Technical field
[0001]
　The present invention relates to monolithic refractories which are used primarily in steel-making apparatus.
　This application claims the September 29, 2015, 2015-191739 Patent Application No. filed in Japan, and, on September 15, 2016, priority based on Japanese Patent Application No. 2016-180517 filed in Japan and, the contents of which are incorporated here.
Background technique
[0002]
　In steelmaking processing apparatus, a refractory in contact with molten steel and slag, alumina - magnesia, alumina - monolithic refractory of spinel are frequently used, generally the alumina in the binder of the monolithic refractory cement is used. These monolithic refractory is given shape is given by the construction methods poured after water kneaded, alumina cement Ca of the binder during curing 2+ ions and Al (OH) 4 - and ions are eluted precipitated form hydrates, required strength is expressed as a structure. Further, Ca eluted from alumina cement 2+ ions and Al (OH) 4 - Since ions agglutinate micronized, strength is also expressed by this agglomeration. Generally alumina cement, CaO · Al 2 O 3 , CaO · 2Al 2 O 3 was used as a main component, a portion of the alumina cement 12CaO · 7Al 2 O 3 and Al 2 O 3 and also contain the like, CaO Al · 2 O 3 , CaO · 2Al 2 O 3 and 12CaO · 7Al 2 O 3 from Ca 2+ ions and Al (OH) 4 - ions are eluted.
[0003]
　Thus, while alumina cement is an important raw material for imparting strength to the monolithic refractories, since the alumina cement has a high content of CaO, occur in other raw materials and steel making process in monolithic refractories to form the TeiTorubutsu reacts with slag, there is a drawback of lowering the corrosion resistance against slag monolithic refractories.
[0004]
　Therefore, and monolithic refractories which is cured by a reaction of a polyvalent metal salt of magnesia and oxycarboxylic acid without using alumina cement disclosed in Patent Document 1, Ca is shown in Patent Document 2 X Sr 1- X Al 2 O 4 castable refractory for use as a binder has been proposed.
CITATION
Patent Document
[0005]
Patent Document 1: Japanese Patent Laid-Open 11-130550 Patent Public
Patent Document 2: Japanese Patent No. 2008-290934 PR
Summary of the Invention
Problems that the Invention is to Solve
[0006]
　Monolithic refractory which is cured by a reaction of the polyvalent metal salt of magnesia and oxycarboxylic acids shown in Patent Document 1, Mg eluted from magnesia raw 2+ polyvalent metal salt ion and oxy-acid is reacted coupling part is produced by gelling Te. Therefore, in order to obtain sufficient cure conditions, it must be used very fine active magnesia feedstock. If you do not use the very fine active magnesia raw materials, Mg 2+ for elution rate of ions is slow, monolithic refractories strength development is very slow, and becomes low intensity. On the other hand very finely active magnesia raw material, and carbonation by carbon dioxide in the air, may hydroxide by steam is to inert occurs, the magnesia raw material by storage conditions is thus inactivate , monolithic refractories are very slow strength development, and become low intensity.
[0007]
　Further, Ca is shown in Patent Document 2 X Sr 1-X Al 2 O 4 castable refractory for use as a binder, as compared with monolithic refractories using conventional alumina cement hydrate slow strength development for production of slow and low intensity. Ca X Sr 1-X Al 2 O 4 from, Ca 2+ ions and Al (OH) 4 - Sr addition to ion 2+ because ions are eluted, to increase the strength by agglomeration to increase the amount of ultrafine powder is possible some, but for sintering proceeds at a high temperature by increasing the amount of ultrafine powder, castable refractory is heat spalling resistance decreases, the greater the occurrence of cracking peeling during use.
[0008]
　Therefore, an object of the present invention is to solve is not using alumina cement, or to quickly strength development of the amount of alumina cement is very low, CaO content is less castable refractory, and, It is to a high strength.
Means for Solving the Problems
[0009]
　The present invention is summarized as follows.
(1) One aspect of the present invention, a percentage of the 100% by mass of the refractory raw material particle size 8 mm, Ca X Sr 1-X Al 2 O 4 (where, 0 ≦ X ≦ 0.5) a content of 0.5 wt% to 10 wt%, the content of the polyvalent metal salts of oxycarboxylic acid is monolithic refractory which is more than 0.05 wt% 1.0 wt% or less.
(2) In the monolithic refractory according to (1), the content of the polyvalent metal salt of the hydroxycarboxylic acid may be 1.0% by mass or less than 0.1 wt%.
