JP2012106899A - Furnace material and method for producing the furnace material - Google Patents
Furnace material and method for producing the furnace material Download PDFInfo
- Publication number
- JP2012106899A JP2012106899A JP2010261310A JP2010261310A JP2012106899A JP 2012106899 A JP2012106899 A JP 2012106899A JP 2010261310 A JP2010261310 A JP 2010261310A JP 2010261310 A JP2010261310 A JP 2010261310A JP 2012106899 A JP2012106899 A JP 2012106899A
- Authority
- JP
- Japan
- Prior art keywords
- mgo
- furnace material
- mass
- furnace
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/20—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in magnesium oxide, e.g. forsterite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
- C04B35/05—Refractories by fusion casting
- C04B35/051—Refractories by fusion casting containing chromium oxide or chrome ore
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/101—Refractories from grain sized mixtures
- C04B35/1015—Refractories from grain sized mixtures containing refractory metal compounds other than those covered by C04B35/103 - C04B35/106
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
Abstract
Description
本発明は特に、耐リチウム反応性に優れた軽量の炉材に関するものである。 The present invention particularly relates to a lightweight furnace material excellent in lithium resistance.
金属リチウム電池、リチウムイオン電池、リチウムポリマー電池等に代表される二次電池の正極材料としては、コバルト酸リチウム（ＬｉＣｏＯ２）、マンガン酸リチウム（ＬｉＭｎＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ２）、リン酸鉄リチウム（ＬｉＦｅＰＯ４）等のリチウム遷移金属が挙げられる。現在用いられている正極材料としては、コバルト酸リチウムが主流である。 As positive electrode materials of secondary batteries represented by metal lithium batteries, lithium ion batteries, lithium polymer batteries, etc., lithium cobaltate (LiCoO 2 ), lithium manganate (LiMnO 2 ), lithium nickelate (LiNiO 2 ), phosphorus Examples thereof include lithium transition metals such as lithium iron oxide (LiFePO 4 ). As the positive electrode material currently used, lithium cobaltate is the mainstream.
例えば、ＬｉＣｏＯ２ を製造する場合、原料として水酸化リチウム又は硝酸リチウムと、酸化コバルト、水酸化コバルト又は炭酸コバルトとの混合物を、容器に入れて固定炉又はトンネル炉等で焼成するか、又は直接回転炉に入れて焼成する。この焼成は、酸素雰囲気にて１０００℃付近の温度で行われる。 For example, when producing LiCoO 2 , a mixture of lithium hydroxide or lithium nitrate and cobalt oxide, cobalt hydroxide or cobalt carbonate as raw materials is put in a container and fired in a fixed furnace or a tunnel furnace, or directly Place in a rotary furnace and fire. This firing is performed at a temperature around 1000 ° C. in an oxygen atmosphere.
該焼成を行う焼成炉を構成する炉材としては、一般的に、通常工業用の耐火炉で使用されるアルミナ、ムライト、コーディエライト等の耐熱セラミックス材料が使用されている。 As the furnace material constituting the firing furnace for performing the firing, generally, a heat-resistant ceramic material such as alumina, mullite, cordierite and the like which are usually used in an industrial refractory furnace is used.
しかし、該耐熱セラミックス材料を炉材とする焼成炉を使用して、前記焼成温度条件下でＬｉＣｏＯ２ を製造すると、その焼成中にリチウム化合物が融解し、更に、該化合物由来のリチウム元素が炉内の高温条件下で蒸発し、該耐熱セラミックス材料に浸入する現象が生じる。このため、焼成炉の繰り返しの使用を経て、炉材にひび割れや剥離が生じ、炉材の頻繁な交換が必要であるという問題があった。 However, when LiCoO 2 is produced under the firing temperature condition using a firing furnace using the heat-resistant ceramic material as a furnace material, the lithium compound melts during the firing, and the lithium element derived from the compound is further transformed into the furnace. Evaporation occurs under high temperature conditions, and the phenomenon of entering the heat-resistant ceramic material occurs. For this reason, after repeated use of the firing furnace, there was a problem that cracks and peeling occurred in the furnace material, and frequent replacement of the furnace material was necessary.
なお、焼成用耐火物の耐反応性の向上を図る技術として、骨材としてＭｇＯ質燒結体を使用する各種の技術が開示されている（例えば、特許文献１、特許文献２）。 In addition, as a technique for improving the reaction resistance of the refractory for firing, various techniques using an MgO sintered body as an aggregate are disclosed (for example, Patent Document 1 and Patent Document 2).
しかし、従来のＭｇＯ質燒結体では、骨材がガラス質の結合層で結合された構造を有しており、炉材の軽量化を目的として焼結体の気孔率を上昇させた場合、ガラス質の結合層がＬｉ成分によって浸食されやすくなるため、当該現象を回避するため、焼結体の気孔率を低く抑えた重量が大きいものが通常であり、例えば、複数階構造の焼成炉には採用できない問題があった。 However, the conventional MgO sintered body has a structure in which the aggregate is bonded with a glassy bonding layer, and when the porosity of the sintered body is increased for the purpose of reducing the weight of the furnace material, In order to avoid this phenomenon, the bonded layer of the quality is likely to be eroded by the Li component, so that the sintered body has a large weight while keeping the porosity of the sintered body low. There was a problem that could not be adopted.
本発明の目的は前記問題を解決し、骨材部分および結合層部分共に耐リチウム反応性に優れ、かつ、軽量の炉材および炉材の製造方法を提供することである。尚、炉材とは、炉体を構成する煉瓦と粉末処理用に用いられる匣鉢を表す。 An object of the present invention is to solve the above-mentioned problems and to provide a lightweight furnace material and a method for producing the furnace material, which are excellent in lithium resistance resistance in both the aggregate part and the bonding layer part. In addition, a furnace material represents the brick which comprises a furnace body, and the mortar used for powder processing.
上記課題を解決するためになされた本発明の炉材は、ＭｇＯの含有率が３３〜９９．５質量％、ＭｇＯ と Ａｌ2Ｏ3 との合計含有率がＭｇＯ +Ａｌ2Ｏ3＝９５質量％以上、ＭｇＯ とＡｌ2Ｏ3との含有比率が、各質量％比で、Ａｌ2Ｏ3 / ＭｇＯ=０．００３ 〜 ２．１、嵩比重が１．０〜２．５であることを特徴とするものである。 The furnace material of the present invention made to solve the above problems has an MgO content of 33 to 99.5% by mass, and a total content of MgO and Al 2 O 3 is MgO + Al 2 O 3 = 95 mass. % Or more, the content ratio of MgO and Al 2 O 3 is Al 2 O 3 /MgO=0.003 to 2.1, and the bulk specific gravity is 1.0 to 2.5 in each mass% ratio. It is a feature.
