JP2011051830A - Molded material and method for manufacturing the same, and high temperature superheated steam generating system equipped with the same - Google Patents
Molded material and method for manufacturing the same, and high temperature superheated steam generating system equipped with the same Download PDFInfo
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Abstract
Description
本発明は、成形材料及びその製造方法並びにこれを備える高温過熱蒸気生成システムに関し、更に詳しくは、安定した電磁誘導型発熱体を構成する成形材料及びその製造方法、並びに、これを備え、過熱蒸気を安定製造することができる高温過熱蒸気生成システムに関する。 The present invention relates to a molding material, a method for producing the same, and a high-temperature superheated steam generation system including the same, and more particularly, a molding material constituting a stable electromagnetic induction heating element, a method for producing the same, and a superheated steam provided with the same. The present invention relates to a high-temperature superheated steam generation system that can stably manufacture a gas.
過熱蒸気生成システムは、大型のセラミックス成形体の乾燥、粉体処理、金型の表面改質、水素製造装置、食品加工（加熱、乾燥、解凍、焼き、蒸し、殺菌、滅菌、脱臭等）等の分野に広く展開されている。例えば、食品加工の分野においては、過熱水蒸気が急速に普及しており、そのための過熱水蒸気生成装置としては、電磁誘導によって発熱させるための、鉄、ニッケル、チタン等の金属、ステンレス鋼及びカーボンセラミック等の材料からなる、所定形状（例えば、球状）の発熱体と、複数の発熱体を充填させつつこれらを接触状態で収容する収容体（炉体）と、この収容体の外側に配された励磁コイルとを備えるものが知られている（特許文献１、２等参照）。この過熱水蒸気生成装置においては、励磁コイルから発生させた磁界変化により発熱体を発熱させ、収容体に導入した水蒸気をこの発熱体に接触させ、過熱水蒸気を生成させている。 Superheated steam generation system, drying of large ceramic molded body, powder processing, mold surface modification, hydrogen production equipment, food processing (heating, drying, thawing, baking, steaming, sterilization, sterilization, deodorization, etc.), etc. Widely deployed in the field. For example, in the field of food processing, superheated steam is rapidly spreading, and as a superheated steam generator for that purpose, metals such as iron, nickel, titanium, stainless steel, and carbon ceramic for generating heat by electromagnetic induction are used. A heating element having a predetermined shape (for example, a spherical shape) made of a material such as a container, a container (furnace) that contains a plurality of heating elements in a contact state while being filled, and is disposed outside the container. A thing provided with an exciting coil is known (refer to patent documents 1 and 2 grades). In this superheated steam generator, the heating element is heated by a change in the magnetic field generated from the exciting coil, and the steam introduced into the container is brought into contact with the heating element to generate superheated steam.
上記のように、電磁誘導型の発熱体を複数備える過熱水蒸気生成装置の場合、使用を重ねるにつれ、発熱体どうしの接触部において、局所的に流れた大電流に起因する材料の溶融等により、凹部が形成されたり（図９参照）、変質したりする欠陥が発生することがあった。
本発明の目的は、電磁誘導により、物品、気体等の熱処理等のために、５００℃以上といった高温域の所望の温度に発熱させることができ、耐久性に優れた電磁誘導型発熱体として好適な成形材料、特に、この成形材料を複数用い、互いに接触状態として発熱構造体を形成した場合に、上記温度への発熱の安定性に優れる成形材料及びその製造方法、この成形材料を複数備え、使用を重ねても、発熱体（成形材料）の表面における欠陥の発生が抑制され、水蒸気、水蒸気を含む混合気体等の気体の加熱による過熱蒸気を安定製造することができる高温過熱蒸気生成システムを提供することにある。
As described above, in the case of the superheated steam generating device including a plurality of electromagnetic induction type heating elements, as the use is repeated, in the contact portion between the heating elements, due to the melting of the material caused by the large current that flows locally, etc. In some cases, a recess was formed (see FIG. 9) or a defect such as alteration occurred.
The object of the present invention is to generate heat to a desired temperature in a high temperature range of 500 ° C. or higher for heat treatment of articles, gases, etc. by electromagnetic induction, and is suitable as an electromagnetic induction type heating element with excellent durability. When a plurality of molding materials are used and a heat generating structure is formed in contact with each other, a molding material excellent in the stability of heat generation to the above temperature and a method for producing the same, and a plurality of the molding materials are provided. A high-temperature superheated steam generation system that can suppress the occurrence of defects on the surface of a heating element (molding material) even after repeated use, and can stably produce superheated steam by heating a gas such as water vapor or a mixed gas containing water vapor. It is to provide.
本発明者らは、ランタン系ペロブスカイト型酸化物を含む基部の表面に、Ｌａ及びＳｉを含む複合酸化物を含む被覆部を形成させてなる成形材料を、電磁誘導を利用した発熱体として用いることで、耐久性に優れた高温過熱蒸気生成システムが得られたことを見出した。 The present inventors use a molding material in which a covering portion containing a composite oxide containing La and Si is formed on the surface of a base portion containing a lanthanum perovskite oxide as a heating element utilizing electromagnetic induction. Thus, it was found that a high-temperature superheated steam generation system having excellent durability was obtained.
本発明は、以下に示される。
１．下記一般式（１）で表される化合物を含む基部と、この基部の表面に配された、下記一般式（２）で表される化合物を含む被覆部と、を備えることを特徴とする成形材料。
Ｌａ１−ｘＭ１ ｘＭ２Ｏ３−ｙ （１）
〔式中、Ｍ１は、Ｍｇ、Ｃａ、Ｓｒ及びＢａから選ばれた少なくとも１種の元素であり、Ｍ２は、Ｃｒ、Ｃｏ及びＭｎから選ばれた少なくとも１種の元素であり、０＜ｘ≦０．５、且つ、０≦ｙ≦０．１である。〕
Ｌａ２Ｏ３・ｎ（ＳｉＯ２） （２）
〔式中、ｎは、１以上２以下の数である。〕
２．上記一般式（１）において、元素Ｍ１がＳｒであり、元素Ｍ２がＭｎであり、且つ、０．１≦ｘ≦０．３である上記１に記載の成形材料。
３．形状が、棒体、板体、球体又は多面体である上記１又は２に記載の成形材料。
４．上記１に記載の成形材料の製造方法であって、
下記一般式（１）で表される化合物を含む成形体を得る成形体作製工程と、ポリシラザンを含む溶液を用いて、上記成形体の表面にポリシラザンを含む塗膜を形成する塗膜形成工程と、上記塗膜を、熱処理し、下記一般式（２）で表される化合物を含む皮膜を形成する皮膜化工程と、を備えることを特徴とする成形材料の製造方法。
Ｌａ１−ｘＭ１ ｘＭ２Ｏ３−ｙ （１）
〔式中、Ｍ１は、Ｍｇ、Ｃａ、Ｓｒ及びＢａから選ばれた少なくとも１種の元素であり、Ｍ２は、Ｃｒ、Ｃｏ及びＭｎから選ばれた少なくとも１種の元素であり、０＜ｘ≦０．５、且つ、０≦ｙ≦０．１である。〕
Ｌａ２Ｏ３・ｎ（ＳｉＯ２） （２）
〔式中、ｎは、１以上２以下の数である。〕
５．上記１乃至３のいずれかに記載の成形材料を有する高温過熱蒸気生成システムであって、上記成形材料の複数が積み上げられて形成された、上下方向に通気可能な発熱構造体と、この発熱構造体を収容し、且つ、略筒状である収容体と、この収容体の一方の開口部に連通された気体供給装置と、上記収容体の外側にあって、少なくとも上記発熱構造体を包囲するように配設された励磁コイルと、を備えることを特徴とする高温過熱蒸気生成システム。
６．上記収容体の内壁面の構成材料が、Ａｌ２ＴｉＯ５を含む上記５に記載の高温過熱蒸気生成システム。
The present invention is shown below.
1. A molding comprising: a base portion containing a compound represented by the following general formula (1); and a covering portion containing a compound represented by the following general formula (2) disposed on the surface of the base portion. material.
La 1-x M 1 x M 2 O 3-y (1)
[Wherein, M 1 is at least one element selected from Mg, Ca, Sr and Ba, M 2 is at least one element selected from Cr, Co and Mn, and 0 < x ≦ 0.5 and 0 ≦ y ≦ 0.1. ]
La 2 O 3 · n (SiO 2 ) (2)
[In the formula, n is a number of 1 or more and 2 or less. ]
2. 2. The molding material according to 1 above, wherein in the general formula (1), the element M 1 is Sr, the element M 2 is Mn, and 0.1 ≦ x ≦ 0.3.
3. 3. The molding material according to 1 or 2 above, wherein the shape is a rod, plate, sphere or polyhedron.
4). A method for producing the molding material according to 1 above,
A molded body preparation step for obtaining a molded body containing a compound represented by the following general formula (1), and a coating film forming step for forming a coating film containing polysilazane on the surface of the molded body using a solution containing polysilazane. And a film-forming step of heat-treating the coating film to form a film containing a compound represented by the following general formula (2).
La 1-x M 1 x M 2 O 3-y (1)
[Wherein, M 1 is at least one element selected from Mg, Ca, Sr and Ba, M 2 is at least one element selected from Cr, Co and Mn, and 0 < x ≦ 0.5 and 0 ≦ y ≦ 0.1. ]
La 2 O 3 · n (SiO 2 ) (2)
[In the formula, n is a number of 1 or more and 2 or less. ]
5). A high-temperature superheated steam generation system comprising the molding material according to any one of 1 to 3 above, wherein the heating structure is formed by stacking a plurality of the molding materials and is vertically permeable, and the heating structure A body that is substantially cylindrical, a gas supply device that communicates with one opening of the container, and is located outside the container and surrounds at least the heat generating structure. And a high temperature superheated steam generation system.
6). The high-temperature superheated steam generation system according to 5 above, wherein the constituent material of the inner wall surface of the container includes Al 2 TiO 5 .