(3) In the monolithic refractory according to (1) or (2), a proportion of 100 mass% of the refractory material grain size 8 mm, Ca X Sr 1-X Al 2 O 4 (where, 0 ≦ X ≦ 0.5) and Ca Y Sr 1-Y Al 4 O 7 (where, 0 ≦ Y ≦ 0.5) and 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3 (where, 0 ≦ Z total content of ≦ 0.5) may be not more than 10 wt%.
(4) In the monolithic refractory according to any one of the above (1) to (3), a proportion of the refractory raw material 100 wt%, the content of the particle diameter 0.1mm or less magnesia raw material 3 it may be less mass% to 12 mass%.
(5) In the monolithic refractory according to any one of the above (1) to (3), a proportion of the refractory raw material 100 wt%, the content of the particle diameter 0.1mm or less of the spinel material 5 it may be less mass% to 25 mass%.
(6) above (1) in the monolithic refractory according to any one of (5), a proportion of the refractory raw material 100% by weight, mean particle diameter of 0.1mm super 8mm following alumina raw material and a spinel material at least one total content of may be not more than 75 wt% or more 55% by weight.
It is in.
Effect of the invention
[0010]
　According to this aspect of the present invention, Ca as a binder X Sr 1-X Al 2 O 4 By using a combination of polyvalent metal salt of the hydroxycarboxylic acid, polyvalent metals conventional magnesia and oxycarboxylic acid faster curing than those using a combination of salts, and can obtain a monolithic refractory of high strength, aging in the case of long-term storage becomes very small. Further, Ca X Sr 1-X Al 2 O 4 fast much cure than using alone, and it is possible to obtain a monolithic refractory of high strength. That is, according to the above aspect of the present invention, not using alumina cement, or the amount of the alumina cement is very low, and faster strength development of CaO content is less castable refractory, and high it is possible to strength, it is possible to reduce the change over time during long-term storage.
DESCRIPTION OF THE INVENTION
[0011]
　Hereinafter, the monolithic refractory according to an embodiment of the present invention will be described in detail.
　Monolithic refractory according to the present embodiment mainly, alumina - magnesia castable refractory, alumina - may be applied to the spinel monolithic refractories.
[0012]
　Monolithic refractory according to the present embodiment is alumina - when a monolithic refractory of magnesia, typically, the main raw material of alumina raw material, magnesia raw material and ultrafine silica, Ca X Sr 1-X Al 2 O 4 (where, 0 ≦ X ≦ 0.5) composed of and a binding material consisting of polyvalent metal salts of oxycarboxylic acids, and admixtures for use in conventional monolithic refractory admixture. However, if there is no problem with the digestion of magnesia during drying, such as if the hot strength is important, it is not to use ultrafine silica. Further, for the purpose of enhancing corrosion resistance, a portion of the alumina raw material and a magnesia raw material can be used in replacement of the spinel material.
[0013]
　Monolithic refractory alumina according to the present embodiment - when a monolithic refractory of spinel is typically a main raw material comprising alumina raw material and a spinel raw material, Ca X Sr 1-X Al 2 O 4 (where, 0 ≦ X ≦ 0.5) composed of and a binding material consisting of polyvalent metal salts of oxycarboxylic acids, and admixtures for use in conventional monolithic refractory admixture. Further, for the purpose of increasing the corrosion resistance or heat spalling resistance, a portion of the alumina raw material and a spinel material can be used to replace the magnesia raw material.
[0014]
　Here, the admixture, organic fibers, Al powder used in conventional castable refractory, means a metal fiber or the like, the admixtures, water-reducing agents used in conventional castable refractory, AE agent, a defoaming agent, curing modifiers, fluidity modifiers, magnesia digestion inhibitor refers to explosion inhibitor like. And in this specification, the entire raw materials of the monolithic refractory excluding the admixture of the refractory material.
[0015]
　Monolithic refractory according to the present embodiment, as a binder, Ca X Sr 1-X Al 2 O 4 (where, 0 ≦ X ≦ 0.5) using a polyvalent metal salt of hydroxycarboxylic acid with . Ca of monolithic refractories in that water and kneaded X Sr 1-X Al 2 O 4 is, Sr 2+ ions, Ca 2+ ions, Al (OH) 4 - eluted ions, polyvalent metal salts of oxycarboxylic acid It reacts with these ions eluted gelled strength is expressed. Ca X Sr 1-X Al 2 O 4 in the use of only the intensity expressed to produce the slow hydrates slow, and when it becomes low intensity, a combination of a polyvalent metal salt of a hydroxycarboxylic acid, oxy since the formation of the coupling portion due to gelation of the polyvalent metal salt of a carboxylic acid is added, early strength development, and become high strength.
