INSULATING, REFRACTORY MOLDED BODY, ESPECIALLY PLATE, AND PROCESS FOR ITS MANUFACTURE AND ITS USAGE

Abstract

An unfired, refractory molded body (1), especially a plate, especially for thermal insulation of molten metal and/or an ingot solidifying from molten metal, that includes a binding agent matrix (2) of a set binder and aggregate grains (3) of biogenic silicic acid, preferably of rice husk ash, which are incorporated into the binding agent matrix (2), wherein the binding agent matrix (2) consists of silica gel, as well as a process for its production and its usage.

Claims

1. An unfired, refractory molded body (1), especially plate, especially for thermal insulation of molten metal and/or an ingot (14) solidifying from molten metal, comprising a binding agent matrix (2) of a set binding agent and aggregate grains (3) of biogenic silicic acid, preferably of rice husk ash, which are incorporated into the binding agent matrix (2), characterized in that the binding agent matrix (2) is comprised of silica gel.

2. The molded body (1) according to claim 1, characterized in that the biogenic silicic acid is rice husk ash and/or diatomaceous earth and/or silica shale and/or diagenetically fossilized radiolaria skeletons or opal sponges.

3. The molded body (1) according to claim 1, characterized in that the aggregate of the molded body (1) is comprised of at least 50 wt. %, preferably of at least 80 wt. %, more preferably of at least 90 wt. %, especially preferably 100 wt. % of biogenic silicic acid, preferably of rice husk ash, with respect to the total dry mass of aggregate materials.

4. (canceled)

5. The molded body (1) according to claim 1, characterized in that the molded body (1) has a dry apparent density .sub.0 from 0.3 to 1.5 g/cm.sup.3, more preferably from 0.5 to 1.3 g/cm.sup.3 according to DIN EN 1094-4 (09/1995).

6. The molded body (1) according to claim 1, characterized in that the molded body (1) has a porosity of 60 to 90%, preferably from 70 to 80% according to DIN EN 1094-4 (09/1995).

7. The molded body (1) according to claim 1, characterized in that the molded body (1) has a cold compression strength of 0.5 to 15.0 MPa, preferably of 1.0 to 10.0 MPa according to DIN EN 993-5 (12/1998).

8. The molded body (1) according to claim 1, characterized in that the molded body (1) has a cold bending strength of 0.3 to 7.0 MPa, preferably of 0.5 to 5.0 MPa according to DIN EN 993-6 (04/1995).

9. The molded body (1) according to claim 1, characterized in that the molded body (1) has a hot bending strength of 0.5 to 5.0 MPa, preferably of 1.0 to 3.0 MPa according to DIN EN 993-7 (04/1995).

10. The molded body (1) according to claim 1, characterized in that the molded body (1) has a softening point, determined with a heating microscope according to DIN EN 51730 (09/2007), of 1500 to 1700 C., preferably of 1650 to 1700 C.

11. The molded body (1) according to claim 1, characterized in that the molded body (1) has the following thermal conductivities according to DIN EN 993-15 (07/2005): TABLE-US-00008 Thermal Conductivity [W/mK] Preferably At 26 C. 0.10 to 0.14 0.11 to 0.13 At 307 C. 0.12 to 0.16 0.13 to 0.15 At 700 C. 0.17 to 0.21 0.18 to 0.20 At 995 C. 0.25 to 0.29 0.26 to 0.28

12. (canceled)

13. A process for producing a molded body (1) according to claim 1, characterized by the following steps: a) Producing of a mixture comprising the biogenic silicic acid and silica sol, b) Filling the mixture into a mold, c) Compacting of the mixture, d) Demolding the green molded body (1), and e) Allowing the molded body (1) to set.

14. The process according to claim 13, characterized in that the composition of the mixture is adjusted such that the mixture has a slumpdetermined in reference to DIN EN ISO 1927-4 (03/2013)of 200 to 500 mm, preferably 250 to 350 mm.