本発明の成形材料によれば、電磁誘導により、物品、気体等の熱処理等のために、５００℃以上の高温域の所望の温度に発熱させることができる電磁誘導型発熱体として好適である。そして、この成形材料を複数用い、互いに接触状態として発熱構造体を形成した場合に、その耐久性に優れ、上記温度における加熱の安定性に優れる。
上記一般式（１）において、元素Ｍ１がＳｒであり、元素Ｍ２がＭｎであり、且つ、０．１≦ｘ≦０．３である場合には、本発明の成形材料を、より優れた耐久性を有しつつ、電磁誘導により、好ましくは６００℃〜９００℃といった高温域の所望の温度に発熱させることができる電磁誘導型発熱体として好適に用いることができる。また、上記温度における加熱により、水蒸気、水蒸気を含む混合気体（水蒸気及び空気からなる混合気体等）等の気体を、安定して過熱蒸気とすることができ、特に、水蒸気を更に加熱して過熱水蒸気とした場合に耐食性に優れ、使用を重ねたことによる表面の損傷が抑制された電磁誘導型発熱体とすることができる。
The molding material of the present invention is suitable as an electromagnetic induction heating element capable of generating heat to a desired temperature in a high temperature range of 500 ° C. or higher due to electromagnetic induction for heat treatment of articles, gases, and the like. When a plurality of the molding materials are used and the heat generating structures are formed in contact with each other, the durability is excellent and the heating stability at the above temperature is excellent.
In the general formula (1), when the element M 1 is Sr, the element M 2 is Mn, and 0.1 ≦ x ≦ 0.3, the molding material of the present invention is more excellent. In addition, it can be suitably used as an electromagnetic induction heating element capable of generating heat to a desired temperature in a high temperature range such as 600 ° C. to 900 ° C. by electromagnetic induction while having high durability. Further, by heating at the above temperature, a gas such as water vapor or a mixed gas containing water vapor (a mixed gas composed of water vapor and air, etc.) can be stably converted into superheated steam. When water vapor is used, the electromagnetic induction heating element is excellent in corrosion resistance and suppressed surface damage due to repeated use.
本発明の成形材料の製造方法によれば、基部を構成する成形体の形状に依存することなく、その表面に、緻密な被覆部を構成することとなる皮膜を形成することができ、成形体（基部）及び皮膜（被覆部）の密着性、耐久性に優れた成形材料を、効率よく製造することができる。 According to the method for producing a molding material of the present invention, it is possible to form a film that forms a dense covering portion on the surface without depending on the shape of the molding constituting the base portion. The molding material excellent in the adhesion and durability of the (base) and the coating (covering portion) can be efficiently produced.
本発明の高温過熱蒸気生成システムによれば、収容体内に導入された、水蒸気、水蒸気を含む混合気体（水蒸気及び空気からなる混合気体等）等の気体を、電磁誘導により発熱させた発熱構造体によって、加熱して、５００℃以上、好ましくは６００℃〜９００℃といった所望の高い温度の気体（過熱蒸気）を、容易に且つ安定して製造及び供給することができる。
上記収容体の内壁面の構成材料が、Ａｌ２ＴｉＯ５を含む場合には、耐熱性、断熱性、耐衝撃性、耐水蒸気性等にも優れた収容体を備える高温過熱蒸気生成システムとすることができる。
According to the high-temperature superheated steam generation system of the present invention, a heat generating structure in which a gas such as water vapor or a mixed gas containing water vapor (a mixed gas composed of water vapor and air) or the like introduced into the container is heated by electromagnetic induction. By heating, a desired high temperature gas (superheated steam) of 500 ° C. or higher, preferably 600 ° C. to 900 ° C. can be easily and stably produced and supplied.
When the constituent material of the inner wall surface of the container includes Al 2 TiO 5 , a high-temperature superheated steam generation system including a container excellent in heat resistance, heat insulation, impact resistance, water vapor resistance, and the like is provided. be able to.
以下、本発明を詳しく説明する。
１．成形材料
本発明の成形材料は、下記一般式（１）で表される化合物（以下、「特定酸化物」ともいう。）を含む基部と、この基部の表面に配された、下記一般式（２）で表される化合物を含む被覆部と、を備えることを特徴とする。
Ｌａ１−ｘＭ１ ｘＭ２Ｏ３−ｙ （１）
〔式中、Ｍ１は、Ｍｇ、Ｃａ、Ｓｒ及びＢａから選ばれた少なくとも１種の元素であり、Ｍ２は、Ｃｒ、Ｃｏ及びＭｎから選ばれた少なくとも１種の元素であり、０＜ｘ≦０．５、且つ、０≦ｙ≦０．１である。〕
Ｌａ２Ｏ３・ｎ（ＳｉＯ２） （２）
〔式中、ｎは、１以上２以下の数である。〕
The present invention will be described in detail below.
1. Molding Material The molding material of the present invention has a base containing a compound represented by the following general formula (1) (hereinafter also referred to as “specific oxide”) and the following general formula ( And a covering portion containing the compound represented by 2).
La 1-x M 1 x M 2 O 3-y (1)
[Wherein, M 1 is at least one element selected from Mg, Ca, Sr and Ba, M 2 is at least one element selected from Cr, Co and Mn, and 0 < x ≦ 0.5 and 0 ≦ y ≦ 0.1. ]
La 2 O 3 · n (SiO 2 ) (2)
[In the formula, n is a number of 1 or more and 2 or less. ]
上記基部に含まれる、上記一般式（１）で表される酸化物（特定酸化物）において、元素Ｍ１は、Ｍｇ、Ｃａ、Ｓｒ及びＢａから選ばれた少なくとも１種であり、これらのうちの１種のみであってよいし、２種以上の組合せであってもよい。本発明においては、上記元素Ｍ１は、Ｓｒを含むことが好ましく、この場合の酸化物は、下記一般式（３）及び（４）で表すことができる。
Ｌａ１−ｘＳｒｘＭ２Ｏ３−ｙ （３）
Ｌａ１−ｘＳｒｘｚＭ１１ ｘ−ｘｚＭ２Ｏ３−ｙ （４）
〔但し、Ｍ１１は、Ｍｇ、Ｃａ及びＢａから選ばれた少なくとも１種の元素であり、Ｍ２は、Ｃｒ、Ｃｏ及びＭｎから選ばれた少なくとも１種の元素であり、０＜ｘ≦０．５、０≦ｙ≦０．１、且つ、０．５≦ｚ＜１である。〕
上記一般式（３）及び（４）で表される酸化物は、単独で用いてよいし、組み合わせて用いてもよい。
In the oxide (specific oxide) represented by the general formula (1) included in the base, the element M 1 is at least one selected from Mg, Ca, Sr and Ba, and among these, It may be only 1 type of these, and the combination of 2 or more types may be sufficient. In the present invention, the element M 1 preferably contains Sr, and the oxide in this case can be represented by the following general formulas (3) and (4).
La 1-x Sr x M 2 O 3-y (3)
La 1-x Sr xz M 11 x-xz M 2 O 3-y (4)
[However, M 11 is at least one element selected from Mg, Ca, and Ba, and M 2 is at least one element selected from Cr, Co, and Mn, and 0 <x ≦ 0. 0.5, 0 ≦ y ≦ 0.1, and 0.5 ≦ z <1. ]
The oxides represented by the general formulas (3) and (4) may be used alone or in combination.
また、上記一般式（１）、（３）及び（４）で表される酸化物において、元素Ｍ２は、Ｃｒ、Ｃｏ及びＭｎから選ばれた少なくとも１種であり、これらのうちの１種のみであってよいし、２種以上の組合せであってもよい。本発明においては、上記元素Ｍ２は、Ｍｎを含むことが好ましい。 Similarly, the general formula (1), (3) and in the oxide represented by (4), the element M 2 is at least one selected Cr, Co and Mn, one of these May be a combination of two or more. In the present invention, the element M 2 preferably contains Mn.
上記一般式（１）、（３）及び（４）で表される酸化物において、電磁誘導により５００℃以上に発熱させたときの安定性の観点から、０＜ｘ≦０．５である。また、被熱処理物（物品、気体等）の種類によらず、長期及び繰り返し使用可能等の観点から、好ましくは０＜ｘ≦０．４、より好ましくは０．１≦ｘ≦０．３である。 In the oxides represented by the general formulas (1), (3), and (4), 0 <x ≦ 0.5 from the viewpoint of stability when heat is generated to 500 ° C. or more by electromagnetic induction. In addition, from the viewpoint of long-term use and repetitive use regardless of the type of the heat-treated material (article, gas, etc.), preferably 0 <x ≦ 0.4, more preferably 0.1 ≦ x ≦ 0.3. is there.
本発明においては、上記特定酸化物は、上記一般式（１）において、元素Ｍ１がＳｒである化合物、即ち、上記一般式（３）で表される化合物であって、元素Ｍ２がＭｎであり、且つ、０．１≦ｘ≦０．３である化合物であることが好ましい。本発明の成形材料における基部が、この化合物を含むと、電磁誘導により、５００℃以上、好ましくは６００℃〜９００℃といった高温域の所望の温度に発熱させやすく、この温度において過熱水蒸気を生成させる際の耐食性に特に優れる。 In the present invention, the specific oxide is a compound in which the element M 1 is Sr in the general formula (1), that is, a compound represented by the general formula (3), and the element M 2 is Mn. And preferably a compound satisfying 0.1 ≦ x ≦ 0.3. When the base in the molding material of the present invention contains this compound, it is easy to generate heat to a desired temperature in a high temperature range of 500 ° C. or higher, preferably 600 ° C. to 900 ° C. by electromagnetic induction, and superheated steam is generated at this temperature. Especially excellent in corrosion resistance.
上記基部は、上記特定酸化物を含むものであるが、この特定酸化物の製造に際して生成した不可避的不純物及び下記一般式（５）で表される酸化物を含有してもよい。
ＬａＭ２Ｏ３−ｙ （５）
〔式中、Ｍ２は、Ｃｒ、Ｃｏ及びＭｎから選ばれた少なくとも１種の元素であり、且つ、０≦ｙ≦０．１である。〕
Although the said base contains the said specific oxide, you may contain the oxide represented by the inevitable impurity produced | generated at the time of manufacture of this specific oxide, and following General formula (5).