[0016]
　According to monolithic refractories according to the present embodiment, faster strength development than a method of producing a bonded portion by a combination of a multivalent metal salt of a conventional very fine active magnesia raw material and an oxycarboxylic acid, and high It becomes strength. This, Mg of magnesia feedstock 2+ Ca than ion elution amount X Sr 1-X Al 2 O 4 Sr from 2+ ions, Ca 2+ ions, Al (OH) 4 - that elution of ions is large, further, Ca than using magnesia raw material X Sr 1-X Al 2 O 4 with mixing water is considered to be because become high pH. The reaction between MgO and water, MgO + H 2 O → Mg (OH) 2 was, Mg (OH) 2 in the dissolved amount of the water 100 g (25 ° C.) of about 1 mg, pH of the dissolved water of about 10. 5 is. In contrast, Ca X Sr 1-X Al 2 O 4 reacting with SrO and water in the, SrO + H 2 O → Sr (OH) 2 is, Sr (OH) 2 to water 100 g (25 ° C.) dissolution amount is about 1 g, pH of the dissolved water is about 13.5. Thus, Sr (OH) 2 is the amount of dissolved water more, i.e. Ca X Sr 1-X Al 2 O 4 Sr from 2+ estimated that many elution of ions, mixing water when dissolved goes high pH It is. Polyvalent metal salts of oxycarboxylic acid gelation proceeds the pH is high, for example, basic aluminum lactate, which is one of the polyvalent metal salts of oxycarboxylic acids when the pH is 10 or higher, gelation progresses It has been reported. Ca X Sr 1-X Al 2 O 4 how to use, many elution of ions than using the conventional magnesia raw material, and, since a high pH, the polyvalent metal salt of hydroxycarboxylic acid fast gelation, it is estimated that many of the gel formed.
[0017]
　Also, combinations of polyvalent metal salts of conventional magnesia raw material and an oxycarboxylic acid for express strength only by gel formation of the polyvalent metal salts of oxycarboxylic acids, Ca X Sr 1-X Al 2 O 4 polyvalent combination of metal salt, polyvalent gel-forming metal salt and Ca of oxycarboxylic acids and oxycarboxylic acids X Sr 1-X Al 2 O 4 of the hydrate formation will occur at the same time, further high strength complexed Do coupling portion is estimated to be generated. Again it, monolithic refractories according to the present embodiment is faster strength development than prior art, and is considered as a factor to be high strength.
[0018]
　Furthermore, a method of producing a bonded portion by a combination of a multivalent metal salt of conventional magnesia raw material and an oxycarboxylic acid, Mg of magnesia as described above 2+ since ion elution amount is small, and fast production of the joint, in order to increase the production amount, it is necessary to use a very fine active magnesia feedstock. However, very fine active magnesia raw material, and carbonation by carbon dioxide in the air, may hydroxide by steam is to inert occurs, the magnesia raw material by storage conditions is thus inactivate , monolithic refractories are very slow strength development, and becomes a low-intensity, Ca in this embodiment X Sr 1-X Al 2 O 4 in the use of less deterioration due to such changes over time.
[0019]
　A combination of a polyvalent metal salt of a conventional magnesia raw material and an oxycarboxylic acid, to deduce how to use a combination of polyvalent metal salts of the same alkaline earth which is an oxide of a metal strontia (SrO) material and oxycarboxylic acid can, but simply applying this combination, monolithic refractories are flowability becomes difficult construction reduced in a short time when kneaded with water. This strontia a large amount of Sr reacts with vigorous exothermic water 2+ so rapidly eluted ions is considered gelling polyvalent metal salts of oxy-acids are also to be because proceed rapidly. We refer to strontia Ca X Sr 1-X Al 2 O 4 when used as a composite oxide, Sr 2+ elution rate of ions can be suppressed, therefore, gelation rate of the polyvalent metal salt of hydroxycarboxylic acid can also control the curing speed suitable for the construction of suppressed castable refractory was found to be a high strength as described above.