15. The process according to claim 13, characterized in that the mixture has the following composition in relation to the total dry mass, wherein the individual components add up to 100 wt. %: TABLE-US-00009 Amount [wt. %] Preferably Biogenic silicic acid, preferably rice husk 40.0 to 95.0 65.0 to 90.0 Silicon dioxide as binding agent 5.0 to 30.0 10.0 to 20.0 Additional aggregate materials 0 to 20.0 0 to 10.0 Other components 0 to 10.0 0 to 5.0

16. The process according to claim 13, characterized in that the aggregate grains (3) of biogenic silicic acid are agglomerated with water and/or silica sol into granulate grains before mixing with the remaining components of the mixture, and the granulate grains are mixed with the remaining components of the mixture in a ductile state.

17. A use of a molded body (1) according to claim 1 for thermal insulation of molten metal, especially molten steel, and/or a metallic ingot (14) solidifying from the molten metal, preferably in steel production.

18. The use according to claim 17, characterized in that the molded body (1) is used for thermal insulation of the molten metal, particularly the molten steel, within a metallurgical vessel, and/or an ingot (14) within a metallurgical vessel, from the vessel and/or from the atmosphere.

19. The use according to claim 17, characterized in that the molded body (1) is used for thermal insulation of the molten metal, particularly of the molten steel, and/or of the ingot (14) in rising ingot casting.

20. The use according to claim 19, characterized in that the molded body (1) is used for thermal insulation of an ingot head (15) of the ingot (14).

21. The use according to claim 17, characterized in that the molded body is used as a cover plate (10) for covering and thermally insulating a metal bath (8), particularly a steel bath, within an ingot mold (7).

22. The use according to claim 17, characterized in that the molded body is used as a cover plate (19) for covering and thermally insulating a metal bath ((8), particularly a steel bath, within a casting distributor (20).

23. The use according to claim 21, characterized in that the cover plate (10; 19) is used for covering the metal bath (8) within the ingot mold (7) or the casting distributor (20) in rising or falling ingot casting.

24. A use of a molded body (1) according to claim 1 for thermal insulation of a refractory lining, especially in multi-layer masonry or in heat-treatment ovens or as a corrosion barrier, for example against alkali attack, or as a fire protection lining or as filter material for hot gases.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In the following, the present disclosure will be explained exemplarily in greater detail with the help of an illustration. Shown here:

[0026] FIG. 1schematically shows a cross-section through the molded body according to the present disclosure;

[0027] FIG. 2schematically and in a greatly simplified manner shows an ingot mold with a cover plate for rising ingot casting before the start of the casting process;

[0028] FIG. 3shows the ingot mold according to FIG. 2 during the casting process;

[0029] FIG. 4shows the ingot mold according to FIG. 2 at the end of the casting process;

[0030] FIG. 5schematically and in a greatly simplified manner shows a casting distributor before the casting; and

[0031] FIG. 6shows the casting distributor according to FIG. 5 after the casting.

[0032] The drawings are provided herewith for purely illustrative purposes and are not intended to limit the scope of the present invention.

DETAILED DESCRIPTION

[0033] The following description is merely exemplary in nature and is in no way intended to limit the present disclosure or its application or uses. It should be understood that throughout the description, corresponding reference numerals indicate like or corresponding parts and features.

[0034] The unfired refractory molded body 1 according to the present disclosure (FIGS. 1-6) comprises a binding agent matrix 2 of at least one set binding agent, in which aggregate grains 3 of biogenic silicic acid, preferably of rice husk ash, are embedded or incorporated. The aggregate grains 3 are distributed in the binding agent matrix 2.

[0035] According to the present disclosure, the binding agent matrix 2 consists entirely of silica gel. Silica gel is an amorphous silicon dioxide. As a result, the binding agent matrix 2 according to the present disclosure consists of amorphous silicon dioxide. As is known, silica gel is formed from silica sol, an aqueous, solvent-free, colloidal solution of amorphous silicon dioxide, by gelling to form SiOSi bridges and drying.