LaM 2 O 3-y (5)
[Wherein M 2 is at least one element selected from Cr, Co and Mn, and 0 ≦ y ≦ 0.1. ]
上記基部に含まれる特定酸化物の含有割合は、すべての化合物の合計を１００質量％とした場合、好ましくは８０質量％以上、より好ましくは９５〜１００質量％である。この特定酸化物の含有割合が高いほど、５００℃以上、好ましくは６００℃〜９００℃といった高い発熱温度に対する安定性に優れる。 The content ratio of the specific oxide contained in the base is preferably 80% by mass or more, more preferably 95 to 100% by mass, when the total of all the compounds is 100% by mass. The higher the content ratio of the specific oxide, the better the stability to a high exothermic temperature of 500 ° C or higher, preferably 600 ° C to 900 ° C.
一方、上記被覆部は、上記基部の表面を覆う部分（層）であり、上記一般式（２）で表される化合物を含む。即ち、この被覆部は、上記一般式（２）で表される化合物のみからなる部分であってよいし、上記一般式（２）で表される化合物と、他の化合物とからなる部分であってもよい。上記一般式（２）で表される化合物の含有量は、本発明の成形材料の耐久性の観点から、上記被覆部を構成する化合物の全量に対して、好ましくは４０質量％以上、より好ましくは５０質量％以上、更に好ましくは６０質量％以上、特に好ましくは６５〜１００質量％である。 On the other hand, the said coating | coated part is a part (layer) which covers the surface of the said base, and contains the compound represented by the said General formula (2). That is, the covering portion may be a portion composed only of the compound represented by the general formula (2), or a portion composed of the compound represented by the general formula (2) and another compound. May be. From the viewpoint of durability of the molding material of the present invention, the content of the compound represented by the general formula (2) is preferably 40% by mass or more, more preferably, based on the total amount of the compound constituting the covering portion. Is 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 65 to 100% by mass.
上記被覆部に含まれる、上記一般式（２）で表される化合物は、１種のみであってよいし、２種以上であってもよい。
上記一般式（２）において、ｎ＝１及びｎ＝２の場合の化合物、即ち、Ｌａ２Ｏ３・ＳｉＯ２及びＬａ２Ｏ３・２ＳｉＯ２は、安定化合物である。また、１＜ｎ＜２の化合物の場合、この構成の成形材料を、電磁誘導の利用による発熱体として用いると、時間とともに、ｎ＝１及び／又はｎ＝２の化合物に変化する傾向にある。
上記被覆部を構成する一般式（２）で表される化合物の構造は、Ｘ線回折等により、同定（定性分析）することができる。
The compound represented by the general formula (2) contained in the covering portion may be only one kind or two or more kinds.
In the general formula (2), compounds in the case of n = 1 and n = 2, that is, La 2 O 3 .SiO 2 and La 2 O 3 .2SiO 2 are stable compounds. Further, in the case of a compound of 1 <n <2, when the molding material having this configuration is used as a heating element by using electromagnetic induction, it tends to change to a compound of n = 1 and / or n = 2 with time. .
The structure of the compound represented by the general formula (2) constituting the covering portion can be identified (qualitative analysis) by X-ray diffraction or the like.
上記被覆部が、他の化合物を含む場合、例えば、下記一般式（６）で表される化合物が挙げられる。
ｐ（Ｍ２Ｏ）・ｑ（ＳｉＯ２） （６）
〔式中、Ｍ２Ｏは、Ｃｒ、Ｃｏ及びＭｎから選ばれた少なくとも１種の元素Ｍ２の酸化物の１種又は２種以上であり、且つ、０≦ｐ／ｑ≦１０である。〕
この一般式（６）の構造もまた、Ｘ線回折等により、同定（定性分析）することができる。
When the said coating | coated part contains another compound, the compound represented by following General formula (6) is mentioned, for example.
p (M 2 O) · q (SiO 2 ) (6)
[Wherein, M 2 O is one or more of oxides of at least one element M 2 selected from Cr, Co, and Mn, and 0 ≦ p / q ≦ 10. ]
The structure of the general formula (6) can also be identified (qualitative analysis) by X-ray diffraction or the like.
本発明においては、上記一般式（６）で表される化合物を構成する元素Ｍ２は、上記基部に含まれる特定酸化物（上記一般式（１）で表される化合物）を構成する元素Ｍ２と同一元素を含むことが好ましい。例えば、上記特定酸化物がＬａ１−ｘＳｒｘＭｎＯ３である場合には、他の化合物を表す上記一般式（６）における元素Ｍ２がＭｎであることが好ましい。従って、他の化合物は、下記式（７）で表すことができる。
ｐ１（ＭｎＯ）・ｐ２（Ｍｎ２Ｏ３）・ｑ（ＳｉＯ２） （７）
上記式（７）において、ｐ１＝１のとき、好ましくは０≦ｐ２≦３、０．５≦ｑ≦１である。
In the present invention, the element M 2 constituting the compound represented by the general formula (6) is the element M constituting the specific oxide (compound represented by the general formula (1)) contained in the base. 2 is preferably contained. For example, if the specific oxide is La 1-x Sr x MnO 3, it is preferable elements M 2 in the general formula (6) representing the other compound is Mn. Therefore, another compound can be represented by the following formula (7).
p 1 (MnO) · p 2 (Mn 2 O 3 ) · q (SiO 2 ) (7)
In the above formula (7), when p 1 = 1, preferably 0 ≦ p 2 ≦ 3 and 0.5 ≦ q ≦ 1.
上記被覆部は、上記一般式（２）で表される化合物を含む層が積層されて形成されたものであってもよい。 The covering portion may be formed by laminating layers containing the compound represented by the general formula (2).
上記被覆部の厚さは、電磁誘導を利用した発熱体としての安定性、発熱体自身と被覆部との熱膨張係数差の影響を軽減する等の観点から、好ましくは０．５〜５０μｍ、より好ましくは１〜１０μｍ、更に好ましくは２〜５μｍである。 The thickness of the covering portion is preferably 0.5 to 50 μm from the viewpoint of stability as a heating element using electromagnetic induction, reducing the influence of a difference in thermal expansion coefficient between the heating element itself and the covering portion, etc. More preferably, it is 1-10 micrometers, More preferably, it is 2-5 micrometers.
上記被覆部の形成方法は、特に限定されないが、後述する、本発明の成形材料の製造方法におけるポリシラザンを用いた方法、ゾルゲル法、溶射法等が挙げられる。 The method for forming the covering portion is not particularly limited, and examples thereof include a method using polysilazane, a sol-gel method, a thermal spraying method, and the like described later in the method for producing a molding material of the present invention.
本発明の成形材料の形状は、特に限定されず、定形体及び不定形体のいずれでもよい。好ましい形状は、棒体、線体、板体、球体（楕円球体を含む）、多面体等の定形体であり、特に好ましくは、棒体、板体、球体及び多面体である。尚、本発明の成形材料は、凸部、凹部、貫通孔等の部位を有してもよい。図１に、板体の一例である円板型成形材料１１１を示す。 The shape of the molding material of the present invention is not particularly limited, and may be either a regular shape or an irregular shape. Preferred shapes are fixed shapes such as rods, lines, plates, spheres (including elliptical spheres), and polyhedrons, and rods, plates, spheres, and polyhedrons are particularly preferred. In addition, the molding material of this invention may have sites, such as a convex part, a recessed part, and a through-hole. FIG. 1 shows a disk-shaped molding material 111 which is an example of a plate body.
本発明の成形材料は、電磁誘導型発熱体として好適であり、電磁誘導により、９００℃程度の高い温度にまで、自身が分解、変質、脱ガス、変形粒成長等することなく発熱させることができる。
被熱処理物に対する電磁誘導型発熱体の使用方法としては、気体を加熱する場合には、発熱している電磁誘導型発熱体の周辺及び／又は内部に通気させる方法がある。一方、固体を加熱する場合には、その構成材料、形状等により、接触加熱及び非接触加熱から選択される。
The molding material of the present invention is suitable as an electromagnetic induction-type heating element, and can heat itself up to a high temperature of about 900 ° C. without being decomposed, altered, degassed, deformed grain growth or the like by electromagnetic induction. it can.
As a method of using the electromagnetic induction heating element for the object to be heat-treated, there is a method of venting around and / or inside the electromagnetic induction heating element that is generating heat when the gas is heated. On the other hand, when heating a solid, it is selected from contact heating and non-contact heating depending on its constituent material, shape and the like.
本発明の成形材料の製造方法は、下記一般式（１）で表される化合物を含む成形体を得る成形体作製工程と、ポリシラザンを含む溶液を用いて、上記成形体の表面にポリシラザンを含む塗膜を形成する塗膜形成工程と、上記塗膜を、熱処理し、下記一般式（２）で表される化合物を含む皮膜を形成する皮膜化工程と、を備えることを特徴とする。
Ｌａ１−ｘＭ１ ｘＭ２Ｏ３−ｙ （１）
〔式中、Ｍ１は、Ｍｇ、Ｃａ、Ｓｒ及びＢａから選ばれた少なくとも１種の元素であり、Ｍ２は、Ｃｒ、Ｃｏ及びＭｎから選ばれた少なくとも１種の元素であり、０＜ｘ≦０．５、且つ、０≦ｙ≦０．１である。〕
Ｌａ２Ｏ３・ｎ（ＳｉＯ２） （２）
〔式中、ｎは、１以上２以下の数である。〕
The method for producing a molding material of the present invention includes a polysilazane on the surface of the molded body by using a molded body preparation step for obtaining a molded body including a compound represented by the following general formula (1) and a solution containing polysilazane. A coating film forming process for forming a coating film, and a film forming process for heat-treating the coating film to form a film containing a compound represented by the following general formula (2).