[0020]
　A combination of a multivalent metal salt of an alumina cement and oxycarboxylic acids, Ca eluted from alumina cement 2+ ions, Al (OH) 4 - is a polyvalent metal salt of a hydroxycarboxylic acid is Strength gelled by ionic, Ca X Sr 1-X Al 2 O 4 and towards the combination of polyvalent metal salts of oxycarboxylic acid strength development is faster and become high strength. This reaction between CaO and water in the alumina cement is CaO + H 2 O → Ca (OH) 2 is, Ca (OH) 2 pH amount dissolved in 0.14g of the water 100 g (25 ° C.) is since about 12.4, Ca X Sr 1-X Al 2 O 4 towards is ion elution amount is large, presumably because the water for kneading is higher pH. Further, since the amount of CaO of irregular shaped refractories are many turned to the corrosion resistance decreases when using the alumina cement, Ca for use in severe conditions X Sr 1-X Al 2 O 4 with a hydroxycarboxylic acid multilingual monolithic refractory according to the present embodiment using valent metal salt are suitable.
[0021]
　In monolithic refractory according to the present embodiment, Ca X Sr 1-X Al 2 O 4 usage is less than 10 mass% to 0.5 mass% as a proportion of 100 mass% of the refractory material grain size 8mm to. Is less than 0.5 wt%, the curing of the castable refractory is slow and the strength is insufficient. Further, curing is too fast for monolithic refractories and is more than 10 wt%, heat spalling resistance decreases more likely to sintering at high temperatures. Further, Ca X Sr 1-X Al 2 O 4 for the value of X in the 0 ≦ X ≦ 0.5. This is because X is increased many becomes the CaO content than 0.5, the corrosion resistance of monolithic refractories is degraded. X is better is as small as possible, since the CaO content in the castable refractory is small, the corrosion resistance of monolithic refractories increases and may be zero.
[0022]
　In the monolithic refractories according to the present embodiment, Ca X Sr 1-X Al 2 O 4 in the same CaO-SrO-Al 2 O 4 is a solid solution of Ca Y Sr 1-Y Al 4 O 7 ( However, 0 ≦ Y ≦ 0.5) and 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3 (provided that can be used ≦ Z ≦ 0 0.5), Ca X Sr 1 -X Al 2 O 4 and Ca Y Sr 1-Y Al 4 O 7 and 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3 the total amount of 100 mass% of the refractory material grain size 8mm of it is preferable that the 10 mass% or less as a percentage of the. When many consisting 10% by weight is easily sintered at a high temperature heat spalling resistance is lowered. Although for the Y and Z values and 0 ≦ Y ≦ 0.5,0 ≦ Z ≦ 0.5, which is Ca X Sr 1-X Al 2 O 4 when the same Y and Z and is more than 0.5 becomes large CaO content, the corrosion resistance of monolithic refractories is lowered. Ca Y Sr 1-Y Al 4 O 7 With Ca X Sr 1-X Al 2 O 4 than slower curing of monolithic refractories, 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3 because cured when using the faster, easily adjust the curing time of monolithic refractories by used in combination.
[0023]
　In the monolithic refractories according to the present embodiment, if necessary Ca X Sr 1-X Al 2 O 4 , Ca Y Sr 1-Y Al 4 O 7 , 12 (CaO) Z (SrO) 1- Z · 7Al 2 O 3 may be used, alumina cement in addition to, the CaO contained in the alumina cement reduces the corrosion resistance of monolithic refractories, Ca X Sr 1-X Al 2 O 4 , Ca Y sr 1-Y Al 4 O 7 , 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3 , 0 total CaO contained in the alumina cement is a proportion of 100 mass% of the refractory material grain size 8mm it is preferable that the .5 mass or less.
[0024]
　Ca X Sr 1-X Al 2 O 4 as a production method of, limestone (primarily CaCO 3 ), quicklime (mainly CaO), purified alumina (alpha-Al 2 O 3 , Al (OH) 3 ) or bauxite ( al 2 O 3 raw material), stolons thiane ore (SrCO 3 ) and celestite (SrSO 4 a) as a raw material, blended material so that the molar ratio of the desired composition, an electric furnace, a reverberatory furnace, open-hearth, vertical in type furnace or shaft kiln or a rotary kiln, 1100 ° C. or more, preferably 1300 ° C. or more, more preferably include a method of melting or firing at a high temperature of at least 1500 ° C.. CaO in the raw material, Al 2 O 3 and that the sum of high purity more than 98% by weight of SrO is preferred. TiO contained in bauxite and celestite 2 , MgO, Fe 2 O 3 impurities such is thereby degrades the physical properties at high temperatures, it is preferable that as much as possible small quantities.
[0025]
　These temperatures and melting and firing time are those vary specifications such furnace volume and heating capacity, actually confirmed the formation phase after melting and firing the sample in X-ray diffraction, an object of the Ca X Sr 1- X Al 2 O 4 it is important to confirm the formation presence or absence of.