[0036] The biogenic silicic acid is preferably exclusively rice husk ash. However, it can also be diatomaceous earth (kieselguhr) or silica shale or diagenetically fossilized radiolaria or opal sponges. Mixtures of various biogenic silicic acids can also be present as an aggregate material.

[0037] Furthermore, the molded body 1 can also comprise additional aggregate materials of refractory material. Aggregate materials in the sense of the present disclosure are in general materials whose grains are distributed in the binding agent matrix 2 and are incorporated or embedded into it. During setting, the aggregate materials do not react or only superficially react with the binding agent. The aggregate grains are therefore essentially mechanically incorporated into the binding agent matrix 2.

[0038] The additional aggregate materials therefore preferably also consist of SiO.sub.2 like the biogenic silicic acid. In particular, they are microsilica, preferably pyrogenic and/or precipitated silicic acid. This has the advantage that the molded body 1 according to the present disclosure comprises a very high alkali resistance, as both the binding agent matrix 2 and the aggregate materials consist of amorphous SiO.sub.2.

[0039] The molded body 1 can also contain further aggregate materials which are not solely composed of SiO.sub.2. For example, the molded body can include expanded perlite and/or expanded vermiculite and/or expanded clay and/or inorganic fibers, preferably mineral and/or slag and/or glass and/or ceramic fibers, and/or fly ash and/or (power plant) filter dust as aggregate material. However, the amount of such aggregate material is preferably <20 wt. %, especially preferably <10 wt. %, in relation to the total content (dry mass) of aggregate materials.

[0040] Additionally, the aggregate of the molded body 1 consists preferably at least 50 wt. %, more preferably at least 80 wt.-%, especially preferably at least 90 wt. % of biogenic silicic acid, preferably of rice husk ash, with respect to the total content (dry mass) of aggregate materials. It is advantageous if the molded body 1 comprises exclusively biogenic silicic acid, preferably exclusively rice husk ash, as an aggregate material. The aggregate of the molded body 1 thereby consists preferably 100 wt. % of biogenic silicic acid, preferably 100 wt. % of rice husk ash.

[0041] The production of the molded body 1 according to the present disclosure takes place as follows. First, the dry components are mixed. The dry components are the biogenic silicic acid and if applicable the other additives as well as possibly amorphous silicon dioxide as a binding agent. Next, water is added to the dry mixture to moisten the silicon dioxide, so that the silicic acid is activated.

[0042] It is advantageous, however, to add the amorphous silicon dioxide already in dissolved, dispersed, or colloidally dispersed form, i.e. as silica sol, as a liquid to the dry mixture of the other components. The amorphous silicon dioxide can also be mixed with the other components partially in dry form and partially as silica sol.

[0043] The composition of the finished mixture is preferably adjusted so that the mixture comprises a slumpdetermined in reference to DIN EN ISO 1927-4 (03/2013)of 200 to 500 mm, preferably 250 to 350 mm, without separation of the coarse and fine grain fractions taking place, as is the case with pure rice husk ash.

[0044] Preferably the finished mixture/the batch for production of the molded body 1 comprises the following composition of dry components in relation to the total dry mass, wherein the individual components add up to 100 wt. %:

TABLE-US-00001 Amount [wt. %] Preferably Biogenic silicic acid, preferably rice husk 40.0 to 95.0 65.0 to 90.0 ash Silicon dioxide as binding agent 5.0 to 30.0 10.0 to 20.0 Other components 0 to 30.0 0 to 15.0
Furthermore, the weight ratio of the liquid solvent, preferably of the water, to the dry ingredients is preferably 2:1 to 1:9, more preferably 1:1 to 3:7.