La 1-x M 1 x M 2 O 3-y (1)
[Wherein, M 1 is at least one element selected from Mg, Ca, Sr and Ba, M 2 is at least one element selected from Cr, Co and Mn, and 0 < x ≦ 0.5 and 0 ≦ y ≦ 0.1. ]
La 2 O 3 · n (SiO 2 ) (2)
[In the formula, n is a number of 1 or more and 2 or less. ]
上記成形体作製工程は、上記一般式（１）で表される化合物、即ち、特定酸化物を含む成形体を得る工程である。この工程においては、特定酸化物からなる粉末を含む原料組成物（成形用バインダー、焼結助剤等を含んでもよい）を、金型プレス、ＣＩＰ等のプレス成形等に供して所定の形状体（棒体、線体、板体、球体、多面体等）とし、これを、大気等の酸素含有雰囲気、又は、真空雰囲気にて、例えば、１，２００℃〜１，６００℃の温度で熱処理することにより、成形体とすることができる。上記範囲の温度で熱処理することで、十分な焼結性が得られる。
成形用バインダーとしては、アクリル系重合体、ニトロセルロース、メチルセルロース、エチルセルロース、ポリビニルアルコール、ポリビニルブチラール、デンプン、ワックス等が挙げられる。この成形用バインダーの使用量の上限は、上記特定酸化物を１００質量部とした場合に、通常、２０質量部である。
The said molded object preparation process is a process of obtaining the molded object containing the compound represented by the said General formula (1), ie, a specific oxide. In this step, a raw material composition containing a powder made of a specific oxide (which may contain a molding binder, a sintering aid, etc.) is subjected to press molding such as a die press, CIP, etc., and has a predetermined shape. (Rod, wire, plate, sphere, polyhedron, etc.), and this is heat-treated at a temperature of, for example, 1,200 ° C. to 1,600 ° C. in an oxygen-containing atmosphere such as air or a vacuum atmosphere. By this, it can be set as a molded object. Sufficient sinterability can be obtained by heat treatment at a temperature within the above range.
Examples of the molding binder include acrylic polymers, nitrocellulose, methylcellulose, ethylcellulose, polyvinyl alcohol, polyvinyl butyral, starch, and wax. The upper limit of the amount of the molding binder used is usually 20 parts by mass when the specific oxide is 100 parts by mass.
尚、上記特定酸化物の製造方法について、簡単に説明する。
原料は、Ｌａ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｃｒ、Ｃｏ又はＭｎを含む、酸化物、水酸化物、炭酸塩、硝酸塩、金属アルコキシド等、通常のセラミックス製造に用いられる化合物を、所定の割合に配合し、固体状態で、あるいは、水及び／又は有機溶媒に溶解若しくは分散させたものである。この原料は、必要に応じて、バインダー等を配合されたものであってもよい。従って、上記各成分を、乾式混合又は湿式混合により混合、分散させ、乾式混合の場合には粉末混合物を、湿式混合の場合にはスラリーを調製した後、乾燥し、粉末混合物、即ち、原料を得る。
湿式混合を適用し、媒体として水を用いる場合には、製造しようとする酸化物の電子伝導性及び耐熱性を維持するために、塩基性成分の混入が抑制されたイオン交換水、蒸留水等を用いることが好ましい。また、必要に応じて、公知の分散剤を適量添加してもよい。湿式混合の場合は、得られたスラリーをスプレードライヤー等により乾燥させるが、このときの乾燥温度は、使用した媒体の沸点によって、適宜、設定すればよく、混合、分散させた各原料粉末が分離しないように、できるだけ短時間で乾燥させることが好ましい。
次いで、得られた粉末混合物に対して熱処理を行うことにより、上記特定酸化物が製造される。熱処理条件としては、温度は、好ましくは１，２００℃〜１，６００℃の範囲、より好ましくは１，４００℃〜１，６００℃の範囲であり、雰囲気は、大気等の酸素含有雰囲気が好ましい。尚、このようにして得られた熱処理物の構成成分の大半は、上記特定酸化物であるが、バインダー由来成分、分散剤由来成分、副生成物等の不可避的不純物を含むことがある。
In addition, the manufacturing method of the said specific oxide is demonstrated easily.
The raw material contains La, Mg, Ca, Sr, Ba, Cr, Co, or Mn, and oxides, hydroxides, carbonates, nitrates, metal alkoxides, and the like, which are used in normal ceramic production, in a predetermined ratio. And dissolved or dispersed in water and / or an organic solvent. This raw material may be blended with a binder or the like as required. Accordingly, each of the above components is mixed and dispersed by dry mixing or wet mixing, and in the case of dry mixing, a powder mixture is prepared, and in the case of wet mixing, a slurry is prepared and then dried, and the powder mixture, that is, the raw material is prepared. obtain.
When wet mixing is applied and water is used as the medium, ion-exchanged water, distilled water, etc. in which mixing of basic components is suppressed to maintain the electronic conductivity and heat resistance of the oxide to be produced. Is preferably used. Moreover, you may add a suitable quantity of a well-known dispersing agent as needed. In the case of wet mixing, the obtained slurry is dried with a spray dryer or the like, and the drying temperature at this time may be appropriately set according to the boiling point of the medium used, and the mixed and dispersed raw material powders are separated. It is preferable to dry in as short a time as possible.
Next, the specific oxide is produced by performing a heat treatment on the obtained powder mixture. As heat treatment conditions, the temperature is preferably in the range of 1,200 ° C. to 1,600 ° C., more preferably in the range of 1,400 ° C. to 1,600 ° C., and the atmosphere is preferably an oxygen-containing atmosphere such as air. . Most of the constituent components of the heat-treated product thus obtained are the specific oxides, but may contain inevitable impurities such as binder-derived components, dispersant-derived components, and by-products.
その後、上記塗膜形成工程において、ポリシラザンを含む溶液（以下、「ポリシラザン溶液」という。）を用いて、上記成形体の表面にポリシラザンを含む塗膜が形成される。 Thereafter, in the coating film forming step, a coating film containing polysilazane is formed on the surface of the molded body using a solution containing polysilazane (hereinafter referred to as “polysilazane solution”).
上記ポリシラザンは、下記一般式（８）で表される単位を含み、数平均分子量が、好ましくは３０，０００〜１２０，０００、より好ましくは３２，０００〜８０，０００、更に好ましくは３６，０００〜５４，０００の化合物である。
上記ポリシラザン溶液における溶媒は、ポリシラザンを溶解する化合物が好ましく、トルエン、キシレン、メシチレン、２−ブタノン、メチルイソブチルケトン、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。これらは、単独で用いてよいし、２つ以上を組み合わせて用いてもよい。
上記ポリシラザン溶液におけるポリシラザンの濃度は、特に限定されない。
上記ポリシラザン溶液は、市販品を用いることができ、例えば、ＡＺエレクトロニックマテリアルズ社製ポリシラザン溶液「ＮＮ３１０−３０」（商品名）を用いることができる。
The solvent in the polysilazane solution is preferably a compound that dissolves polysilazane, and examples thereof include toluene, xylene, mesitylene, 2-butanone, methyl isobutyl ketone, and propylene glycol monomethyl ether acetate. These may be used alone or in combination of two or more.
The concentration of polysilazane in the polysilazane solution is not particularly limited.
A commercial item can be used for the said polysilazane solution, for example, the polysilazane solution "NN310-30" (brand name) by AZ Electronic Materials can be used.
上記塗膜形成工程において、塗膜の形成方法は、特に限定されず、ディッピング法、スプレー法、スピンコート法等が適用される。また、塗膜形成時の温度も、特に限定されず、室温等とすることができる。 In the coating film forming step, the method for forming the coating film is not particularly limited, and a dipping method, a spray method, a spin coating method, or the like is applied. Moreover, the temperature at the time of coating film formation is not specifically limited, either, Room temperature etc. can be used.
次に、皮膜化工程により、上記成形体の表面の塗膜が熱処理され、上記一般式（２）で表される化合物を含む皮膜が形成される。この工程においては、ポリシラザンが、それ自身の又は水分との反応によって分解されて、Ｓｉ−Ｏ−Ｓｉネットワークが形成されると同時に、このＳｉ元素と、上記成形体を構成する上記一般式（１）で表される化合物におけるＬａ元素とからなる複合酸化物、即ち、上記一般式（２）で表される化合物が形成される。尚、上記一般式（１）で表される化合物の種類によっては、上記一般式（６）で表される化合物が皮膜（被覆部）中に併存する場合がある。 Next, in the film forming step, the coating film on the surface of the molded body is heat-treated to form a film containing the compound represented by the general formula (2). In this step, polysilazane is decomposed by reaction with itself or with water to form a Si—O—Si network, and at the same time, the Si element and the general formula (1) constituting the molded body are formed. ), A compound oxide composed of La element, that is, a compound represented by the general formula (2) is formed. Depending on the type of the compound represented by the general formula (1), the compound represented by the general formula (6) may coexist in the film (coating portion).
上記皮膜化工程において、熱処理条件としては、温度は、好ましくは９００℃〜１，５００℃の範囲、より好ましくは１，１００℃〜１，３００℃の範囲であり、雰囲気は、大気等の酸素含有雰囲気が好ましい。上記温度において、昇温、温度の保持、降温等を組み合わせてもよい。尚、熱処理時間は、上記成形体の大きさ、塗膜の厚さ等によって、適宜、選択される。 In the film forming step, as the heat treatment conditions, the temperature is preferably in the range of 900 ° C. to 1,500 ° C., more preferably in the range of 1,100 ° C. to 1,300 ° C., and the atmosphere is oxygen such as air. A containing atmosphere is preferred. The above temperature may be combined with temperature rise, temperature maintenance, temperature drop, and the like. The heat treatment time is appropriately selected depending on the size of the molded body, the thickness of the coating film, and the like.
本発明の成形材料の製造方法において、塗膜形成工程及び皮膜化工程を、それぞれ、複数回行ってもよい。この場合、得られた成形材料における皮膜部は、上記一般式（２）で表される化合物を含むものの、皮膜部の元素分布を断面方向で調べると、傾斜構造を有する場合がある。 In the method for producing a molding material of the present invention, the coating film forming step and the film forming step may each be performed a plurality of times. In this case, although the film part in the obtained molding material contains the compound represented by the general formula (2), when the element distribution of the film part is examined in the cross-sectional direction, it may have an inclined structure.
２．高温過熱蒸気生成システム
本発明の高温過熱蒸気生成システム１は、上記成形材料の複数が積み上げられて形成された、上下方向に通気可能な発熱構造体１１と、この発熱構造体１１を収容し、且つ、略筒状である収容体１２と、この収容体１２の一方の開口部１９ａに連通された気体供給装置（図示せず）と、上記収容体１２の外側にあって、少なくとも上記発熱構造体１１を包囲するように配設された励磁コイル１４と、を備えることを特徴とする（図５参照）。
2. High-temperature superheated steam generation system The high-temperature superheated steam generation system 1 of the present invention accommodates a heat generating structure 11 that is formed by stacking a plurality of the molding materials and that can vent in the vertical direction, and the heat generating structure 11. In addition, the container 12 having a substantially cylindrical shape, a gas supply device (not shown) communicated with one opening 19a of the container 12, and the outside of the container 12, at least the heat generating structure. And an exciting coil 14 disposed so as to surround the body 11 (see FIG. 5).