[0026]
　Before melting or firing, it is preferable that an average diameter of 50% of these ingredients with a pulverizer is pulverized to about 0.5 ~ 100 [mu] m. To include coarse particles than this, there are cases where part of the unreacted remaining number, the original effect of the monolithic refractory according to the present embodiment is less likely to be exhibited. Also, after melting or firing, then cooled, it is preferred to granulated into 1 ~ 20 [mu] m about particle size by a pulverizer. The particle size, laser diffraction method or a laser scattering method, or a result of measurement by the particle size analysis equipment such as sedimentation balance method, represents the 50% average diameter.
[0027]
　The mixing of the raw materials, can be homogenized Eirich mixer, rotary drum, a cone blender, V type blender, omni mixer, Nauta mixer, a mixing machine such as a pan type mixer.
[0028]
　The crusher can be used a vibration mill, tube mill, a ball mill, industrial pulverizer such as a roller mill. It is also possible to use pulverized part of the material used for monolithic refractories simultaneously. For example, Ca X Sr 1-X Al 2 O 4 when the use by grinding calcined alumina simultaneously, Ca in monolithic refractories X Sr 1-X Al 2 O 4 so that the calcination of alumina uniformly dispersed , be kneaded with a small water monolithic refractories better the fluidity, strength is increased.
[0029]
　Ca Y Sr 1-Y Al 4 O 7 and 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3 is, Ca X Sr 1-X Al 2 O 4 in the same manner as, the composition of interest raw material can be produced by blending such that the molar ratio. Further, Ca X Sr 1-X Al 2 O 4 not only phase, Ca Y Sr 1-Y Al 4 O 7 phase or 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3 phase and to coexist raw material blended can be produced in a similar manner.
[0030]
　In monolithic refractory according to the present embodiment, the amount of polyvalent metal salts of oxycarboxylic acids, and 0.05 mass% to 1.0 mass% as a proportion of 100 mass% of the refractory material 8mm . 0.05 is less than mass% is insufficient slow curing strength of monolithic refractories, is more than 1.0% by mass when cured during the drying of monolithic refractories, which is considered to be generated by the contraction of the gel contraction increases, volume stability is poor. If a short time to implement de-frame of the mold and cores, or if the construction at a low temperature, the amount of the polyvalent metal salts of oxycarboxylic acid to hasten hardening, 8 mm below the refractory material 100 wt% preferably 0.1 wt% to 1.0 wt% or less as a percentage of the.
[0031]
　Examples of the polyvalent metal salt of a hydroxycarboxylic acid, glycolic acid, lactic acid, hydroacrylic acid, oxybutyric acid, glyceric acid, malic acid, tartaric acid, aluminum salt of an aliphatic oxycarboxylic acid such as citric acid, iron salts, chromium salts, zirconium salts, normal salts and basic salts such as titanium salts can be used. For example, it is generally aluminum lactate, commercially available basic aluminum lactate, aluminum glycolic acid, lactic acid-glycolic acid aluminum, basic lactic acid-glycolic acid aluminum.
[0032]
　Monolithic refractory according to the present embodiment is alumina - if a magnesia castable refractory, a proportion of 100 mass% of the refractory material grain size 8 mm, Ca X Sr 1-X Al 2 O 4 (where, 0 ≦ X ≦ 0.5) 0.5 wt% to 10 wt%, the multivalent metal salt together containing 1.0 wt% or less than 0.05 wt% of a hydroxycarboxylic acid, further, the particle size 0. preferably includes the following magnesia raw material 1 mm 3 mass% to 12 mass%. With this adjustment, a suitable time for strength development, high strength, high corrosion resistance and slag invasive, and can be heat spalling resistance obtain high monolithic refractories.
[0033]
　Further, monolithic refractories according to the present embodiment is alumina - if a spinel castable refractory, a proportion of 100 mass% of the refractory material grain size 8 mm, Ca X Sr 1-X Al 2 O 4 ( However, 0 ≦ X ≦ 0.5) 0.5 wt% to 10 wt%, a polyvalent metal salt with containing 0.05 mass% to 1.0 mass% of a hydroxycarboxylic acid, further, the particle size preferably it includes the following spinel material 0.1 mm 25 mass% 5 mass% or more or less. With this adjustment, a suitable time for strength development, high strength, high corrosion resistance and slag invasive, and can be heat spalling resistance obtain high monolithic refractories.