[0045] The rice husk ash used also preferably comprises the following chemical composition according to DIN EN ISO 12677 (02/2013), wherein the individual components (without ignition loss) add up to 100 wt. %:

TABLE-US-00002 Amount [wt. %] preferably SiO.sub.2 92 to 98 94 to 97 P.sub.2O.sub.5 0.5 to 2.0 0.5 to 1.5 K.sub.2O 1.0 to 3.0 1.5 to 2.5 Remaining oxides 0.5 to 3.0 1.0 to 2.0

[0046] The biogenic silicic acid used, especially the rice husk ash, also comprises the following grain distribution according to DIN 66165-2 (04/1987) in relation to the dry mass, wherein the individual components add up to 100 wt. %:

TABLE-US-00003 Amount [wt. %] Grain size [mm] preferably 2.0 0 to 3.0 0.01 to 0.5 <2.0-1.0 0.05 to 4.0 0.1 to 2.0 <1.0-0.5 1.0 to 40.0 1.5 to 35.0 <0.5-0.3 3.95 to 40.0 8.39 to 30.0 <0.3 30.0 to 95.0 40.0 to 90.0

[0047] The bulk density of the biogenic silicic acid used, especially of the rice husk ash, according to DIN EN 1097-3 (06/1998) is preferably 0.05 to 0.5 g/cm.sup.3, preferably 0.1 to 0.4 g/cm.sup.3.

[0048] The finished mixture is subsequently put into a mold and compacted within it. Compaction is effected especially by superimposed load vibration or uniaxial pressing.

[0049] For superimposed load vibration, the mold is located on a vibration table. A weight is placed on the finished mixture inside the mold, the vibration table is activated, and the mixture is compacted by vibration. Smaller forms are usually produced by load vibration.

[0050] For uniaxial pressing, the mold filled with the finished mixture is placed into a press, wherein a cover plate is placed onto the mixture. Then the upper stamp of the press is pushed against the cover plate and the mixture is thus compressed with a specific pressure. Preferably, multiple pressing strokes are used. Larger forms are usually produced by uniaxial pressing.

[0051] After compaction, the green molded body is demolded and allowed to set. Setting takes place in particular at temperatures between 110 and 200 C. for preferably 4 to 12 hours. The temperature is chosen such that the binding agent sets or hardens. This range lies beneath the temperature for ceramic firing. Thus the molded body 1 according to the present disclosure is unfired.

[0052] The molded body 1 according to the present disclosure then preferably comprises a dry apparent density .sub.0 between 0.3 and 1.5 g/cm.sup.3, more preferably between 0.5 and 1.3 g/cm.sup.3 according to DIN EN 1094-4 (09/1995).

[0053] Additionally, the molded body 1 preferably has a porosity of 60 to 90%, preferably between 70 and 80% according to DIN EN 1094-4 (09/1995).

[0054] The cold compression strength of the molded body 1 preferably lies at 0.5 and 15.0 MPa, more preferably at 1.0 and 10.0 MPa according to DIN EN 993-5 (12/1998).

[0055] The cold bending strength of the molded body 1 is preferably at 0.3 and 7.0 MPa, more preferably at 0.5 and 5.0 MPa according to DIN EN 993-6 (04/1995).

[0056] The hot bending strength of the molded body 1 preferably amounts to 0.5 to 5.0 MPa, more preferably to 1.0 to 3.0 MPa according to DIN EN 993-7 (04/1995).

[0057] Additionally, the molded body 1 preferably has a softening point, determined with a hot stage microscope according to DIN EN 51730 (09/2007), between 1500 and 1700 C., preferably between 1650 and 1700 C. Therefore the molded body 1 is ideal for long-duration/permanent use at very high temperatures.

[0058] Additionally, the molded body 1 preferably has the following thermal conductivities according to DIN EN 993-15 (07/2005):

TABLE-US-00004 Thermal Conductivity [W/mK] Preferably At 26 C. 0.10 to 0.14 0.11 to 0.13 At 307 C. 0.12 to 0.16 0.13 to 0.15 At 700 C. 0.17 to 0.21 0.18 to 0.20 At 995 C. 0.25 to 0.29 0.26 to 0.28

[0059] The molded body 1 according to the present disclosure also preferably comprises the following chemical composition according to DIN EN ISO 12677 (02/2013), wherein the individual components add up to 100 wt. %:

TABLE-US-00005 Grain size [mm]Amount [wt. %] Preferably SiO.sub.2 93.0 to 99.0 95.0 to 98.0 P.sub.2O.sub.5 0.2 to 1.5 0.5 to 1.3 K.sub.2O 0.3 to 2.5 0.5 to 2.2 Remaining 0.5 to 3.0 1.0 to 1.5

[0060] As already explained, the molded body 1 according to the present disclosure is used for thermal insulation of molten metal, especially molten steel, from the surrounding environment. The molded body 1 is preferably used for thermal ingot head insulation during rising ingot casting.

[0061] An ingot casting apparatus 4 (FIGS. 2 and 3) for rising ingot casting of metal, particularly of steel, usually comprises a sub-frame 5 with a casting channel 6 for feeding the molten metal, particularly the steel. Additionally, the ingot casting apparatus 4 comprises a tubular ingot mold 7 for receiving a bath 8 of molten metal. The ingot mold 7 comprises a lower and an upper, open, ingot mold end 7a;b. The upper ingot mold end 7b forms an ingot mold head 9 of the ingot mold 7.

[0062] According to one favorable aspect of the present disclosure, the molded body 1 is used as a cover plate 10 for covering the upper open ingot mold end 7b. For this purpose, the cover plate 10 is placed on the ingot mold head 9 before beginning the ingot casting (FIG. 2). The placement on the ingot mold 7 thus takes place without direct contact with the metal bath 8. The metal bath 8 is thereby indirectly, i.e. without direct contact, thermally insulated by the cover plate 10. A casting powder bag filled with casting powder is fastened on the cover plate 10 in such a way that it hangs down from the cover plate 10 inside the ingot mold 7. For fastening the casting powder bag 11, the cover plate 10 preferably comprises a central recess 12 extending from one plate surface to the other.

[0063] At this point the molten metal, particularly the molten steel, is fed through the casting channel 6 into the ingot mold 7 from below, and rises upward within it (FIG. 3). The metal bath 8, particularly the steel bath, generally has a temperature of approximately 1550 C. Therefor the casting powder bag 11 burns away in a short time due to the intense heat of the molten steel, so that the casting powder is distributed over the surface 8a of the molten metal and forms a superficial casting powder layer 13. The casting powder is additionally distributed between the ingot mold 7 and the metal bath 8 and acts as a separating and a lubricant agent.

[0064] The metal bath 8 rises to the cover plate 10 during pouring and forms a solidifying ingot 14 with an upper ingot head 15 (FIG. 4). The cover plate 10 isolates the ingot head 15 from the atmosphere and thereby provides for slow cooling of the ingot head 15.

[0065] According to a further favorable aspect of the present disclosure, the molded body 1 is used as an insulating plate 16 for a casting hood/insulating hood 17 for thermal insulation of the ingot head 15 from the ingot mold 7, especially from the ingot mold head 9. The ring-shaped insulating hood 17 consists of multiple insulating plates 16 which are connected with one another and which are adjacent to one another in a circumferential direction. It serves as an inner lining of the ingot mold head 9. The insulating hood 17 thus lies on the inside of the ingot mold wall 18. It can also project over the ingot mold 7 on the upper ingot mold end 7b (not shown). In this case it is used particularly together with loose bulk material for insulating the surface 8a of the metal bath 8, which is suctioned away at the end of the casting process.

[0066] The insulating hood 17 can also be constructed as a single piece and the molded body 1 is thus used as an insulating hood 17.

[0067] The molded body 1 can also advantageously be used as a cover plate for covering/insulating the free surface 8a of the metal bath 8 in a different metallurgical vessel, open at the top. In particular, the molded body 1 can be used as a cover plate 19 for a casting distributor 20 (FIGS. 5 and 6), preferably a continuous casting distributor (tundish).

[0068] Before casting, the casting distributor 20 is preferably covered with multiple cover plates 19 (FIG. 5). During casting, the metal bath 8 rises to the cover plates 19. These form a continuous insulating cover layer covering the surface 8a of the metal bath 8.