２−１．収容体
この収容体１２は、略筒状であり、通常、円形、楕円形、多角形等の断面形状を有する筒状体が用いられる。この収容体１２は、単層型筒状体であってよいし、同一の又は異なる材料からなる複層型筒状体であってもよい。尚、目的、用途等に応じて、ふくれ、くびれ、曲がり等の部分、内壁面に凹部、凸部、溝部等を有してもよい。
2-1. Container The container 12 has a substantially cylindrical shape, and a cylindrical body having a cross-sectional shape such as a circle, an ellipse, or a polygon is usually used. The container 12 may be a single-layer cylindrical body, or may be a multi-layer cylindrical body made of the same or different materials. Depending on the purpose, application, etc., there may be a concave portion, a convex portion, a groove portion or the like on the inner wall surface, such as blistering, constriction, or bending.
上記収容体１２の構成材料は、電磁誘導により発熱せず、且つ、耐火性を有するものであれば、特に限定されないが、上記収容体１２の内壁面の構成材料が、Ａｌ２ＴｉＯ５（チタン酸アルミニウム、五酸化チタン二アルミニウム）を含むことが好ましい。このＡｌ２ＴｉＯ５の含有割合は、好ましくは７０体積％以上、より好ましくは８０体積％以上、更に好ましくは９０体積％以上である。このＡｌ２ＴｉＯ５を含むことにより、９００℃程度までの高い温度に対して安定であることから耐熱性に優れ、更に、断熱性、耐衝撃性、耐水蒸気性等にも優れた収容体とすることができる。尚、上記Ａｌ２ＴｉＯ５と併用可能な材料としては、コージェライト、アルミナ、ジルコニア、石英ガラス等が挙げられる。
本発明においては、この収容体１２全体がＡｌ２ＴｉＯ５のみからなる単層型筒状体又は複層型筒状体であることが特に好ましい。
The constituent material of the container 12 is not particularly limited as long as it does not generate heat due to electromagnetic induction and has fire resistance, but the constituent material of the inner wall surface of the container 12 is Al 2 TiO 5 (titanium). (Aluminum acid aluminum, titanium aluminum pentoxide). The content ratio of Al 2 TiO 5 is preferably 70% by volume or more, more preferably 80% by volume or more, and still more preferably 90% by volume or more. By containing this Al 2 TiO 5 , it is stable against high temperatures up to about 900 ° C., so it has excellent heat resistance, and further has excellent heat insulation, impact resistance, water vapor resistance, etc. can do. Examples of materials that can be used in combination with the Al 2 TiO 5 include cordierite, alumina, zirconia, and quartz glass.
In the present invention, it is particularly preferable that the entire container 12 is a single-layered cylindrical body or a multilayered cylindrical body made of only Al 2 TiO 5 .
２−２．発熱構造体
この発熱構造体１１は、上記本発明の成形材料の複数が積み上げられて形成された、上下方向に通気可能な複合物である（図２、図３及び図４参照）。そして、上記発熱構造体１１は、全体として、各成形材料の接触により連結した連続体を形成している。これにより、成形材料における被覆部の構成材料によらず、発熱構造体１１の電子伝導性を維持することができ、電磁誘導により発熱させることができる。また、複数の成形材料により形成される空間が、少なくとも上下方向に連続しているので、気体の加熱が効率よく進められる。
2-2. Heat-generating structure The heat-generating structure 11 is a composite that is formed by stacking a plurality of the molding materials of the present invention and that allows ventilation in the vertical direction (see FIGS. 2, 3, and 4). And the said heat generating structure 11 forms the continuous body connected by the contact of each molding material as a whole. Thereby, the electronic conductivity of the heat generating structure 11 can be maintained regardless of the constituent material of the covering portion in the molding material, and heat can be generated by electromagnetic induction. Moreover, since the space formed by the plurality of molding materials is continuous at least in the vertical direction, the heating of the gas is efficiently advanced.
図２の発熱構造体１１は、円板型成形材料１１１ａを５枚準備し、各円板の中心を結んだときに正五角形を形成するように、円板の側面を互いに接触させて配置し、これを上方にずらしながら複数段積層した積層物であり、（ａ）は斜視図を、（ｂ）は上方から見た図を示す。図２の発熱構造体１１は、各段における円板が接触して、見かけ上、円柱体の中心を上下方向にくり抜いたような、略筒状を有しているので、そのくり抜かれている部分が気体の流路となる。円板を用いずに、多角形状、楕円形状等の板を用い、適宜、所定間隔を設けながら積層した発熱構造体とすることもできる。
図３の発熱構造体１１は、棒体（角柱等の柱状体）１１１ｂを交互に半周期ずらしながら交互積層してなるウッドパイル型構造を示す斜視図である。各棒体の配置方法によっては、上方から見たときの通気経路（流路）が直線状である場合、波線状である場合等がある。
図４の発熱構造体１１は、球体１１１ｃを面方向に最密充填し、各球体の中心を結んだときに正三角形を形成するように配置及び積層した、逆オパール構造を示す斜視図である。最密充填せずに、球体を、各球体の中心を結んだときに正方形を形成するように真上に積み上げてなるオパール構造の発熱構造体とすることもできる。また、球体を用いずに、立方体、直方体等の多面体、楕円球等を積み上げてなる発熱構造体、球体、立方体等の表面から棒体、線体等が放射状に突き出してなる発熱構造体等とすることもできる。
尚、上記複合体の形成に用いる部材は、形状及び大きさがいずれも同じものを用いる必要はなく、互いに同一形状であって大きさが異なる部材の組合せ、異なる形状どうしの組合せ等とすることができる。
The heat generating structure 11 of FIG. 2 is prepared by preparing five disk-shaped molding materials 111a and placing the side surfaces of the disks in contact with each other so that a regular pentagon is formed when the centers of the disks are connected. FIG. 4 is a laminate in which a plurality of layers are laminated while shifting this upward, (a) is a perspective view, and (b) is a view as seen from above. The heat generating structure 11 of FIG. 2 has a substantially cylindrical shape such that the discs at each stage are in contact with each other, and the center of the cylindrical body is apparently hollowed out in the vertical direction. The part becomes a gas flow path. Instead of using a circular plate, a polygonal shape, an elliptical shape, or the like may be used, and a heating structure that is laminated while providing a predetermined interval may be used.
The heat generating structure 11 in FIG. 3 is a perspective view showing a woodpile structure in which rods (columnar bodies such as prisms) 111b are alternately stacked while being alternately shifted by a half cycle. Depending on the arrangement method of each rod, the ventilation path (flow path) when viewed from above may be linear, wavy, or the like.
The heat generating structure 11 of FIG. 4 is a perspective view showing an inverted opal structure in which the spheres 111c are closely packed in the surface direction and arranged and stacked so as to form an equilateral triangle when the centers of the spheres are connected. . A heat generating structure having an opal structure in which the spheres are stacked directly above so as to form a square when the centers of the spheres are connected can also be used without close packing. Also, without using a sphere, a polyhedron such as a cube or a rectangular parallelepiped, a heat generating structure in which elliptical spheres are stacked, a heat generating structure in which rods, lines, etc. protrude radially from the surface of a sphere, a cube, etc. You can also
In addition, it is not necessary to use the same shape and size for the members used for the formation of the composite, but the combination of members having the same shape but different sizes, combinations of different shapes, etc. Can do.
図２〜図４により示される複合体は、いずれも隣り合う部材が面接触、線接触又は点接触することにより連結した連続体を構成し、乱れのない一定構造を備える発熱構造体１１であることから、誘導加熱による発熱を誘起しやすく、この発熱構造体１１から均一な輻射熱を与えることができ、導入される気体に対する効率的な加熱を進めることができる。 The composite body shown by FIGS. 2-4 is the heat generating structure 11 which comprises the continuous body which all connected by the surface contact, line contact, or point contact of the adjacent member, and is provided with the fixed structure without disorder. Therefore, heat generation by induction heating can be easily induced, uniform radiant heat can be given from the heat generating structure 11, and efficient heating of the introduced gas can be promoted.
本発明の高温過熱蒸気生成システムにおいて、上記発熱構造体１１は、上記収容体１２の内部空間の、好ましくは、発熱構造体１１の表面から収容体１２の内壁までの距離がほぼ一定となるような位置に配設される。尚、上記発熱構造体１１の外径、及び、上記収容体１２の内径、の長さの関係は、導入される気体の加熱効率の観点から、好ましくは、前者＜後者である。 In the high-temperature superheated steam generation system according to the present invention, the heat generating structure 11 is configured such that the distance from the inner space of the container 12, preferably from the surface of the heat generating structure 11 to the inner wall of the container 12 is substantially constant. It is arranged at a position. The length relationship between the outer diameter of the heat generating structure 11 and the inner diameter of the container 12 is preferably the former <the latter from the viewpoint of the heating efficiency of the introduced gas.
２−３．気体供給装置
この気体供給装置は、上記収容体１２の内部に、水蒸気、水蒸気を含む混合気体（水蒸気及び空気からなる混合気体等）等の気体を供給するために、上記収容体１２の一方の開口部（気体導入口）１９ａに連通された装置である。
本発明においては、過熱水蒸気、又は、水蒸気を含む混合気体の過熱蒸気を生成させる場合、この気体供給装置が、水蒸気供給装置又は混合気体供給装置であることが好ましい。混合気体供給装置は、各気体を独立して供給するものであってよいし、予め、特定の気体又は全ての気体を混合してなる混合ガスを供給するものであってもよい。
2-3. Gas supply device This gas supply device is configured to supply gas such as water vapor or a mixed gas containing water vapor (a mixed gas composed of water vapor and air) or the like into the inside of the housing 12. It is an apparatus communicated with the opening (gas inlet) 19a.