[0034]
　In monolithic refractory according to the present embodiment, the particle size 0.1mm super 8mm below the refractory material comprising an aggregate can mainly constituting at least one of alumina raw material and a spinel material. Typically, a proportion of the particle size 8mm following refractory raw material 100% by weight, mean particle diameter of 0.1mm at least one total of 75 mass 55 mass% or more in a content of super 8mm following alumina raw material and a spinel material % or less.
[0035]
　To illustrate the refractory raw material (main raw material) which can be suitably used for monolithic refractories according to the present embodiment described above is as follows.
[0036]
　The alumina raw material, using a raw material which is produced by fused or sintered particle size control, the raw material produced by the Bayer process which is called a calcined alumina. Alumina raw material which is produced the particle size adjusted by fused or sintering, Al 2 O 3 content of 90 mass% or more, preferably used not less than 99 mass%. Calcined alumina is a material called a reactive Alumina or Calcined Alumina.
[0037]
　The spinel material, MgO-Al 2 O 3 with a compound of the type, chemical composition MgO · Al 2 O 3 stoichiometry and MgO or Al of 2 O 3 non-stoichiometric compounds having the composition is excessively dissolved , and the use of raw material which is produced is size adjusted by fused or sintered. Spinel and alumina can also be used raw materials combined.
[0038]
　The magnesia raw material, using a raw material which is particle size control is produced by fused or sintered. As cracks magnesia raw material according to volume expansion digestion does not occur during drying, it is preferable to digestion resistant uses high magnesia raw material. The digestion resistant high magnesia raw material, CaO and SiO as impurities 2 CaO / SiO in the 2 is low, having no fracture surface, which is like those surface coating. Since the magnesia raw material to produce a spinel by reacting with alumina raw material in use, the fine spinel to generate and use a magnesia raw material becomes fine increased corrosion resistance and slag invasive, volume expansion by using the coarse magnesia raw material cracks less indicates residual expandable to monolithic refractories with the speed of the spinel product is slowed continues showing.
[0039]
　Ultrafine silica, silica flour, silica fume, fumed silica, micro silica, evaporated silica, or particle size, referred to as silica dusts following amorphous SiO 1 [mu] m 2 in feedstocks, Si, Fe-Si, ZrO 2 which SiO gas generated during the production of the like produced by oxidation in air is generally used. Ultrafine silica, alumina - the magnesia castable refractory, digestion prevention of magnesia material, reducing the expansion due to the spinel product, for the purpose of imparting such creep property during use, 100 mass% of the refractory material grain size 8mm a proportion of it is preferably used in a range of 2 mass% or less.
[0040]
　As the refractory raw material of the monolithic refractory according to the present embodiment, it is also possible to use the recycled spent refractory bricks, or a castable refractory, the so-called recycle material. As the recycle material, alumina - spinel, or alumina - and refractory bricks of the used of magnesia, it is preferable to reuse the monolithic refractories.
[0041]
　Furthermore, the castable refractory according to the present embodiment, to reduce the occurrence of cracking and peeling preventing extension of cracks, or for the purpose of enhancing the corrosion resistance by dense large aggregate particle size is larger than 8mm refractory raw material it is also possible to use. However, its amount is preferably below 40 wt% by outer percentage based on 100 mass% of the refractory material grain size 8 mm.
[0042]
　Further, the monolithic refractory according to the present embodiment, as other refractory material, zirconia, mullite, alumina - zirconia, zirconia - mullite, but it is also possible to use chromia, etc., these usage, grain a proportion of 100 mass% of the refractory material diameter 8 mm, it is preferable to 10 wt% or less.
[0043]
　Monolithic refractory according to the present embodiment described above can be suitably used for casting construction, wet spray installation.
Example
[0044]
　Tables 1 to 3 illustrate Examples 1 to 29 and Comparative Examples 1 to feed configurations and evaluation results of 5 of the present invention.
[0045]
[Table 1]

[0046]
[Table 2]

[0047]
[table 3]

[0048]
　Each of the embodiments, in the comparative example, as a refractory raw material, Al 2 O 3 content is a particle size range 99.5 wt% 8-0.1Mm and 0.1mm or less sintering alumina, MgO content 27 sintered spinel particle size range is less 8-0.1mm and 0.1mm in mass%, calcined alumina having an average particle diameter of 1.5 [mu] m, MgO content is a particle size range 95.2 wt% 0. 1mm or less of the sintered magnesia, MgO content of 97.7% by weight BET specific surface area of 144m 2 active magnesia / g, SiO 2 average particle size in a content of 98 mass% is 0.2μm silica flour, CaO 25 wt% of alumina cement content, Ca X Sr 1-X Al 2 O 4 , Ca Y Sr 1-Y Al 4 O 7 , 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3, oxy polyvalent metal salt of a carboxylic acid, Polycarboxylic acid-based water reducing agent and the curing modifier was appropriately using 0.2 mass% in total as fine admixture.