請求項２記載の発明は、請求項１記載の炉材において、ＭｇＯ成分の２〜９２％がスピネルであることを特徴とするものである。 The invention according to claim 2 is characterized in that, in the furnace material according to claim 1, 2 to 92% of the MgO component is spinel.
請求項３記載の発明は、請求項１記載の炉材において、該炉材がＣｏ、Ｍｎ、Ｎｉ、Ｆｅ、Ｐから選択された1種類以上の元素とリチウムとの複合酸化物の熱処理に用いる、リチウム複合酸化物の熱処理用炉材であることを特徴とするものである。 The invention according to claim 3 is the furnace material according to claim 1, wherein the furnace material is used for heat treatment of a composite oxide of lithium and one or more elements selected from Co, Mn, Ni, Fe, and P. It is a furnace material for heat treatment of lithium composite oxide.
請求項４記載の発明は、請求項１記載の炉材において、ＳｉＯ２の含有率が、０．１〜３．０質量％であることを特徴とするものである。 The invention according to claim 4 is characterized in that, in the furnace material according to claim 1, the content of SiO 2 is 0.1 to 3.0% by mass.
請求項５記載の発明は、請求項１記載の炉材において、常温圧縮強度が１．０〜５０MPaであることを特徴とするものである。 A fifth aspect of the present invention is the furnace material according to the first aspect, wherein the normal temperature compressive strength is 1.0 to 50 MPa.
請求項６記載の発明は、請求項２記載の炉材を製造する方法であって、骨材原料として、平均粒径０．８〜２ｍｍのペリクレースまたはスピネルを用い、全原料中５〜２０質量％を、平均粒径１０〜１００μｍのＡｌ2Ｏ3粉末とし、造孔材とともに全原料を混練および成形後、１４００〜１７００℃で焼成することを特徴とするものである。 Invention of Claim 6 is a method of manufacturing the furnace material of Claim 2, Comprising: As an aggregate raw material, the average particle diameter of 0.8-2 mm uses a periclase or spinel, 5-20 mass in all the raw materials % Is an Al 2 O 3 powder having an average particle diameter of 10 to 100 μm, and all the raw materials are kneaded and molded together with the pore former, and then fired at 1400 to 1700 ° C.
本発明に係る炉材は、ＭｇＯの含有率が３３〜９９．５質量％、ＭｇＯ と Ａｌ2Ｏ3 との合計含有率がＭｇＯ +Ａｌ2Ｏ3＝９５質量％以上、ＭｇＯ とＡｌ2Ｏ3との含有比率がＡｌ2Ｏ3 / ＭｇＯ（質量％比）=０．００３ 〜 ２．１、嵩比重が１．０〜２．５の構成を有する。当該構成によれば、ガラス質の結合層が形成されないため、従来、ガラス質の結合層がＬｉ成分によって浸食されていた問題が回避可能となり、かつ、軽量の炉材を実現できる。 The furnace material according to the present invention has a MgO content of 33 to 99.5% by mass, a total content of MgO and Al 2 O 3 of MgO + Al 2 O 3 = 95% by mass, MgO and Al 2 O 3 and Al 2 O 3 / MgO (mass% ratio) = 0.003 to 2.1, and the bulk specific gravity is 1.0 to 2.5. According to this configuration, since the vitreous bonding layer is not formed, it is possible to avoid the problem that the vitreous bonding layer has been eroded by the Li component in the past, and a lightweight furnace material can be realized.
炉材は、通常、骨材がガラス質の結合層で結合された構造を有するが、請求項６記載の発明では、平均粒径０．８〜２ｍｍのペリクレースまたはスピネルを用い、全原料中５〜２０質量％を、平均粒径１０〜１００μｍのＡｌ2Ｏ3粉末とし、造孔材とともに全原料を混練および成形後、１４００〜１７００℃で焼成することにより、ペリクレース又はスピネルからなる骨材の骨材表面でスピネル型結晶構造を有する結合層を形成している。従来のように、粒界部分がガラス質の結合層で構成された炉材では、該炉材を使用してＬｉを含む原料を焼成後、更に水蒸気雰囲気に暴露すると、時間の経過とともに、炉材を構成する骨材間の結合が崩壊し、炉材がバラバラになる現象が観察される。これに対し、請求項６記載の発明の方法によって、骨材間の粒界部分に、焼成反応によってスピネル層を形成させた場合、該炉材を使用してＬｉを含む原料を焼成後、更に水蒸気雰囲気に暴露した場合であっても、炉材の崩壊を抑制することができる。 The furnace material usually has a structure in which aggregates are bonded by a vitreous bonding layer, but in the invention according to claim 6, periclase or spinel having an average particle diameter of 0.8 to 2 mm is used, and 5% of all raw materials are used. ~ 20% by mass of Al 2 O 3 powder having an average particle diameter of 10 to 100 µm, and kneading and forming all the raw materials together with the pore former, followed by firing at 1400 to 1700 ° C, whereby the aggregate made of periclase or spinel A bonding layer having a spinel crystal structure is formed on the aggregate surface. In a furnace material in which the grain boundary part is composed of a glassy bonding layer as in the prior art, after firing the raw material containing Li using the furnace material and further exposing to a steam atmosphere, It is observed that the bond between aggregates constituting the material is broken and the furnace material is broken apart. On the other hand, when a spinel layer is formed by a firing reaction at the grain boundary portion between aggregates by the method of the invention of claim 6, after firing the raw material containing Li using the furnace material, Even when exposed to a steam atmosphere, the furnace material can be prevented from collapsing.
本発明は、Ｃｏ、Ｍｎ、Ｎｉ、Ｆｅ、Ｐから選択された1種類以上の元素とリチウムとの複合酸化物の熱処理に用いるのに適した炉材および炉材の製造方法に係る発明である。 The present invention relates to a furnace material suitable for use in heat treatment of a complex oxide of one or more elements selected from Co, Mn, Ni, Fe, and P and lithium, and a method for manufacturing the furnace material .
以下、本発明に係る炉材の一実施形態について説明する。 Hereinafter, an embodiment of a furnace material according to the present invention will be described.