In the present invention, when superheated steam or superheated steam of a mixed gas containing water vapor is generated, the gas supply device is preferably a steam supply device or a mixed gas supply device. A mixed gas supply apparatus may supply each gas independently, and may supply the mixed gas formed by mixing specific gas or all the gas beforehand.
上記気体供給装置は、気体製造手段等を備えてもよい。上記気体が水蒸気である場合には、イオン交換水、蒸留水、超純水等を気化させる装置である、公知のボイラー等を用いることができる。気化は、減圧下、常圧下及び加圧下のいずれで行ってもよい。 The gas supply device may include gas production means and the like. When the gas is water vapor, a known boiler, which is a device for vaporizing ion exchange water, distilled water, ultrapure water, or the like can be used. Vaporization may be performed under reduced pressure, normal pressure, or increased pressure.
２−４．励磁コイル
この励磁コイル１４は、上記収容体１２の外側にあって、少なくとも上記発熱構造体１１を包囲するように配設されており、通常、円状又は螺旋状に巻回されている。また、このコイル１４は、高周波交流電源（図示せず）に接続され、この電源からの電力供給により磁力線を発し、上記発熱構造体１１の発熱を誘起する。
2-4. Excitation Coil This excitation coil 14 is located outside the housing 12 and is disposed so as to surround at least the heat generating structure 11, and is usually wound in a circular shape or a spiral shape. The coil 14 is connected to a high-frequency AC power supply (not shown), and generates magnetic lines of force when power is supplied from the power supply to induce heat generation of the heat generating structure 11.
上記励磁コイル１４の周辺部には、発熱構造体１１の発熱時に、収容体１２からの輻射熱の影響を抑制するために、コイル１４を冷却するための冷却手段を備えてもよい。 A cooling means for cooling the coil 14 may be provided around the excitation coil 14 in order to suppress the influence of radiant heat from the housing 12 when the heat generating structure 11 generates heat.
２−５．他の要素
本発明の高温過熱蒸気生成システムは、更に、過熱蒸気を排出するための過熱蒸気排出装置（図示せず）を備えることができる。この装置は、通常、上記収容体１２の他方の開口部（過熱蒸気排出口）１９ｂに連通される。
尚、図５に示す高温過熱蒸気生成システム１は、気密性を向上させるための部材等を含む概略図としている。
2-5. Other Elements The high-temperature superheated steam generation system of the present invention can further include a superheated steam discharge device (not shown) for discharging superheated steam. This apparatus is normally communicated with the other opening (superheated steam discharge port) 19b of the container 12.
Note that the high-temperature superheated steam generation system 1 shown in FIG. 5 is a schematic diagram including members and the like for improving airtightness.
２−６．システムの構成
本発明の高温過熱蒸気生成システムは、上記の発熱構造体１１、収容体１２、気体供給装置及び励磁コイル１４と、高周波交流電源、過熱蒸気排出装置等の要素が一体となったものであってよいし、高周波交流電源、過熱蒸気排出装置等の要素が一体化されたものであってよいし、それぞれ単独の装置あるいは２つ以上を組み合わせ別体として備えられていてもよい。また、図５のシステムは、縦置き型で示しているが、構造を変化させ、横置き型とすることもできる。
2-6. System configuration A high-temperature superheated steam generation system according to the present invention is a system in which the heat generating structure 11, the container 12, the gas supply device and the excitation coil 14, and elements such as a high-frequency AC power supply and a superheated steam discharge device are integrated. Alternatively, elements such as a high-frequency alternating current power supply and a superheated steam discharge device may be integrated, or a single device or a combination of two or more may be provided as separate bodies. Further, although the system of FIG. 5 is shown as a vertical type, the structure can be changed to be a horizontal type.
２−７．過熱蒸気の製造方法
本発明の高温過熱蒸気生成システムを用いて、高周波交流電源により励磁コイル１４に所定の電力を供給し、収容体１２内の発熱構造体１１を発熱させると同時に、又は、発熱させた後、水蒸気、水蒸気を含む混合気体等の気体を供給し、５００℃以上、好ましくは６００℃〜９００℃といった高温域の所望の温度の過熱蒸気を容易に製造することができる。
2-7. Method for Producing Superheated Steam Using the high-temperature superheated steam generation system of the present invention, predetermined power is supplied to the exciting coil 14 by a high-frequency AC power source to heat the heat generating structure 11 in the container 12 or at the same time. Then, by supplying a gas such as water vapor or a mixed gas containing water vapor, superheated steam having a desired temperature in a high temperature range of 500 ° C. or higher, preferably 600 ° C. to 900 ° C. can be easily produced.
以下、図５の高温過熱蒸気生成システムを用い、飽和水蒸気から過熱水蒸気を製造する方法について説明する。
飽和水蒸気は、収容体１２の下方側の開口部（気体導入口）１９ａを通して、一定速度又は一定圧で、気体供給装置（図示せず）から、発熱構造体１１が収容されている収容体１２に導入される。一方、発熱構造体１１は、予め、励磁コイル１４により誘導加熱され発熱しており、導入された飽和水蒸気が発熱構造体１１に接触し、又は、収容体１２内の加熱空間を通気することにより、過熱水蒸気が製造される。その後、この過熱水蒸気は、過熱蒸気排出口１９ｂから排出される。
Hereinafter, a method for producing superheated steam from saturated steam using the high-temperature superheated steam generation system of FIG. 5 will be described.
Saturated water vapor passes through an opening (gas inlet) 19a on the lower side of the container 12 and is supplied at a constant speed or constant pressure from a gas supply device (not shown) to the container 12 in which the heat generating structure 11 is accommodated. To be introduced. On the other hand, the heat generating structure 11 is heated by induction heating by the exciting coil 14 in advance, and the introduced saturated water vapor contacts the heat generating structure 11 or ventilates the heating space in the container 12. Superheated steam is produced. Thereafter, the superheated steam is discharged from the superheated steam discharge port 19b.
尚、上記励磁コイル１４による誘導過熱条件としては、発信周波数を、２０ｋＨｚ〜１００ｋＨｚの範囲から選択して電力を供給することが好ましい。この範囲であれば、発熱構造体１１による、所望の温度（温度範囲６００℃〜９００℃）への発熱を効率的に進めることができる。 In addition, as induction | guidance | derivation overheating conditions by the said excitation coil 14, it is preferable to select a transmission frequency from the range of 20 kHz-100 kHz, and to supply electric power. If it is this range, the heat_generation | fever structure 11 can advance efficiently the heat_generation | fever to desired temperature (temperature range 600 to 900 degreeC).
以下に、実施例を挙げ、本発明を更に詳細に説明するが、本発明の主旨を超えない限り、本発明はかかる実施例に限定されるものではない。尚、下記において、部及び％は、特に断らない限り、質量基準である。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to such examples as long as the gist of the present invention is not exceeded. In the following, “part” and “%” are based on mass unless otherwise specified.
１．円板型成形材料の製造
実施例１
第一稀元素工業社製Ｌａ０．８Ｓｒ０．２ＭｎＯ３粉末を、プレス成形（圧力：２０ＭＰａ）し、その後、ＣＩＰ成形（圧力：６００ＭＰａ）することにより、円板状とした。次いで、酸素気流中、温度１，５００℃で５時間焼成することにより、直径２４ｍｍ及び厚さ１０ｍｍの焼結体（成形体）を得た。
その後、この焼結体をアセトンで超音波洗浄した。そして、焼結体を、２５℃に調整した、ＡＺエレクトロニックマテリアルズ社製ポリシラザン溶液「ＮＮ３１０−３０」（商品名）中に、１０秒間浸漬させた後、これを取り出し、酸素気流中、下記条件で熱処理した。これにより、上記焼結体の表面に、Ｓｉ系の酸化物被膜を形成させ、円板型成形材料を得た。上記商品のポリシラザンは、−（ＳｉＨ２ＮＨ）ｎ−であり、ｎ＝８００〜１，２００の化合物である。
＜熱処理条件＞
塗膜付き焼結体を２時間かけて４５０℃まで昇温加熱し、４５０℃で１時間保持した。その後、５時間かけて１，２００℃まで昇温加熱し、１，２００℃で１時間保持した。次いで、５時間かけて、室温まで降温させた。
1. Example 1 Production of Disc Molding Material
A La 0.8 Sr 0.2 MnO 3 powder manufactured by Daiichi Rare Element Industrial Co., Ltd. was press-molded (pressure: 20 MPa) and then CIP-molded (pressure: 600 MPa) to obtain a disk shape. Subsequently, the sintered body (molded body) having a diameter of 24 mm and a thickness of 10 mm was obtained by firing in an oxygen stream at a temperature of 1,500 ° C. for 5 hours.
Thereafter, this sintered body was ultrasonically cleaned with acetone. And after immersing for 10 second in polysilazane solution "NN310-30" (brand name) by AZ Electronic Materials which adjusted the sintered compact to 25 degreeC, this was taken out and the following conditions were carried out in oxygen stream. And heat treated. As a result, a Si-based oxide film was formed on the surface of the sintered body to obtain a disk-shaped molding material. The polysilazane of the above product is — (SiH 2 NH) n —, which is a compound of n = 800 to 1,200.
<Heat treatment conditions>
The coated sintered body was heated to 450 ° C. over 2 hours and held at 450 ° C. for 1 hour. Thereafter, the temperature was raised to 1,200 ° C. over 5 hours, and the temperature was maintained at 1,200 ° C. for 1 hour. Next, the temperature was lowered to room temperature over 5 hours.
上記円板型成形材料について、リガク社製「ＲＩＮＴ２０００」（型式名）を用いたＸＲＤ測定、及び、ＰＨＩ社製「ＡＤＥＰＴ１０１０」（型式名）を用いたＤ−ＳＩＭＳ測定に供して、それぞれ、被覆部の組成分析、及び、被覆部表面からの深さ方向分析を行った。その結果を図６及び図７に示す。
図６において、（ａ）は、焼結体（成形体）のＸ線回折像であり、（ｂ）は、被覆部を形成させた円板型成形材料のＸ線回折像である。
About the said disk type | mold molding material, it used for the X-RD measurement using "RINT2000" (model name) by Rigaku, and D-SIMS measurement using "ADEPT1010" (model name) by PHI, respectively, and each coat | covered Composition analysis and depth direction analysis from the coating surface. The results are shown in FIGS.