[0049]
　Ca X Sr 1-X Al 2 O 4 , Ca Y Sr 1-Y Al 4 O 7 , 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3 was prepared by the following method, respectively. As raw materials, CaCO having 99 wt% 3 a, SrCO purity 98 wt% 3 and, using high-purity α- alumina purity of 99 mass%. The chemical composition of Table 1 to Table 3 (the value of X, the values of Y, the value of Z) and each raw material was weighed in a balance so that, with respect to raw materials were mixed by a mortar, a 1 mass% in outer percentage after the granule was added water, heat treatment of 48 hours at siliconit electric furnace 1400 ° C., then was allowed to cool at the temperature was lowered to room temperature in air, respectively those pulverized in a ball mill Ca X Sr 1-X Al 2 O 4 , Ca Y Sr 1-Y Al 4 O 7 , 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3 was used as a.
[0050]
　Further, polyvalent metal salts of oxycarboxylic acid, was used polyvalent metal basic aluminum lactate as salt A, polyvalent metal salts basic lactic acid-glycolic acid aluminum as B of oxycarboxylic acids oxycarboxylic acid.
[0051]
　Table 1 "curing time" in through Table 3 is within 8 hours curing time 3 hours or more in the case of curing the kneaded material at 20 ° C. with the amount of water Proper fluidity can be obtained, the steelmaking apparatus and with a ○ mark as appropriate as construction. Further, if less than 2 hours or more 3 hours little short, or with a slightly longer ones △ mark within 12 hours more than 8 hours, less than 2 hours and either very short or a longer than 12 hours is given × are marked.
[0052]
　"Aging" is the curing time of the material stored in the paper bag 90 days was measured in the same conditions as "curing time" in the preceding paragraph, ○ mark that changes in curing time was within 15%, from 15% △ mark those were within large 30%, and with a × mark those greater than 30%.
[0053]
　"Drying shrinkage" is after curing of suitable casting the kneaded material into the shape of 40 × 40 × 160 mm in the amount of water is obtained fluidity, 24 hours dry test piece at 110 ° C. after 24 hours aging at 20 ° C. longitudinal shrinkage after drying is put ○ mark to what was as small as less than 0.1%. Further, with the △ mark those greater than 0.1% were within 0.2%, and with a × mark those greater than 0.2%.
[0054]
　"Flexural strength", "drying shrinkage" measure the three-point bending strength of 110 ° C. after drying the test piece was measured, and with a ○ mark those were high strength and more 8 MPa. Moreover, what it was less than 8MPa at 5MPa or more △ mark, and with the × mark in those was the low intensity than 5MPa.
[0055]
　"Rotation erosion Spall" 24 hours a test piece prepared by casting the kneaded material in the amount of water adequate fluidity is obtained at 20 ° C. curing, after drying for 24 hours at 110 ° C., the slag rotary erosion test device with, [after holding the converter slag charged to 1 hour test piece was heated to 1650 ° C., to discharge the slug 30 minutes cooling] operations repeated 5 times, the crack caused by melting and spalling evaluated. Those occurrence of corrosion and cracking were minor Both ○ mark is either insignificant, if not extremely be other bad △ mark, if not both minor and with the × mark .
[0056]
　"Comprehensive evaluation" is a very good thing ○ also each evaluation Any ◎ mark, △ those remaining is good ● Among one is ○ mark, △ is what the rest of ○ with two △ mark, and the other is with the × mark. ◎, ○, △, it is shown that a bad evaluation in the order of ×.
[0057]
　Table 1, Examples 1-29 in Table 2 is an embodiment of the present invention, the curing time, drying shrinkage, flexural strength, overall evaluation good monolithic refractory of the rotary erosion spall was obtained.
[0058]
　Of the Examples 11 to 15 "Ca X Sr 1-X Al 2 O 4 (where, 0 ≦ X ≦ 0.5) and Ca Y Sr 1-Y Al 4 O 7 (where, 0 ≦ Y ≦ 0.5) and 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3 (where, 0 ≦ Z ≦ 0.5) and the preferred range of total "(10 mass%) is examples 11 to the 14 is the overall evaluation is ◎, example 15 deviating from the scope is good monolithic refractory is obtained, overall evaluation is a little inferior in 〇.