該リチウム複合酸化物の熱処理用炉材は、ＭｇＯの含有率が３３〜９９．５質量％、ＭｇＯ と Ａｌ2Ｏ3 との合計含有率がＭｇＯ +Ａｌ2Ｏ3＝９５質量％以上、ＭｇＯ とＡｌ2Ｏ3との含有比率がＡｌ2Ｏ3 / ＭｇＯ（質量％比）=０．００３ 〜 ２．１の化学組成を有し、スピネル（Ａｌ2Ｏ3・ＭｇＯ）の存在比率が２〜９２％の結晶構造を有している。 The furnace material for heat treatment of the lithium composite oxide has a MgO content of 33 to 99.5% by mass, a total content of MgO and Al 2 O 3 of MgO + Al 2 O 3 = 95% by mass, MgO And Al 2 O 3 have a chemical composition of Al 2 O 3 / MgO (mass% ratio) = 0.003 to 2.1, and an abundance ratio of spinel (Al 2 O 3 .MgO) is 2 It has a crystal structure of ˜92%.
炉材は、通常、骨材がガラス質の結合層で結合された構造を有するが、本発明のリチウム複合酸化物の熱処理用炉材は、炉材の焼成過程において、ペリクレースまたはスピネルからなる骨材の骨材表面でスピネル型結晶構造を有する結合層を形成し、骨材間の粒界部分にスピネル層を有する構造を備えている。 The furnace material usually has a structure in which the aggregate is bonded by a vitreous bonding layer, but the furnace material for heat treatment of the lithium composite oxide of the present invention is a bone made of periclase or spinel in the firing process of the furnace material. A bonding layer having a spinel crystal structure is formed on the aggregate surface of the aggregate, and a structure having a spinel layer at a grain boundary portion between the aggregates is provided.
従来のように、粒界部分がガラス質の結合層で構成された炉材では、該炉材を使用してＬｉを含む原料を焼成後、更に水蒸気雰囲気に暴露すると、時間の経過とともに、炉材を構成する骨材間の結合が崩壊し、炉材がバラバラになる現象が観察されていた。本発明者の推測によると、ＭｇＯを骨材とし、結合層をＭｇＣａＳｉＯ4とする炉材の場合、該炉材を使用してＬｉを含む原料を焼成すると、結合層が、ＭｇＯ・ＣａＯ・ＳｉＯ2（Ｌｉ2Ｏ）の化学組成からなるアモルファスに変化し、このうち、Ｌｉ2Ｏの部分が、大気中の水蒸気およびＣＯ２を吸収しやすく、Ｌｉ2Ｏのカーボネート化により結合層から炉材の崩壊が生じるものと考えられる。これに対し、本発明では、骨材間の粒界部分に、焼成反応によってスピネル層を形成させておくことにより、Ｌｉとの反応による結合層のアモルファス化、および、その後の水蒸気暴露によるＬｉ2Ｏのカーボネート化を抑制し、前記メカニズムによる炉材の崩壊を効果的に抑制可能としている。 In a furnace material in which the grain boundary part is composed of a glassy bonding layer as in the prior art, after firing the raw material containing Li using the furnace material and further exposing to a steam atmosphere, It was observed that the bond between aggregates constituting the material collapsed and the furnace material was broken apart. According to the inventor's guess, in the case of a furnace material in which MgO is an aggregate and the bonding layer is MgCaSiO 4 , when the raw material containing Li is fired using the furnace material, the bonding layer becomes MgO · CaO · SiO. 2 (Li 2 O) is changed to an amorphous material having a chemical composition, and among these, the Li 2 O portion is easy to absorb water vapor and CO 2 in the atmosphere, and from the tie layer to the furnace material by carbonation of Li 2 O It is thought that the collapse of. On the other hand, in the present invention, a spinel layer is formed by a firing reaction at the grain boundary portion between the aggregates, thereby amorphizing the bonding layer by reaction with Li and subsequent Li 2 exposure by water vapor exposure. Carbonation of O is suppressed, and collapse of the furnace material due to the mechanism can be effectively suppressed.
なお、該炉材の嵩比重は１．０〜２．５である。嵩比重が２．５以上になると、炉材の重量が大きくなり、複数階構造の焼成炉には採用困難となるため好ましくない。一方、嵩比重が１．０以下の場合、炉を昇温する際発生する熱応力により、炉材が破損する危険性があり好ましくない。 The bulk density of the furnace material is 1.0 to 2.5. When the bulk specific gravity is 2.5 or more, the weight of the furnace material increases, and it becomes difficult to employ it in a firing furnace having a multi-story structure. On the other hand, when the bulk specific gravity is 1.0 or less, there is a risk that the furnace material may be damaged by the thermal stress generated when the furnace is heated.
該炉材の常温圧縮強度は、１．０MPa以上とすることは必要である。一方、嵩比重を１．０〜２．５とするための気孔率との関係から、常温圧縮強度５０MPaが工業的に実現可能な強度の上限となっている。 It is necessary that the normal temperature compressive strength of the furnace material be 1.0 MPa or more. On the other hand, the normal temperature compressive strength of 50 MPa is the upper limit of the industrially realizable strength from the relationship with the porosity for setting the bulk specific gravity to 1.0 to 2.5.
該炉材は、ＭｇＯの含有率が３３〜９９．５質量％、ＭｇＯ と Ａｌ2Ｏ3 との合計含有率がＭｇＯ +Ａｌ2Ｏ3＝９５質量％以上、ＭｇＯ とＡｌ2Ｏ3との含有比率がＡｌ2Ｏ3 / ＭｇＯ（質量％比）=０．００３ 〜 ２．１、嵩比重が１．０〜２．５とすることでＭｇＯ本来の耐食性を保持しつつ軽量化を実現している。 Furnace material, the content of MgO is 33 to 99.5 wt%, the total content of MgO and Al 2 O 3 is MgO + Al 2 O 3 = 95 wt% or more, of MgO and Al 2 O 3 By making the content ratio Al 2 O 3 / MgO (mass% ratio) = 0.003 to 2.1 and the bulk specific gravity 1.0 to 2.5, weight reduction is achieved while maintaining the original corrosion resistance of MgO. ing.
ＭｇＯの割合が３３％以下の場合、耐リチウム反応性が低下するため好ましくない。 When the proportion of MgO is 33% or less, lithium resistance reactivity is lowered, which is not preferable.