In FIG. 6, (a) is an X-ray diffraction image of a sintered body (molded body), and (b) is an X-ray diffraction image of a disk-shaped molding material on which a covering portion is formed.
ＸＲＤ測定及びＤ−ＳＩＭＳ測定は、以下の通りである。
＜ＸＲＤ測定条件＞
Ｘ線源：Ｃｕ
スキャンステップ：０．０２ｄｅｇ．
スキャンスピード：４．０ｄｅｇ．／ｍｉｎ．
管電圧：４０ｋＶ
管電流：４０ｍＡ
＜Ｄ−ＳＩＭＳ測定条件＞
１次イオン：Ｃｓ＋
１次加速電圧：５．０ｋＶ
検出領域：１００μｍ×１００μｍ
XRD measurement and D-SIMS measurement are as follows.
<XRD measurement conditions>
X-ray source: Cu
Scan step: 0.02 deg.
Scan speed: 4.0 deg. / Min.
Tube voltage: 40 kV
Tube current: 40 mA
<D-SIMS measurement conditions>
Primary ion: Cs +
Primary acceleration voltage: 5.0 kV
Detection area: 100 μm × 100 μm
図６（ｂ）より、被覆部が、Ｌａ９．３３Ｓｉ６Ｏ２６及びＭｎ７ＳｉＯ１２からなることが分かった。また、これらの割合を求めたところ、Ｌａ９．３３Ｓｉ６Ｏ２６が６５質量％であり、Ｍｎ７ＳｉＯ１２が３５質量％であることが分かった。
また、図７より、円板型成形材料の表面から約４μｍのあたりで、Ｓｉ元素の減衰が停滞していることから、被覆部の厚さが約４μｍであることが分かる。
From FIG. 6 (b), it was found that the covering portion was made of La 9.33 Si 6 O 26 and Mn 7 SiO 12 . Furthermore, it was determined these proportions, La 9.33 Si 6 O 26 is 65 wt%, Mn 7 SiO 12 was found to be 35 mass%.
Further, it can be seen from FIG. 7 that the thickness of the covering portion is about 4 μm because the attenuation of the Si element is stagnant at about 4 μm from the surface of the disk molding material.
２．高温過熱蒸気生成システムの製造
実施例２
実施例１で得られた円板型成形材料を５個単位で用い、各側面を密着させて各中心を結んだときに正五角形を形成するように配置してこれを１段とし、図２に示すように、縦方向に３６度ずつずらして５０段積層し、上下方向に通気可能な構造を備える発熱構造体１１を得た。
2. Example 2 Production of a High Temperature Superheated Steam Generation System
The disk-shaped molding material obtained in Example 1 is used in units of 5 pieces, arranged so as to form a regular pentagon when the respective side surfaces are brought into close contact with each other, and this is formed into one step. As shown in Fig. 5, a heat generation structure 11 having a structure in which 50 stages are stacked while being shifted by 36 degrees in the vertical direction and has a structure that allows ventilation in the vertical direction is obtained.
次いで、上記発熱構造体１１を、チタン酸アルミニウム（Ａｌ２ＴｉＯ５）からなる円筒状の収容体１２（内径６９ｍｍ）の中央部に、その内壁に接触しないように、支持台１７１上に設置した。また、この収容体１２の外側であって、発熱構造体１１を包囲するように且つ上記収容体１２の外壁に接触しないように、螺旋状の励磁コイル１４を配設した。そして、以下に説明する他の要素を配設し、図５に示すような高温過熱蒸気生成システム１を作製した。 Next, the heat generating structure 11 was installed on a support base 171 at the center of a cylindrical container 12 (inner diameter 69 mm) made of aluminum titanate (Al 2 TiO 5 ) so as not to contact the inner wall. . In addition, a helical excitation coil 14 is disposed outside the housing 12 so as to surround the heat generating structure 11 and not to contact the outer wall of the housing 12. And the other element demonstrated below was arrange | positioned and the high temperature superheated steam generation system 1 as shown in FIG. 5 was produced.
図５の高温過熱蒸気生成システム１において、収容体１２を励磁コイル１４に対して所定位置に固定し保持するために、非磁性材料（例えば、ステンレス製）からなるブラケット１５１及び１５２並びに非磁性ステンレス製のボルト１５５及びナット１５６が用いられている。
上記収容体１２の下方側には、一方のブラケット１５１に保持される側に、水蒸気等の気体を供給するための気体供給装置（図示せず）から連通させ接続された気体導入口１９ａを有している。一方、この収容体１２の上方側には、他方のブラケット１５２に保持される側に、過熱蒸気排出口１９ｂを有している。
また、この収容体１２の上下の各端部及び外壁面には、それぞれ、これらと接するように、断熱性材料からなるシール材１７５及び断熱層１３が配設されている。更に、上記シール材１７５及び断熱層１３を介して、上記気体導入口１９ａ近傍に開口部材１８ａが、過熱蒸気排出口１９ｂ近傍に開口部材１８ｂが、それぞれ配設されている。各開口部材１８ａ及び１８ｂは、それぞれ、気体導入口１９ａ及び過熱蒸気排出口１９ｂを形成する各外側に突出される管状部を有するとともに、断熱層１３の両端を遮断するための蓋部１８１ａ及び１８１ｂを備えている。
In the high-temperature superheated steam generation system 1 of FIG. 5, brackets 151 and 152 made of a nonmagnetic material (for example, made of stainless steel) and nonmagnetic stainless steel are used to fix and hold the container 12 at a predetermined position with respect to the exciting coil 14. Bolts 155 and nuts 156 are used.
On the lower side of the container 12, there is a gas introduction port 19 a connected to and connected to a gas holding device (not shown) for supplying a gas such as water vapor on the side held by one bracket 151. is doing. On the other hand, an upper side of the container 12 has a superheated steam outlet 19b on the side held by the other bracket 152.
Further, a sealing material 175 made of a heat insulating material and a heat insulating layer 13 are disposed on the upper and lower end portions and the outer wall surface of the container 12 so as to be in contact therewith, respectively. Further, an opening member 18a is disposed in the vicinity of the gas introduction port 19a, and an opening member 18b is disposed in the vicinity of the superheated steam discharge port 19b via the sealing material 175 and the heat insulating layer 13, respectively. Each of the opening members 18a and 18b has a tubular portion protruding outward and forming a gas introduction port 19a and a superheated steam discharge port 19b, respectively, and lid portions 181a and 181b for blocking both ends of the heat insulating layer 13 respectively. It has.
上記励磁コイル１４は、適当なブラケットから連結されて固定されており、この励磁コイル１４に適当な周波数の電圧を供給するための高周波交流電源（図示せず）に接続されている。また、励磁コイル１４への電圧供給による磁界変化を利用して発熱構造体１１を発熱させた際に、収容体１２の外壁より発せられる輻射熱から励磁コイル１４を保護するために、励磁コイル１４の内部に冷却水を供給するための冷却系（図示せず）が備えられている。 The excitation coil 14 is connected and fixed from an appropriate bracket, and is connected to a high-frequency AC power source (not shown) for supplying a voltage of an appropriate frequency to the excitation coil 14. In order to protect the exciting coil 14 from the radiant heat generated from the outer wall of the container 12 when the heat generating structure 11 is heated using the magnetic field change due to the voltage supply to the exciting coil 14, A cooling system (not shown) for supplying cooling water to the inside is provided.
上記収容体１２は、適当な断熱材１７８ａ及び１７８ｂを介して配設されたブラケット１５１及び１５２並びにボルト１５５及びナット１５６により固定されている。また、これらのブラケット１５１及び１５２は、それぞれ、開口部材１８ａ及び１８ｂも固定しており、固定した開口部材１８ａ及び１８ｂによって、気体導入口１９ａ及び過熱蒸気排出口１９ｂを形成している。 The container 12 is fixed by brackets 151 and 152, bolts 155 and nuts 156 disposed via appropriate heat insulating materials 178a and 178b. In addition, the brackets 151 and 152 also fix the opening members 18a and 18b, respectively, and the gas introduction port 19a and the superheated steam discharge port 19b are formed by the fixed opening members 18a and 18b.
上記ブラケット１５１には、ブラケット１５２、ボルト１５５及びナット１５６とともに、上記収容体１２の機械的強度を補うとともに導入された気体及び／又は生成された過熱蒸気の気密性を補うために、スプリングコイル等の弾性体１７２と、台座１５９とを備えている。この弾性体１７２を、台座１５９により圧縮させた状態とし、この台座１５９及びブラケット１５２を、ボルト１５５及びナット１５６を用いて固定することにより、収容体１２において確実な気密性及び機械的強度を確保できるようになっている。 In addition to the bracket 152, the bolt 155, and the nut 156, the bracket 151 includes a spring coil or the like in order to supplement the mechanical strength of the container 12 and the airtightness of the introduced gas and / or generated superheated steam. The elastic body 172 and the pedestal 159 are provided. The elastic body 172 is compressed by the pedestal 159, and the pedestal 159 and the bracket 152 are fixed by using the bolts 155 and the nuts 156, thereby ensuring reliable airtightness and mechanical strength in the container 12. It can be done.
上記収容体１２に収容された発熱構造体１１は、上記のように、５個の円板型成形材料によって環状としこれを１段ごとにずらしながら積層してなる略円筒体を形成している（図２参照）。従って、気体供給装置から気体導入口１９ａを介して導入された水蒸気等の気体を、略筒状の上記発熱構造体１１の貫通孔内に通し、連続した凹凸面を形成している、発熱構造体１１の内壁面との接触効率を高めて、電磁誘導により発熱させた発熱構造体１１により過熱蒸気を生成させるようになっている。生成された過熱蒸気は、その後、過熱蒸気排出口１９ｂから、必要に応じて配設される、過熱蒸気排出装置により排出される。 As described above, the heat generating structure 11 housed in the housing body 12 forms a substantially cylindrical body that is formed of five disk-shaped molding materials and is laminated while being shifted one step at a time. (See FIG. 2). Accordingly, a heat generation structure in which a gas such as water vapor introduced from the gas supply device through the gas introduction port 19a is passed through the through hole of the substantially cylindrical heat generation structure 11 to form a continuous uneven surface. The efficiency of contact with the inner wall surface of the body 11 is increased, and superheated steam is generated by the heat generating structure 11 that generates heat by electromagnetic induction. The generated superheated steam is then discharged from the superheated steam discharge port 19b by a superheated steam discharge device arranged as necessary.