[0059]
　Of the Examples 16 to 20, the preferred range (3-12 wt%) is Examples 17-19 of "particle diameter 0.1mm or less magnesia raw material" overall evaluation is ◎. On the other hand, examples out of the range 16 and 20 is good monolithic refractory is obtained, overall evaluation is 〇.
[0060]
　Also, of the Examples 21-25, the preferred range (5 to 25% by weight) is Examples 22-24 "particle diameter 0.1mm or less of a spinel material" Global assessment is ◎. On the other hand, examples out of the range 21 and 25 is good monolithic refractory is obtained, overall evaluation is 〇.
[0061]
　Example 26 is an example in which a combination of alumina cement, although good monolithic refractory is obtained, overall evaluation △ der.
　Example 29 is within the range of the present invention is an example using a small amount of a hydroxycarboxylic acid. Although good castable refractory is obtained, the curing time is a little long, the strength is a little lower, a comprehensive evaluation is △.
[0062]
　Comparative examples in Table 3 1 is a polyvalent example of using a combination of metal salts of a conventional active magnesia with oxycarboxylic acids, curing rather slowly, aging is very large, the strength is somewhat lower, rotary erosion crack is slightly higher in the spall.
[0063]
　Comparative Example 2, Ca X Sr 1-X Al 2 O 4 is an example usage is less than the scope of the present invention, curing is somewhat slow, temporal change slightly larger, low strength, cracks in the rotary erosion Spall but slightly higher.
[0064]
　Comparative Example 3, Ca X Sr 1-X Al 2 O 4 is an example usage is larger than the range of the present invention, the curing time is slightly shorter, curing shrinkage is slightly large, cracks are often in rotation erosion spall.
[0065]
　Comparative Example 4, Ca X Sr 1-X Al 2 O 4 is greater example than the range of values of X of the present invention, curing shrinkage is slightly large, poor corrosion resistance in rotation erosion spall.
[0066]
　Comparative Example 5, the amount of the polyvalent metal salts of oxycarboxylic acid is less example than the range of the present invention, the curing time is very long, strength is very low.
[0067]
　Comparative Example 6 is an example of the use amount is larger than the range of the present invention polyvalent metal salts of oxycarboxylic acid, the curing time is slightly shorter, drying shrinkage is very large.
Industrial Applicability
[0068]
　According to the present invention, not using alumina cement, or that the amount of alumina cement is very low, and faster strength development of CaO content is less castable refractory, and to high strength it can.
The scope of the claims
[Requested item 1]
　A proportion of 100 mass% of the refractory material grain size 8 mm, Ca X Sr 1-X Al 2 O 4 (where, 0 ≦ X ≦ 0.5) 10% by weight content of 0.5 mass% or more of the following , the content of the polyvalent metal salt of hydroxycarboxylic acid is 1.0 wt% or less than 0.05 wt%
monolithic refractory characterized in that.
[Requested item 2]
　The content of polyvalent metal salt of the hydroxycarboxylic acid is 1.0 wt% or less than 0.1 wt%
monolithic refractory of claim 1, wherein the.
[Requested item 3]
　A proportion of 100 mass% of the refractory material grain size 8 mm, Ca X Sr 1-X Al 2 O 4 (where, 0 ≦ X ≦ 0.5) and Ca Y Sr 1-Y Al 4 O 7 (where 0 ≦ Y ≦ 0.5) and 12 (CaO) Z (SrO) 1-Z · 7Al 2 O 3 (where the total content of 0 ≦ Z ≦ 0.5) is not more than 10 wt%
that monolithic refractory according to claim 1 or 2, characterized.
　A proportion of the refractory raw material 100 wt%, the content of the particle diameter 0.1mm or less magnesia raw material is not more than 3 mass% or more and 12 wt%
to any one of claims 1 to 3, characterized in that monolithic refractory described.
[Requested item 5]
　A proportion of the refractory raw material 100 wt%, the content of the particle diameter 0.1mm or less of the spinel material is 25 wt% or more and 5 mass% or less
in any one of claims 1 to 3, characterized in that monolithic refractory described.
[Requested item 6]
　A proportion of the refractory raw material 100% by weight, content of at least one of the sum of the following alumina raw material and a spinel raw material particle size 0.1mm super 8mm is less than 75 mass% 55 mass% or more
, characterized in that monolithic refractory according to any one of claims 1 to 5.