前記ＭｇＯの含有率は高いほど望ましいが、ＭｇＯはコストが高く、ＭｇＯのみから炉材を構成することは現実的ではない。そこで、Ａｌ2Ｏ3 との混合で使用し、該Ａｌ2Ｏ3とＭｇＯ との合計含有率がＭｇＯ +Ａｌ2Ｏ3＝９５質量％以上、かつ、含有比率がＡｌ2Ｏ3 / ＭｇＯ（質量％比）=０．００３ 〜 ２．１となる構成にすることで、耐反応性を確保することができる。Ａｌ2Ｏ3とＭｇＯ との合計含有率が９５質量％未満である場合には、ＭｇＯの特性である耐食性が有効に発揮されなくなるため好ましくない。また、含有比率がＡｌ2Ｏ3 / ＭｇＯ（質量％比）=０．００３未満の場合には 、ＭｇＯ粒子の焼結が進みにくく、１６５０℃以上の高温焼成が必要となる。Ａｌ2Ｏ3 / ＭｇＯ（質量％比）=２．１を超える場合には 、ＭｇＯの含有量が少なく、耐食性が十分に発揮されない。 The higher the content of MgO, the better. However, MgO is expensive, and it is not realistic to construct the furnace material from MgO alone. Therefore, used in admixture with Al 2 O 3, the Al 2 O 3 and the total content of the MgO is MgO + Al 2 O 3 = 95 wt% or more, and the content ratio of Al 2 O 3 / MgO ( Reaction resistance can be ensured by adopting a structure in which the mass% ratio) = 0.003 to 2.1. When the total content of Al 2 O 3 and MgO is less than 95% by mass, the corrosion resistance, which is a characteristic of MgO, cannot be effectively exhibited, which is not preferable. When the content ratio is less than Al 2 O 3 / MgO (mass% ratio) = 0.003, the sintering of MgO particles is difficult to proceed, and high-temperature firing at 1650 ° C. or higher is required. When Al 2 O 3 / MgO (mass% ratio) exceeds 2.1, the content of MgO is small and the corrosion resistance is not sufficiently exhibited.
以下に、嵩比重が１．０〜２．５である該炉材の製造方法を説明する。 Below, the manufacturing method of this furnace material whose bulk specific gravity is 1.0-2.5 is demonstrated.
（原料）
ＭｇＯ原料として、平均粒径０．８〜２ｍｍのペリクレースまたはスピネルを用い、全原料中５〜２０質量％を、平均粒径１０〜１００μｍのＡｌ2Ｏ3粉末とし、造孔材とともに全原料を混練および成形後、１４００〜１７００℃で焼成することにより、ペリクレースまたはスピネルからなる骨材の表面でスピネル型結晶構造を有する結合層を形成する。平均粒子径は、使用前に予め粉砕処理を行って調整する。
(material)
As the MgO raw material, periclase or spinel with an average particle diameter of 0.8 to 2 mm is used, and 5 to 20% by mass of the total raw material is made into Al 2 O 3 powder with an average particle diameter of 10 to 100 μm. After kneading and forming, firing at 1400 to 1700 ° C. forms a bonding layer having a spinel crystal structure on the surface of the aggregate made of periclase or spinel. The average particle diameter is adjusted by pulverization before use.
ＭｇＯ原料粉末は、ＭｇＯ純度が９５質量％以上であることが好ましく、平均粒子径が０．８ｍｍの粗粒と、平均粒子径が０．１ｍｍの細粒を組み合せとすることが好ましい。 The MgO raw material powder preferably has a MgO purity of 95% by mass or more, and a combination of coarse particles having an average particle size of 0.8 mm and fine particles having an average particle size of 0.1 mm is preferable.
Ａｌ2Ｏ3原料粉末としては、Ａｌ2Ｏ3純度が９９質量％以上であることが好ましい。気孔率を向上させるために、Ａｌ2Ｏ3バブル用いることもできる。該Ａｌ2Ｏ3とＭｇＯ との合計含有率は、ＭｇＯ +Ａｌ2Ｏ3＝９５質量％以上、かつ、含有比率がＡｌ2Ｏ3 / ＭｇＯ（質量％比）=０．００３ 〜 ２．１であることが好ましい。 The Al 2 O 3 raw material powder preferably has an Al 2 O 3 purity of 99% by mass or more. In order to improve the porosity, Al 2 O 3 bubbles can also be used. The total content of the Al 2 O 3 and MgO is MgO + Al 2 O 3 = 95% by mass or more and the content ratio is Al 2 O 3 / MgO (mass% ratio) = 0.003 to 2.1. It is preferable that
各原料には、ＳｉＯ２が不純物として含有されるが、含有するＳｉＯ２は３質量％未満であることが好ましく、より好ましくは１質量％未満である。これらの成分の合計量が３質量％以上の場合、結晶粒界に第２相やガラス相を多く生成し、耐食性が低下するため好ましくない。尚、ＳｉＯ２含有量を０．１質量％以下にまで低下させるためには、極めて高純度の原料の使用が必要となり、コストの観点から工業的には好ましくない。 Each raw material contains SiO 2 as an impurity, and the contained SiO 2 is preferably less than 3% by mass, and more preferably less than 1% by mass. When the total amount of these components is 3% by mass or more, a large amount of the second phase or glass phase is generated at the crystal grain boundary, and the corrosion resistance is lowered, which is not preferable. In order to reduce the SiO 2 content to below 0.1% by weight, it requires the use of very high purity of the raw material is not preferable for industrial view of cost.
（製法）
以上の原料を用いて所定の組成になるように配合し、更に、炉材に気孔を形成するための造孔材として発泡スチロール等の有機物を添加し、湿式で混練を行う混練機（カントーミキサー等）により水または有機溶媒中で混合する。造孔材としての有機物添加量は、表２〜３において、前記の全原料を１００質量％として、ここに更に追加して添加する量として記載しており、これを「外配」と記載している。なお、前記のように、気孔率を向上させるために、Ａｌ2Ｏ3バブル用いる場合には、発泡スチロール等の有機物の添加は必須要件ではない。
(Manufacturing method)
A kneader (such as a can-to-mixer) that is blended so as to have a predetermined composition using the above raw materials, and further added with an organic substance such as polystyrene foam as a pore former for forming pores in the furnace material, and kneaded in a wet manner ) In water or an organic solvent. In Tables 2 and 3, the amount of organic substance added as a pore former is described as an amount to be added in addition to 100% by mass of the total raw materials, and this is described as “external distribution”. ing. As described above, in order to improve the porosity, when Al 2 O 3 bubbles are used, addition of an organic substance such as expanded polystyrene is not an essential requirement.