[0069] The molded body 1 can also advantageously be used as a cover plate for covering/insulating the exposed surface 8a of the metal bath 8 in a ladle or in troughs.

[0070] The molded body 1 can also be placed directly onto the surface 8a of the metal bath 8, so that it floats upon the surface 8a.

[0071] Additionally, the molded body 1 can be used as thermal insulation in multi-layer masonry or for refractory linings in heat-treatment furnaces or as a corrosion barrier (for example against alkali attack) or as a fire protection lining or as filter material for hot gases.

[0072] The molded body 1 according to the present disclosure comprises low thermal conductivity at low temperatures as well as at high temperatures, and thereby comprises outstanding insulating properties. When used for ingot head insulation in rising ingot casting, this ensures a constantly good ingot head quality. The good thermal insulation results in particular from the very good insulating properties of the biogenic silicic acid and its very high melting point of approximately 1650 C.

[0073] Furthermore, the molded body 1 according to the present disclosure is alkali resistant and comprises excellent fire resistance. This results from the combination of alkali-resistant and highly fire-resistant biogenic silicic acid, especially the rice husk ash, with silica sol as a binding agent. This is because the SiO.sub.2 bond of the silica gel ensures a high level of alkali resistance and fire resistance of the binding agent matrix.

[0074] Furthermore, the molded body 1 is free of pollutants. Additionally, the rice husk ash is a natural recycling product.

[0075] By using the cover plate 10 simultaneously as a retaining plate for the casting powder bag 11 and subsequently for insulation of the ingot head 15, an additional step in the process is eliminated. This is because removing the retaining plate and subsequently introducing the loose rice husk ash is not necessary.

[0076] Additionally, dust pollution is markedly reduced. Placement of cover plates 10; 19 on the mold 7 or the casting distributor 20 is also markedly easier than applying loose bulk material to the surface 8a of the metal bath 8. Additionally, this can take place before the pouring of the molten metal, which means a markedly lower temperature stress for the respective worker.

[0077] In the context of the present disclosure, it is also the case that, during production, the biogenic silicic acid, particularly the rice husk ash, is granulated with water and/or silica sol before mixing with the other components, and the soft or ductile, not-yet-set granulate is mixed with the remaining components. In compaction or pressing, the ductile granules are destroyed, so that the molded body is formed with the aggregate grains from the biogenic silicic acid. An advantage of this variant of the process is that there is less dust produced.

EXAMPLE

[0078] A plate according to the present disclosure was produced from a batch with the following composition by uniaxial pressing:

TABLE-US-00006 Amount [wt. %] liquid SiO.sub.2 binding agent (Kstrosol 2030) 50 Rice husk ash (NERMAT BF-E) 50

[0079] The finished mixture was compacted with a surface weight of 0.5 N/mm.sup.2. The plate was demolded and dried at 150 C. for 12 hours in a drying oven on a sheet and allowed to set. The plate comprised the following dimensions: 67067040 mm.sup.3. The plate produced had the following characteristics:

TABLE-US-00007 Dry apparent density .sub.0 (DIN EN 1094-4 (09/1995)) 0.61 g/cm.sup.3 Porosity (DIN EN 1094-4 (09/1995)) 74.65% Cold compression strength (DIN EN 993-5 (12/1998)) 1.5 N/mm.sup.2 Cold bending strength (DIN EN 993-6 (04/1995)) 0.6 N/mm.sup.2

[0080] Within this specification, embodiments have been described in a way which enables a clear and concise specification to be written, but it is intended and will be appreciated that embodiments may be variously combined or separated without parting from the invention. For example, it will be appreciated that all preferred features described herein are applicable to all aspects of the invention described herein.

[0081] While the above description constitutes the preferred embodiments of the present invention, it will be appreciated that the invention is susceptible to modification, variation and change without departing from the proper scope and fair meaning of the accompanying claims.