以上の構成を有する高温過熱蒸気生成システム１を用い、以下の要領で過熱水蒸気を生成させた。尚、気体供給装置として、水蒸気製造用ボイラー及び送気ポンプを、配管を介して気体導入口１９ａと連結した。
まず、高周波交流電源から、励磁コイル１４に周波数５０ｋＨｚの電圧を供給し、電磁誘導により発熱構造体１１を１，１００℃に発熱させた。
その後、気体供給装置から飽和水蒸気を９．０ｋｇ／時で供給して、気体導入口１９ａより導入し、発熱している発熱構造体１１の外表面及び内表面に接触させて、８００℃の過熱水蒸気を生成させ、過熱蒸気排出口１９ｂから９．０ｋｇ／時で排出した。
過熱水蒸気の製造を、１０分間行った後、発熱構造体１１を構成する円板型成形材料を取り出して、表面観察したところ、溶融による変質、凹凸形成、欠け等の欠陥は見られなかった（図８参照）。
Using the high-temperature superheated steam generation system 1 having the above configuration, superheated steam was generated in the following manner. As a gas supply device, a steam production boiler and an air feed pump were connected to the gas inlet 19a via a pipe.
First, a voltage of 50 kHz was supplied to the exciting coil 14 from a high-frequency AC power source, and the heat generating structure 11 was heated to 1,100 ° C. by electromagnetic induction.
Thereafter, saturated steam is supplied from the gas supply device at 9.0 kg / hour, introduced from the gas introduction port 19a, and brought into contact with the outer surface and the inner surface of the heat generating structure 11 which is generating heat, and overheated at 800 ° C. Steam was generated and discharged at 9.0 kg / hour from the superheated steam outlet 19b.
After producing the superheated steam for 10 minutes, the disk-shaped molding material constituting the heat generating structure 11 was taken out and observed on the surface. As a result, defects such as alteration due to melting, formation of irregularities, and chipping were not observed ( (See FIG. 8).
本発明の成形材料によれば、電磁誘導を利用し、目的、用途等に応じた各種形状の発熱体として好適である。特に、耐久性に優れるので、物品、気体等の熱処理等を安定的に、また、効率よく進めることができる。
また、本発明の高温過熱蒸気生成システムは、酸化物、窒化物、炭化物等の無機系化合物等からなる粉体、成形品等の熱処理（加熱、乾燥、焼成等）、金型の表面改質、水素製造、調理を含む食品加工（加熱、乾燥、解凍、焼き、蒸し、殺菌、滅菌、脱臭等）、廃棄物処理等の分野に有用である。特に、潜熱の高い過熱水蒸気の、食品加工の分野への適用に好適である。
According to the molding material of the present invention, electromagnetic induction is used, and it is suitable as a heating element of various shapes according to the purpose and application. In particular, since it is excellent in durability, heat treatment of articles and gases can be stably and efficiently advanced.
In addition, the high-temperature superheated steam generation system of the present invention is a heat treatment (heating, drying, firing, etc.) of powders and molded products made of inorganic compounds such as oxides, nitrides and carbides, and surface modification of molds. It is useful in fields such as hydrogen production, food processing including cooking (heating, drying, thawing, baking, steaming, sterilization, sterilization, deodorization, etc.), waste treatment and the like. In particular, it is suitable for application of superheated steam having high latent heat to the field of food processing.
１：高温過熱蒸気生成システム
１１：発熱構造体
１１１：成形材料
１１１ａ：成形材料（円板）
１１１ｂ：成形材料（棒体）
１１１ｃ：成形材料（球体）
１２：収容体
１３：断熱層
１４：励磁コイル
１５１，１５２：ブラケット
１５９：台座
１７１：支持台
１７２：弾性体
１７５：シール材
１７８ａ，１７８ｂ：断熱材
１８ａ：（気体導入口側）開口部材
１８ｂ：（過熱蒸気排出口側）開口部材
１８１ａ：（気体導入口側）蓋部
１８１ｂ：（過熱蒸気排出口側）蓋部
１９ａ：気体導入口
１９ｂ：過熱蒸気排出口
1: High-temperature superheated steam generation system 11: Heat generating structure 111: Molding material 111a: Molding material (disk)
111b: Molding material (rod)
111c: Molding material (sphere)
12: Container 13: Thermal insulation layer 14: Excitation coil 151, 152: Bracket 159: Base 171: Support base 172: Elastic body 175: Sealing material 178a, 178b: Thermal insulation material 18a: (Gas inlet side) Opening member 18b: (Superheated steam outlet side) Opening member 181a: (Gas inlet side) Lid 181b: (Superheated steam outlet side) Lid 19a: Gas inlet 19b: Superheated steam outlet
Claims (6)
Ｌａ１−ｘＭ１ ｘＭ２Ｏ３−ｙ （１）
〔式中、Ｍ１は、Ｍｇ、Ｃａ、Ｓｒ及びＢａから選ばれた少なくとも１種の元素であり、Ｍ２は、Ｃｒ、Ｃｏ及びＭｎから選ばれた少なくとも１種の元素であり、０＜ｘ≦０．５、且つ、０≦ｙ≦０．１である。〕
Ｌａ２Ｏ３・ｎ（ＳｉＯ２） （２）
〔式中、ｎは、１以上２以下の数である。〕 A molding comprising: a base portion containing a compound represented by the following general formula (1); and a covering portion containing a compound represented by the following general formula (2) disposed on the surface of the base portion. material.
La 1-x M 1 x M 2 O 3-y (1)
[Wherein, M 1 is at least one element selected from Mg, Ca, Sr and Ba, M 2 is at least one element selected from Cr, Co and Mn, and 0 < x ≦ 0.5 and 0 ≦ y ≦ 0.1. ]
La 2 O 3 · n (SiO 2 ) (2)
[In the formula, n is a number of 1 or more and 2 or less. ]
下記一般式（１）で表される化合物を含む成形体を得る成形体作製工程と、
ポリシラザンを含む溶液を用いて、上記成形体の表面にポリシラザンを含む塗膜を形成する塗膜形成工程と、
上記塗膜を、熱処理し、下記一般式（２）で表される化合物を含む皮膜を形成する皮膜化工程と、
を備えることを特徴とする成形材料の製造方法。
Ｌａ１−ｘＭ１ ｘＭ２Ｏ３−ｙ （１）
〔式中、Ｍ１は、Ｍｇ、Ｃａ、Ｓｒ及びＢａから選ばれた少なくとも１種の元素であり、Ｍ２は、Ｃｒ、Ｃｏ及びＭｎから選ばれた少なくとも１種の元素であり、０＜ｘ≦０．５、且つ、０≦ｙ≦０．１である。〕
Ｌａ２Ｏ３・ｎ（ＳｉＯ２） （２）
〔式中、ｎは、１以上２以下の数である。〕 It is a manufacturing method of the molding material according to claim 1,
A molded body preparation step for obtaining a molded body containing a compound represented by the following general formula (1);
Using a solution containing polysilazane, a coating film forming step of forming a coating film containing polysilazane on the surface of the molded body,
The film-forming process which heat-processes the said coating film and forms the film | membrane containing the compound represented by following General formula (2),
A method for producing a molding material, comprising:
La 1-x M 1 x M 2 O 3-y (1)
[Wherein, M 1 is at least one element selected from Mg, Ca, Sr and Ba, M 2 is at least one element selected from Cr, Co and Mn, and 0 < x ≦ 0.5 and 0 ≦ y ≦ 0.1. ]
La 2 O 3 · n (SiO 2 ) (2)
[In the formula, n is a number of 1 or more and 2 or less. ]
上記成形材料の複数が積み上げられて形成された、上下方向に通気可能な発熱構造体と、
該発熱構造体を収容し、且つ、略筒状である収容体と、
該収容体の一方の開口部に連通された気体供給装置と、
上記収容体の外側にあって、少なくとも上記発熱構造体を包囲するように配設された励磁コイルと、
を備えることを特徴とする高温過熱蒸気生成システム。 A high-temperature superheated steam generation system comprising the molding material according to any one of claims 1 to 3,
A heat generating structure that is formed by stacking a plurality of the molding materials, and is capable of venting vertically.
A housing that houses the heat generating structure and is substantially cylindrical;
A gas supply device communicated with one opening of the container;
An excitation coil on the outside of the container and disposed so as to surround at least the heat generating structure;
A high-temperature superheated steam generation system comprising:
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|---|---|---|---|---|
| JPH07505855A (en) * | 1992-04-14 | 1995-06-29 | エス・アール・アイ・インターナシヨナル | Method for increasing the strength of ceramic structural materials by forming a ceramic coating on the surface, and products made thereby |
| JP2002128512A (en) * | 2000-10-16 | 2002-05-09 | Noritake Co Ltd | Ceramic material, ceramic membrane and use thereof |
| JP2005270887A (en) * | 2004-03-25 | 2005-10-06 | Japan Fine Ceramics Center | Silicic stream-proof film, hydrogen gas separation material using the same, and production method thereof |
| JP2008201625A (en) * | 2007-02-20 | 2008-09-04 | Japan Fine Ceramics Center | Material for forming electromagnetic induction type heating element, electromagnetic induction type breathable heating element and system for generating high temperature superheated steam |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07505855A (en) * | 1992-04-14 | 1995-06-29 | エス・アール・アイ・インターナシヨナル | Method for increasing the strength of ceramic structural materials by forming a ceramic coating on the surface, and products made thereby |
| JP2002128512A (en) * | 2000-10-16 | 2002-05-09 | Noritake Co Ltd | Ceramic material, ceramic membrane and use thereof |
| JP2005270887A (en) * | 2004-03-25 | 2005-10-06 | Japan Fine Ceramics Center | Silicic stream-proof film, hydrogen gas separation material using the same, and production method thereof |
| JP2008201625A (en) * | 2007-02-20 | 2008-09-04 | Japan Fine Ceramics Center | Material for forming electromagnetic induction type heating element, electromagnetic induction type breathable heating element and system for generating high temperature superheated steam |
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