成形方法として油圧プレス成形、フリクションプレス成形等の方法を採用する場合、混合スラリーに、必要により公知の成形助剤（例えばアクリル系樹脂、ＰＶＡ等）を添加し、スプレードライヤー等の公知の方法で乾燥させて成形用粉体を作製し、この成形用粉体を金型やゴム型などに充填して成形する。また、鋳込み成形法を採用する場合には、混合スラリーに必要により公知のバインダー（例えばワックスエマルジョン、アクリル系樹脂等）を添加し、石膏型あるいは樹脂型を用いて排泥鋳込法、充填鋳込法、加圧鋳込法などにより成形する。 When adopting a method such as hydraulic press molding or friction press molding as a molding method, a known molding aid (for example, acrylic resin, PVA, etc.) is added to the mixed slurry as necessary, and a known method such as a spray dryer is used. A molding powder is produced by drying, and the molding powder is filled into a mold or a rubber mold and molded. In addition, when adopting a casting method, a known binder (for example, wax emulsion, acrylic resin, etc.) is added to the mixed slurry as required, and a waste mud casting method or a filling casting using a gypsum mold or a resin mold. Molding is performed by squeeze method or pressure casting method.
以上のようにして得た成形体を１３００〜１７００℃、より好ましくは１４５０〜１６５０℃で焼成することによって耐リチウム反応性に優れた軽量の、ＭｇＯ質焼結体からなる炉材を得る。 The molded body obtained as described above is fired at 1300 to 1700 ° C., more preferably 1450 to 1650 ° C., to obtain a light-weight furnace material made of a MgO-based sintered body excellent in lithium resistance.
表１に示す割合で各原料を配合し、更に、造孔材を添加し、湿式で混練を行う混練機（カントーミキサー等）により水または有機溶媒中で混合後、１４５０℃で焼成して２００ｍｍ×２００ｍｍ、高さ３０ｍｍのサンプルを作製した。使用したＭｇＯ原料としては粒度が０．８ｍｍ、０．１ｍｍの何れかで、純度が９５％以上のものを使用した。成形はＰＶＡを添加した後、油圧プレス成形で行った。焼成は１４５０℃で行った。
（耐Ｌｉ反応性評価）
得られた各サンプルより切り出した試験片（２０×２０×５ｔ）と１０ｇのＬｉ２ＣＯ３をアルミナ坩堝に入れ、大気中１１００℃、５時間保持を３サイクル繰り返した。加熱前後での試験片の寸法を測定し、外観と、反応後の膨張率により耐Ｌｉ反応性を評価した。
Each raw material is blended in the proportions shown in Table 1, and further, a pore former is added, mixed in water or an organic solvent by a kneader (such as a Canto mixer) that performs wet kneading, and then fired at 1450 ° C. to 200 mm. A sample having × 200 mm and a height of 30 mm was produced. As the MgO raw material used, one having a particle size of 0.8 mm or 0.1 mm and a purity of 95% or more was used. Molding was performed by hydraulic press molding after adding PVA. Firing was performed at 1450 ° C.
(Li reactivity evaluation)
A test piece (20 × 20 × 5 t) cut out from each sample obtained and 10 g of Li 2 CO 3 were put in an alumina crucible, and maintained at 1100 ° C. in the atmosphere for 5 hours for 3 cycles. The dimensions of the test piece before and after heating were measured, and the Li resistance was evaluated based on the appearance and the expansion rate after the reaction.
（実施例１〜４）
ＭｇＯ原料として、粒度が０．８ｍｍの粗粒と０．１ｍｍの細粒とを、各々表１の割合で混合して使用した。いずれも、優れた耐Ｌｉ反応性を示した。
（比較例１、２）
ＭｇＯ質を添加しない例であり、いずれも、耐Ｌｉ反応性に問題があった。
(Examples 1-4)
As MgO raw materials, coarse particles having a particle size of 0.8 mm and fine particles having a size of 0.1 mm were mixed and used in the ratios shown in Table 1. All showed excellent Li reaction resistance.
(Comparative Examples 1 and 2)
This is an example in which no MgO material is added, and in all cases, there was a problem in Li resistance.
表２に示す割合で各原料を配合し、更に、造孔材を添加し、湿式で混練を行う混練機（カントーミキサー等）により水または有機溶媒中で混合後、１４５０℃で焼成して２００ｍｍ×２００ｍｍ、高さ３０ｍｍのサンプルを作製した。Ａｌ２Ｏ３は、電融Ａｌ2Ｏ3を使用した。実施例５では、発泡スチロールも添加した。ＭｇＯ原料は粒度が２ｍｍ、０．８ｍｍ、０．１ｍｍ、０．００５ｍｍの何れかで、純度が９５％以上のものを使用した。成形はＰＶＡを添加した後、油圧プレス成形で行った。
（耐Ｌｉ反応性評価）
得られた各サンプルより切り出した試験片（２０×２０×５ｔ）と１０ｇのＬｉ２ＣＯ３をアルミナ坩堝に入れ、大気中１１００℃、５時間保持を３サイクル繰り返した。加熱前後での試験片の寸法を測定し、反応による膨張率を評価した。
（成形性評価）
所定の配合に秤量し混合した坏土を、試験用金型（底板：１００×１００×１０ｔ）に入れ、１０ＭＰａの圧力をかけた。金型から取り出す際、成形体に破損が生じるかを評価した。評価は以下の３段階で行った。○：破損なし。△：一部破損。×：取り出せず。無理やり取り出した場合破損。
(焼成評価)
プレス成形後、１００℃の乾燥を行い水分除去した乾燥体を、電気炉にて１４５０℃〜１６５０℃で焼成を行った。焼成後外観を観察し、クラックの有無を検査した。評価は以下の２段階で行った。○：クラック無し。×：クラック有り。
(比重評価)
煮沸法（ＪＩＳ Ｒ２２０５）にてカサ比重を測定評価した。評価は以下の２段階で行った。○：カサ比重 １．０〜２．５。×：それ以外。
Each raw material is blended in the proportions shown in Table 2, and further, a pore former is added, mixed in water or an organic solvent by a kneader (such as a Canto mixer) that performs wet kneading, and then fired at 1450 ° C. to 200 mm. A sample having × 200 mm and a height of 30 mm was produced. As Al 2 O 3 , electrofused Al 2 O 3 was used. In Example 5, styrofoam was also added. The MgO raw material used had a particle size of 2 mm, 0.8 mm, 0.1 mm, or 0.005 mm and a purity of 95% or more. Molding was performed by hydraulic press molding after adding PVA.
(Li reactivity evaluation)
A test piece (20 × 20 × 5 t) cut out from each sample obtained and 10 g of Li 2 CO 3 were put in an alumina crucible, and maintained at 1100 ° C. in the atmosphere for 5 hours for 3 cycles. The dimensions of the test piece before and after heating were measured, and the expansion rate due to the reaction was evaluated.
