5 to 8, the reheating shrinkage rate at 1500 ° C. slightly expands, which is more preferable.

In the blending of the raw material of the present invention, it is possible to replace part of the magnesia clinker and sintered alumina with the cutting powder of the product.
Moreover, it is preferable to replace part of the sintered alumina with calcined alumina because the heat treatment temperature can be relaxed.
Further, in the production of the alumina-spinel refractory heat insulating material of the present invention, it is possible to add a mineralizer for promoting spinelization, such as alkali fluoride, lithium carbonate, boric acid and the like.

The alumina-spinel refractory heat insulating material of the present invention has MgO in the range of 4 to 16 parts by mass, Al ₂ O _{3 in} the range of 80 to 93 parts by mass, CaO in the range of 2 to 4 parts by mass, and MgO: Al ₂ O _3. The mass ratio is 1: 5 to 25, the apparent porosity is 50% by volume or more, the thermal conductivity at 350 ° C. is 0.7 W / (m · K) or less, the compressive strength is 5 MPa or more, and reheating at 1500 ° C. Shrinkage is -0.05% or more.
Here, MgO is in the range of 4 to 16 parts by mass, Al ₂ O ₃ is in the range of 80 to 93 parts by mass, CaO is in the range of 2 to 4 parts by mass, and the mass ratio of MgO: Al ₂ O ₃ is 1: 5 to 25. The reason for the definition is as described above.
In addition, SiO ₂ can be allowed to be mixed as an unavoidable impurity, but it is preferable not to contain it as much as possible.

Next, the reason why the apparent porosity is set to 50% by volume or more is that if it is less than 50% by volume, the thermal conductivity inevitably increases and the heat insulating property is impaired.
The upper limit of the apparent porosity is not particularly specified, but is preferably 70% by volume or less considering the strength.
The thermal conductivity at 350 ° C. was set to 0.7 W / (m · K) or less because the thermal conductivity of the magnesia refractory heat insulating material was 1.3 W / (m · K) and the heat of the alumina refractory heat insulating material. Heat conductivity of furnaces that handle molten metals such as kneading cars, converters, hot metal / molten steel pans, degassing furnaces, and tundishes, with a conductivity that is significantly smaller than that of 1.0 W / (m · K). It is because it can exhibit an excellent heat insulation effect and can greatly save energy. The lower limit of the thermal conductivity is not particularly specified, but is preferably 0.2 W / (m · K) or more in view of strength.

The reason why the compressive strength is set to 5 MPa or more is that the compressive strength is considered to be equal to or higher than those of A, B, and C of JIS standard heat insulating bricks that have been used stably in terms of strength.
Since the upper limit of the compressive strength is preferably as high as possible, it is not particularly specified.
Furthermore, the reason why the reheat shrinkage rate at 1500 ° C. is set to −0.05% or more is that shrinkage cracks do not occur at the time of use, and it is possible to prevent gaps from being generated between panels in the expandable joint mortar. It depends. The upper limit value of the reheating shrinkage rate is not particularly specified, but is preferably set to -0.01% or less.

As another embodiment of the present invention, in performing the above-described method of the present invention, in addition to the pore forming material, hydrogen peroxide water, or hydrogen peroxide water and a foaming agent are added, and cast molding is performed. Heat treatment may be performed after the apparent porosity is changed continuously or stepwise in the vertical direction from the casting surface.
Specifically, for example, after first kneading only with water, hydrogen peroxide solution or hydrogen peroxide solution and foaming agent are added, mixed uniformly, and then cured in a dryer at 45 ° C. for 24 hours. . Thereafter, drying and baking are further performed.
Further, the foaming agent is not particularly limited as long as foaming foam is stabilized as fine as possible, but examples include zinc stearate, calcium stearate, aluminum stearate, zinc maleate, and maleene. Fatty acid metal salts such as calcium acid, castor oil surfactants, animal proteins such as casein, and the like can be used.

By such a method, it is possible to obtain a heat insulating material whose apparent porosity is changed continuously or stepwise (hereinafter, sometimes referred to as an inclined material).
This graded material has the advantage that it is dense on the working surface side close to the hot metal and molten steel, and has higher corrosion resistance and higher apparent porosity and lower thermal conductivity on the iron skin side, so it can retain heat insulation. Can be used for permanent or semi-permanent tensioning of kiln furnace facilities that hold

The construction method of the heat insulating material for attaching the heat insulating material of the present invention to at least a part of the kiln container is to form the heat insulating material into a brick shape or a panel shape, provide a fixing hole in the heat insulating material, The heat insulating material may be fixed to the iron shell of the furnace vessel with a bolt, and the bolt head may be covered with a refractory castable or mortar.
Here, a material such as a refractory castable covering the bolt head or a high alumina plastic material is suitable.

According to such a construction method, the heat insulating material of the present invention formed into a brick shape or a panel shape is applied as a refractory for permanent tension or semi-permanent tension on a part or the whole surface of the furnace vessel. Therefore, there is an advantage that simplification of the furnace construction work and prevention of falling off during tilting and reversal of the furnace vessel can be realized.
Also, through the fixing holes provided in this heat insulating material, the heat insulating material is fixed to the iron skin of the furnace vessel with bolts, and the bolt head is covered with refractory castable or mortar, There is an advantage that, unlike brick construction, no molten metal or molten steel is inserted into the joints, and at the same time, the locally damaged parts can be replaced without skill.

Moreover, the heat insulating material of the present invention is used hot in the above-mentioned kiln furnace container, reaches the end of its life after being used for a predetermined time, and becomes a waste material.
In general, permanent or semi-permanent materials have not been recycled because of the high content of SiO _{2 in the form} of a waxy brick or chamotte brick.
However, the waste material of the heat insulating material according to the present invention can be utilized as a highly fire-resistant aggregate because the material itself has received a sufficient heat history and has no volume change, and has an alumina-spinel quality. Become. Therefore, the waste material can be recycled as a refractory raw material by pulverizing and sizing.
The refractory raw material can be recycled into, for example, a wear material or a spray repair material.

Example 1
13 parts by mass of magnesia clinker powder with a purity of 95% by mass and a maximum particle size of 100 μm (all), 22 parts by mass of sintered alumina with a purity of 99% by mass and a maximum particle size of 310 μm (all), coarse powder of calcined alumina After adding 15 parts by mass of alumina cement to 15 parts by mass of alumina cement and 15 parts by mass of alumina cement after adding 20 parts by mass of average grain size of 50 μm, 30 parts by mass of average particle diameter of 4 μm calcined alumina, and adding 15 L of expanded polystyrene as a pore-forming material After mixing and adding 29 parts by mass of added moisture, the mixture was kneaded, cast into an inner size of 250 mm × 130 mm × 85 mm, demolded, dried with a dryer, and then fired at 1500 ° C. in a tunnel kiln.

  The physical properties of the resulting alumina-spinel refractory heat insulating material according to Example 1 are as shown in Table 1 below. The apparent porosity is 50% by volume or more, and the thermal conductivity at 350 ° C. is 0.7 W / (m · K). Hereinafter, the reheating shrinkage rate at a compressive strength of 5 MPa or more and 1500 ° C. could be −0.05% or more. Each physical property value was measured in accordance with JIS shown in Table 1 below.

(Example 2)
15 parts by mass of magnesia clinker powder with a purity of 95% by mass and a maximum particle size of 100 μm (all through), 20 parts by mass of sintered alumina with a purity of 99% by mass and a maximum particle size of 310 μm (all through), and coarse particles of calcined alumina After adding 24 parts by mass of 50 μm in diameter, 28 parts by mass of the average particle size of calcined alumina 4 μm, and 13 parts by mass of alumina cement, 17 L of expanded polystyrene was added to and mixed with 100 kg of the mixed raw material as a pore forming material. After adding and kneading 29 parts by mass of added water, the mixture was cast into an internal size of 250 mm × 130 mm × 85 mm, demolded, dried with a dryer, and then fired at 1500 ° C. in a tunnel kiln.

  The physical properties of the obtained alumina-spinel refractory heat insulating material according to Example 2 are as shown in Table 2 below. The apparent porosity is 50% by volume or more, and the thermal conductivity at 350 ° C. is 0.7 W / (m · K) or less. Further, the compressive strength was 5 MPa or more, and the reheating shrinkage rate at 1500 ° C. could be −0.05% or more.

(Evaluation by slag rotation erosion method)
The slag rotation erosion method (for example, see the Refractory Notebook '99. P.64 Refractory Technology Association (1999)) for the corrosion resistance test of the heat insulating material manufactured in Example 1 and Example 2 and general refractory bricks. Were used for comparison. As test conditions, the gas burner temperature was adjusted to 1550 ° C., and molten steel pan slag having a basicity (CaO / SiO _{2 on a} mass basis) of 3.2 was added for 4 hours, and the amount of wear was investigated. In addition, the general refractory brick used as a comparative example employ | adopted the thing of the alumina spinel quality, the high alumina quality, and the wax quality. Table 3 shows the evaluation results of Examples 1 and 2 and the comparative example.

According to this result, the refractory insulation according to Example 1 and Example 2 has an apparent porosity of 50% by volume or more, a thermal conductivity at 350 ° C. of 0.7 W / (m · K) or less, and a compressive strength. The reheat shrinkage rate at 5 MPa or more and 1500 ° C. was −0.05% or more, had excellent heat insulation properties, was excellent in corrosion resistance, and exhibited excellent properties from the viewpoint of crack prevention.
On the other hand, in the alumina-spinel refractory brick of the comparative example, although the thermal conductivity was satisfactory, the strength characteristics and the reheating shrinkage ratio were large, and the cracks were generated after the erosion test.
On the other hand, the high alumina refractory bricks and the fauxite refractory bricks of the comparative examples do not satisfy the heat insulation in terms of thermal conductivity.

(Example 3)
3 L of expanded polystyrene is added to and mixed with 100 kg of the mixed raw material as a pore forming material to the raw material blended in Example 1, and after adding 29 parts by mass of added water and kneading, hydrogen peroxide (concentration of 10 mass) as a blowing agent. %) When 5 parts by mass are quickly added and uniform, the curing temperature is maintained at 30 ° C., the apparent porosity is continuously changed in the casting direction, and the panel has a thickness of 60 mm, a height of 400 mm, and a width of 500 mm. I made a board.
As a result, the apparent porosity of the panel plate according to Example 3 on the operating surface side of about 30 mm was 58% and the back surface was 70%.

The panel board which concerns on this Example 3 was applied to the permanent tension material of a 300-ton molten steel pan. As a result, even when the end of the service life was reached after 300 times (accepting and discharging the molten steel once), the molten steel did not leak and could be applied without permanent damage.
About the molten steel temperature loss during this period, compared with the case of applying general waxy brick, the molten steel temperature drop from molten steel receiving steel to the completion of casting averaged 5.5 ° C / heat throughout the furnace. It turns out that there are few.

Example 4
Next, a part of the permanent upholstery material applied to Example 3 was dismantled and collected, and after crushing and magnetic separation, the particle size of 1 to 3 mm was adjusted with a sieve, and the alumina-spinel wet spraying material was externally hooked. 15% by mass was added and applied to the side wall of the molten steel pan.
As a result, compared with the case where the wet spraying material which does not apply the recycled material was used, the durability which was inferior was shown. That is, the average life span of the wet-sprayed material of alumina-spinel containing no recycled material is 20 heat, while the wet spray material added with 15% by weight of the recycled material of the present invention has an average life of 20 heat. The number of useful lifespans was shown, and it was possible to contribute to reducing the basic unit of repair materials.

Claims (8)

4 to 17 parts by mass of magnesia clinker powder having a purity of 95% by mass or more and a maximum particle size of 100 μm or less, 70 to 82 parts by mass of alumina powder having a purity of 99% by mass or more and a maximum particle size of 310 μm or less, and 10 to 20 parts by mass of alumina cement And MgO is 4 to 16 parts by mass, Al2O3 is 80 to 93 parts by mass, CaO is 2 to 4 parts by mass, and the mass ratio of MgO: Al2O3 is 1: 5 to 25. Then
A method for producing a heat insulating material, comprising adding a pore forming material and performing a heat treatment.   In addition to the pore-forming material, hydrogen peroxide solution or hydrogen peroxide solution and foaming agent are added and cast to change the apparent porosity continuously or stepwise in the vertical direction from the casting surface. After that, the heat processing is performed, The manufacturing method of the heat insulating material of Claim 1 characterized by the above-mentioned. MgO is 4 to 16 parts by mass, Al ₂ O ₃ is 80 to 93 parts by mass, CaO is 2 to 4 parts by mass, SiO ₂ is not contained except for inevitable impurities, and MgO: Al ₂ O ₃ Reheating shrinkage at a mass ratio of 1: 5 to 25, an apparent porosity of 50% by volume or more, a thermal conductivity at 350 ° C. of 0.7 W / (m · K) or less, a compressive strength of 5 MPa or more and 1500 ° C. Alumina-spinel refractory heat insulating material characterized by a rate of -0.05% or more. 4. The alumina-spinel refractory heat insulating material according to claim 3, wherein the apparent porosity changes continuously or stepwise.   A kiln furnace container characterized in that the heat insulating material according to claim 3 or 4 formed into a brick shape or a panel shape is attached to at least a part thereof.   Through the fixing hole provided in the heat insulating material, the heat insulating material is fixed to the iron skin of the furnace vessel with a bolt, and the bolt head is covered with a refractory castable or mortar. The kiln furnace container according to claim 5. A heat insulating material construction method for attaching the heat insulating material according to claim 3 or 4 to at least a part of a kiln container,
The heat insulating material is molded into a brick shape or a panel shape,
A fixing hole is provided in the heat insulating material, and the heat insulating material is fixed to the iron skin of the furnace vessel with a bolt through the hole.
A method for constructing a heat insulating material, wherein the bolt head is covered with a fireproof castable or mortar.   A method for recycling a heat insulating material, wherein the waste material of the heat insulating material used hot in the kiln container according to claim 5 or 6 is used as a refractory raw material.