(Formability evaluation)
The kneaded clay weighed and mixed in a predetermined composition was put into a test mold (bottom plate: 100 × 100 × 10 t), and a pressure of 10 MPa was applied. When taking out from the mold, it was evaluated whether or not the molded body was damaged. Evaluation was performed in the following three stages. ○: No damage. Δ: Partially damaged. X: Not taken out. Damaged when forced exchange.
(Firing evaluation)
After press molding, the dried body from which moisture was removed by drying at 100 ° C. was fired at 1450 ° C. to 1650 ° C. in an electric furnace. After firing, the appearance was observed and the presence or absence of cracks was inspected. Evaluation was performed in the following two stages. ○: No crack. X: There is a crack.
(Specific gravity evaluation)
The bulk density was measured and evaluated by the boiling method (JIS R2205). Evaluation was performed in the following two stages. ○: Bulk specific gravity 1.0-2.5. X: Other than that.
（実施例５〜９）
ＭｇＯ原料として、粒度が２ｍｍ又は０．８ｍｍの粗粒と０．１ｍｍ又は０．００５ｍｍの細粒とを、各々表2の割合で混合して使用した。いずれも、優れた耐Ｌｉ反応性・成形性を示した。また、焼成によるクラック発生の問題は生じなかった。比重も小さく、軽量化が実現された。
（比較例３）
ＭｇＯ原料として、粒度が０．００５ｍｍの細粒のみを使用した。耐Ｌｉ反応性には問題がなかったが、成形性に劣り、焼成時にクラックが観察された。
（比較例４）
ＭｇＯ原料として、粒度が２ｍｍの粗粒のみを使用した。耐Ｌｉ反応性がやや劣り、成形中に取り扱い中の欠けが観察された。
(Examples 5 to 9)
As MgO raw materials, coarse particles having a particle size of 2 mm or 0.8 mm and fine particles having a size of 0.1 mm or 0.005 mm were mixed and used in the ratios shown in Table 2, respectively. All showed excellent Li reaction resistance and moldability. Moreover, the problem of the crack generation by baking did not arise. The specific gravity is small and light weight is realized.
(Comparative Example 3)
As the MgO raw material, only fine particles having a particle size of 0.005 mm were used. Although there was no problem in Li resistance, the moldability was inferior and cracks were observed during firing.
(Comparative Example 4)
As the MgO raw material, only coarse particles having a particle size of 2 mm were used. The Li reactivity was slightly inferior, and chipping during handling was observed during molding.
表３に示す割合で各原料を配合し、更に、造孔材を添加し、湿式で混練を行う混練機（カントーミキサー等）により水または有機溶媒中で混合後、１４５０℃で焼成して２００ｍｍ×２００ｍｍ、高さ３０ｍｍのサンプルを作製した。実施例１０〜１２および比較例５では、Ａｌ２Ｏ３は、Ａｌ2Ｏ3バブル使用した。実施例１３および比較例６では、発泡スチロールを添加した。ＭｇＯ原料は粒度が２ｍｍ、０．８ｍｍ、０．１ｍｍ、０．００５ｍｍの何れかで、純度が９５％以上のものを使用した。実施例１４では、フリクションプレスで、２００ｍｍ×２００ｍｍ、で高さ５０ｍｍの匣鉢成形を行った。焼成は１４５０℃で行った。
（ＸＲＤ測定）
焼成後のサンプルについてＸＲＤ測定を行い、ＭｇＯ質がスピネル型結晶構造として存在する割合を評価した。ＸＲＤ測定は、ＲＩＮＴ−１１００ Ｘ−ｒａｙ ｄｉｆｆｒａｃｍｅｔｅｒ（Ｒｉｇａｋｕ製）を用いて行い、測定条件は下記の通りとした。（２θ：２５〜４５°、ステップ幅：０．０４、係数時間：２、電圧：４０ｋＶ、電流：２０ｍＡ）
（耐Ｌｉ反応性評価）
得られた各サンプルより切り出した試験片（２０×２０×５ｔ）と１０ｇのＬｉ２ＣＯ３をアルミナ坩堝に入れ、大気中１１００℃、５時間保持を繰り返した。加熱前後での試験片の寸法を測定し、試験片の寸法が１０％膨張した通窯回数を測定した。評価は以下の◎、○、×で行った。◎：７回以上、○：４回〜７回未満、×：４回未満。
（比重評価）
煮沸法（ＪＩＳ Ｒ２２０５）に準拠しカサ比重を測定した。評価は以下の○、×で行った。○：カサ比重 １．０〜２．５。×：それ以外。
（圧縮強度評価）
２０００ＫＮ圧縮試験機（ＪＴトーシ株式会社製）にて最大荷重を測定し、ＪＩＳ Ｒ２２０６に準拠し圧縮強度を測定した。評価は以下の○、×で行った。○：圧縮強度 １．０ＭＰａ以上。×：圧縮強度 １．０ＭＰａよりも下。
Each raw material is blended in the proportions shown in Table 3, and further, a pore former is added, mixed in water or an organic solvent by a kneader (such as a Canto mixer) that performs wet kneading, and then fired at 1450 ° C. to 200 mm. A sample having × 200 mm and a height of 30 mm was produced. In Examples 10 to 12 and Comparative Example 5, Al 2 O 3 were used Al 2 O 3 bubbles. In Example 13 and Comparative Example 6, styrene foam was added. The MgO raw material used had a particle size of 2 mm, 0.8 mm, 0.1 mm, or 0.005 mm and a purity of 95% or more. In Example 14, mortar molding of 200 mm × 200 mm and a height of 50 mm was performed by a friction press. Firing was performed at 1450 ° C.
(XRD measurement)
The XRD measurement was performed on the sample after firing, and the proportion of the MgO material present as a spinel crystal structure was evaluated. The XRD measurement was performed using a RINT-1100 X-ray diffractometer (manufactured by Rigaku), and the measurement conditions were as follows. (2θ: 25 to 45 °, step width: 0.04, coefficient time: 2, voltage: 40 kV, current: 20 mA)
(Li reactivity evaluation)
A test piece (20 × 20 × 5 t) cut out from each sample obtained and 10 g of Li 2 CO 3 were put in an alumina crucible, and the holding at 1100 ° C. in the atmosphere for 5 hours was repeated. The dimension of the test piece before and after heating was measured, and the number of times the kiln was expanded by 10% was measured. Evaluation was performed by the following ◎, ○, ×. (Double-circle): 7 times or more, (circle): 4 times-less than 7 times, x: less than 4 times.
(Specific gravity evaluation)
The bulk density was measured according to the boiling method (JIS R2205). Evaluation was performed by the following (circle) and x. ○: Bulk specific gravity 1.0-2.5. X: Other than that.
(Compressive strength evaluation)
The maximum load was measured with a 2000 KN compression tester (manufactured by JT Toshi Co., Ltd.), and the compressive strength was measured according to JIS R2206. Evaluation was performed by the following (circle) and x. ○: Compressive strength 1.0 MPa or more. X: Compressive strength Below 1.0 MPa.
（実施例１０〜１４）
ＭｇＯ原料として、粒度が２ｍｍ又は０．８ｍｍの粗粒と０．１ｍｍ又は０．００５ｍｍの細粒とを、各々表３の割合で混合して使用した。いずれも、良好な耐Ｌｉ反応性・圧縮強度を示した。比重も小さく、軽量化が実現された。
（実施例１５）
ＭｇＯ原料として、粒度が０．８ｍｍの粗粒を使用し、さらにスピネルを、表３の割合で混合して使用した。良好な耐Ｌｉ反応性・圧縮強度を示した。比重も小さく、軽量化が実現された。
（実施例１６〜１８）
ＭｇＯ原料として、粒度が０．８ｍｍの粗粒と０．１ｍｍの細粒とを、各々表３の割合で混合して使用、さらにＡｌ2Ｏ3原料として、粒度が０．０５mmの微粉末、（実施例１６では更にスピネル）を、表３の割合で混合して使用した。いずれも、極めて良好な耐Ｌｉ反応性を示した。その他、圧縮強度も良好であり、比重も小さく、軽量化が実現された。
（実施例１９）
ＭｇＯ原料として、粒度が０．１ｍｍの細粒を使用し、さらにＡｌ2Ｏ3原料として、粒度が０．０５mmの微粉末、および、Ａｌ2Ｏ3バブルを、各々表３の割合で混合して使用した。いずれも、良好な耐Ｌｉ反応性・圧縮強度を示した。比重も小さく、軽量化が実現された。
（比較例５）
ＭｇＯ原料として、粒度が０．００５ｍｍの細粒のみを使用した。耐Ｌｉ反応性には問題がなかったが、圧縮強度に劣る問題があった。
（比較例６）
Ａｌ2Ｏ3バブル使用せず、代わりに発泡スチロールのみを使用した。耐Ｌｉ反応性には問題がなかったが、圧縮強度に劣る問題があった。
（比較例７）
Ａｌ2Ｏ3バブルも発泡スチロールも使用しなかった。耐Ｌｉ反応性・圧縮強度には問題がなかったが、比重が大きくなる問題があった。
（比較例８）
ペリクレースあるいはスピネルの何れも使用せず、ＭｇＯ原料を無添加とした。耐Ｌｉ反応性に欠ける問題があった。
（比較例９）
スピネルを１％添加した。添加量が少ないため、耐Ｌｉ反応性に欠ける問題があった。
(Examples 10 to 14)
As MgO raw materials, coarse particles having a particle size of 2 mm or 0.8 mm and fine particles having a particle size of 0.1 mm or 0.005 mm were mixed and used in the ratios shown in Table 3, respectively. All showed good Li reaction resistance and compressive strength. The specific gravity is small and light weight is realized.
(Example 15)
As the MgO raw material, coarse particles having a particle size of 0.8 mm were used, and spinel was further mixed at a ratio shown in Table 3. Good Li reaction resistance and compressive strength were exhibited. The specific gravity is small and light weight is realized.
(Examples 16 to 18)
As MgO raw material, and a fine coarse and 0.1mm particle size is 0.8 mm, used in a ratio of each table 3, as further Al 2 O 3 raw material, fine powder of particle size 0.05 mm, (Further spinel in Example 16) was mixed and used at the ratio shown in Table 3. All showed extremely good Li reaction resistance. In addition, the compression strength was good, the specific gravity was small, and the weight was reduced.
(Example 19)
Fine particles with a particle size of 0.1 mm are used as the MgO raw material, and fine powder with a particle size of 0.05 mm and Al 2 O 3 bubbles are mixed as the Al 2 O 3 raw material in the proportions shown in Table 3, respectively. Used. All showed good Li reaction resistance and compressive strength. The specific gravity is small and light weight is realized.
(Comparative Example 5)
As the MgO raw material, only fine particles having a particle size of 0.005 mm were used. Although there was no problem in Li resistance, there was a problem inferior in compressive strength.
(Comparative Example 6)
Al 2 O 3 bubbles were not used, and only styrene foam was used instead. Although there was no problem in Li resistance, there was a problem inferior in compressive strength.
(Comparative Example 7)
Neither Al 2 O 3 bubbles nor styrofoam was used. Although there was no problem in Li resistance and compressive strength, there was a problem that specific gravity increased.
(Comparative Example 8)
Neither periclase nor spinel was used, and no MgO raw material was added. There was a problem of lack of resistance to Li reaction.
(Comparative Example 9)
1% of spinel was added. Since the amount added was small, there was a problem of lack of resistance to Li reaction.
以上を考察すると、
表１に示すように、耐Ｌｉ反応性を確保する観点から、ＭｇＯ質は必須要件である。表２に示すように、成形性を確保する観点から、ＭｇＯ原料は粗粒と細粒を組み合わせて使用することが好ましい。表３に示すように、長期間にわたって極めて良好な耐Ｌｉ反応性を確保する観点から、ＭｇＯ原料に添加して使用するＡｌ2Ｏ3原料として微粉末のものを選択することが好ましい。また、同じく、長期間にわたって極めて良好な耐Ｌｉ反応性を確保する観点から、ＸＲＤ測定での結果として、ＭｇＯ質がスピネル型結晶構造として存在する割合が０．５〜８％であることが好ましい。
Considering the above,
As shown in Table 1, MgO quality is an indispensable requirement from the viewpoint of ensuring Li resistance. As shown in Table 2, from the viewpoint of ensuring moldability, the MgO raw material is preferably used in combination of coarse particles and fine particles. As shown in Table 3, it is preferable to select a finely powdered Al 2 O 3 raw material to be used by adding to the MgO raw material from the viewpoint of ensuring extremely good Li resistance over a long period of time. Similarly, from the viewpoint of ensuring extremely good Li-reactivity over a long period of time, it is preferable that the ratio of MgO quality present as a spinel crystal structure is 0.5 to 8% as a result of XRD measurement. .
Claims (6)
ＭｇＯ と Ａｌ2Ｏ3 との合計含有率がＭｇＯ +Ａｌ2Ｏ3＝９５〜９９．９質量％、
ＭｇＯ とＡｌ2Ｏ3との含有比率が、各質量％比で、Ａｌ2Ｏ3 / ＭｇＯ=０．００３ 〜 ２．１、嵩比重が１．０〜２．５であることを特徴とする炉材。 MgO content is 33-99.5 mass%,
The total content of MgO and Al 2 O 3 is MgO + Al 2 O 3 = 95 to 99.9% by mass,
The content ratio of MgO and Al 2 O 3 is, in each mass% ratio, Al 2 O 3 /MgO=0.003 to 2.1, and the bulk specific gravity is 1.0 to 2.5. Furnace material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010261310A JP5732680B2 (en) | 2009-12-01 | 2010-11-24 | Brick and mortar and method for producing the same |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009273111 | 2009-12-01 | ||
| JP2009273111 | 2009-12-01 | ||
| JP2010237168 | 2010-10-22 | ||
| JP2010237168 | 2010-10-22 | ||
| JP2010261310A JP5732680B2 (en) | 2009-12-01 | 2010-11-24 | Brick and mortar and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012106899A true JP2012106899A (en) | 2012-06-07 |
| JP5732680B2 JP5732680B2 (en) | 2015-06-10 |
Family
ID=44395931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010261310A Expired - Fee Related JP5732680B2 (en) | 2009-12-01 | 2010-11-24 | Brick and mortar and method for producing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5732680B2 (en) |
| KR (1) | KR101719823B1 (en) |
| CN (1) | CN102167599B (en) |
| TW (1) | TW201130777A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478474A (en) * | 2014-12-23 | 2015-04-01 | 山东鲁阳股份有限公司 | Light refractory brick and preparation method thereof |
| CN111718203A (en) * | 2020-07-28 | 2020-09-29 | 中国一冶集团有限公司 | Refractory castable for converter sublance and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557680B (en) * | 2011-11-24 | 2015-04-08 | 中钢集团耐火材料有限公司 | Super-micro powder combined impervious spinel brick for refining furnace lining and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003165767A (en) * | 2001-11-28 | 2003-06-10 | Noritake Co Ltd | Spinel refractory and use of the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07126061A (en) * | 1993-09-10 | 1995-05-16 | Kounoshima Kagaku Kogyo Kk | Magnesia-based sintered material and production thereof |
| CN1382665A (en) * | 2001-04-26 | 2002-12-04 | 河南省登封市第二耐火材料总厂 | Synthetic MgAl spinal and its preparing process |
| JP2007112670A (en) | 2005-10-21 | 2007-05-10 | Toshiba Ceramics Co Ltd | Firing vessel |
| JP4721947B2 (en) | 2006-04-19 | 2011-07-13 | 株式会社ニッカトー | Corrosion-resistant magnesia sintered body, heat treatment member comprising the same, and method for producing the sintered body |
| CN101712554B (en) * | 2009-10-28 | 2012-04-04 | 郑州真金耐火材料有限责任公司 | Production method of magnesium-aluminum spinel bricks |
-
2010
- 2010-11-23 TW TW099140322A patent/TW201130777A/en unknown
- 2010-11-24 JP JP2010261310A patent/JP5732680B2/en not_active Expired - Fee Related
- 2010-11-26 KR KR1020100118773A patent/KR101719823B1/en active IP Right Grant
- 2010-12-01 CN CN201010576327.5A patent/CN102167599B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003165767A (en) * | 2001-11-28 | 2003-06-10 | Noritake Co Ltd | Spinel refractory and use of the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478474A (en) * | 2014-12-23 | 2015-04-01 | 山东鲁阳股份有限公司 | Light refractory brick and preparation method thereof |
| CN111718203A (en) * | 2020-07-28 | 2020-09-29 | 中国一冶集团有限公司 | Refractory castable for converter sublance and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102167599B (en) | 2015-08-19 |
| JP5732680B2 (en) | 2015-06-10 |
| KR101719823B1 (en) | 2017-03-24 |
| KR20110061484A (en) | 2011-06-09 |
| TW201130777A (en) | 2011-09-16 |
| CN102167599A (en) | 2011-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105698542B (en) | A kind of anti-lithium battery high temperature corrosion stratiform saggar and preparation method thereof | |
| JP5039640B2 (en) | Pot for producing positive electrode active material for lithium ion battery and method for producing the same | |
| JP5241868B2 (en) | sheath | |
| CN103570364B (en) | One does not burn Mg-Al spinel brick | |
| JP2012224487A (en) | Kiln tool for manufacturing positive electrode active material of lithium secondary battery, and method for manufacturing the same | |
| CN107108376B (en) | Heat insulating unshaped refractory | |
| CN103755363A (en) | Lightweight siliceous mullite composite brick and preparation method thereof | |
| CN106167398A (en) | honeycomb ceramic heat accumulator and preparation method thereof | |
| CN108424124B (en) | Spinel reinforced magnesium oxide base crucible synthesized in situ by magnesium oxide whisker and preparation method thereof | |
| CN109400137A (en) | Anode material of lithium battery firing fire-clay crucible and preparation method thereof | |
| JP6386801B2 (en) | Alumina fusion cast refractory and method for producing the same | |
| CN108546093B (en) | Alumina short fiber reinforced magnesium oxide base crucible and preparation method thereof | |
| JP5732680B2 (en) | Brick and mortar and method for producing the same | |
| JP2003165767A (en) | Spinel refractory and use of the same | |
| CN106365654B (en) | A kind of anti-lithium electric material erosion fire-clay crucible adding ZrN-SiAlON | |
| CN115417658A (en) | Novel magnesium aluminate spinel brick for cement kiln burning zone and production method thereof | |
| CN113716940A (en) | Novel heat storage brick and preparation method thereof | |
| CN112250423A (en) | Anti-seepage high-strength forsterite light heat-insulating brick and preparation method thereof | |
| JP2006206338A (en) | Highly corrosion-resistant refractory | |
| JP4488444B2 (en) | Method for producing porous ceramics and porous ceramics | |
| KR20130051290A (en) | Kiln furniture and its composition for sintering cathode material of secondary battery | |
| CN110452009A (en) | A kind of preparation method of in-situ preparation magnesium aluminate spinel whisker skeletal porous ceramics | |
| EP3421571B1 (en) | Precast refractory block for coke oven | |
| CN109095902A (en) | A kind of glass furnace paving brick and its production technology | |
| CN114105630A (en) | Petalite combined calcium hexaluminate sagger and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120807 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130205 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130215 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130409 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131101 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131219 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20131219 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140627 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140730 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20141209 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20150105 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150106 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150317 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150325 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5732680 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |