JP7083235B2 - Silver oxide and its manufacturing method - Google Patents
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Description
本発明は、新規な酸化銀などに関する。 The present invention relates to novel silver oxide and the like.
酸化銀は、様々な産業分野において使用されうる材料である。 Silver oxide is a material that can be used in various industrial fields.
例えば、特許文献１には、平均粒径５～３０μｍの単粒子からなり、嵩密度１．４ｇ／ｃｍ３以上、比表面積（ＢＥＴ値）０．０４～０．５ｍ２／ｇであって、解砕量１５％以下の酸化銀が電池用として好適であること、嵩密度の上限が２．５ｇ／ｃｍ３程度であることが記載されている。 For example, Patent Document 1 describes a single particle having an average particle size of 5 to 30 μm, a bulk density of 1.4 g / cm 3 or more, and a specific surface area (BET value) of 0.04 to 0.5 m 2 / g. It is described that silver oxide having a crushing amount of 15% or less is suitable for a battery, and that the upper limit of the bulk density is about 2.5 g / cm 3 .
本発明の目的は、新規な酸化銀を提供することにある。 An object of the present invention is to provide a novel silver oxide.
本発明の他の目的は、酸化銀の新規な製造方法を提供することにある。 Another object of the present invention is to provide a novel method for producing silver oxide.
本発明者らは、鋭意検討した結果、特定の方法を採用すること等により、新規な酸化銀（例えば、比較的高い開気孔率や嵩密度を有する酸化銀）が得られること等を見出し、本発明を完成した。 As a result of diligent studies, the present inventors have found that a novel silver oxide (for example, silver oxide having a relatively high porosity and bulk density) can be obtained by adopting a specific method or the like. The present invention has been completed.
なお、前記特許文献１では、酸化銀粒子をアルカリ溶液中で加熱加圧処理することで、酸化銀粒子をアルカリ溶液中で粒成長させ、酸化銀粒子を得ることを目的としている。
このような方法は、酸化銀粒子の粒成長を伴うものであり、得られる粒子は、緻密なものとなる。実際、特許文献１では、開気孔を形成させること、ましてや開気孔率を高めることを全く想定していない。
The object of Patent Document 1 is to obtain silver oxide particles by growing silver oxide particles in an alkaline solution by heat-pressuring the silver oxide particles in an alkaline solution.
Such a method involves grain growth of silver oxide particles, and the obtained particles become dense. In fact, Patent Document 1 does not assume that open pores are formed, let alone increase the open pore ratio.
すなわち、本発明の酸化銀は、例えば、開気孔率が１７％以上の酸化銀であってもよい。
本発明の酸化銀は、また、嵩密度が３ｇ／ｃｍ３以上の酸化銀であってもよい。
That is, the silver oxide of the present invention may be, for example, silver oxide having an open porosity of 17% or more.
The silver oxide of the present invention may also be silver oxide having a bulk density of 3 g / cm 3 or more.
本発明の酸化銀は、回折角３３°付近のピーク強度Ｉ３３と、回折角４４°付近のピーク強度Ｉ４４との強度比Ｉ４４／Ｉ３３が、０．１以下の酸化銀であってもよい。 The silver oxide of the present invention is silver oxide having an intensity ratio I 44 / I 33 of a peak intensity I 33 near a diffraction angle 33 ° and a peak intensity I 44 near a diffraction angle 44 ° of 0.1 or less. May be good.
代表的な本発明の酸化銀には、
開気孔率が１８～２５％であり、
嵩密度が４～７ｇ／ｃｍ３であり、
回折角３３°付近のピーク強度Ｉ３３と、回折角４４°付近のピーク強度Ｉ４４との強度比Ｉ４４／Ｉ３３が、０．０５以下である、酸化銀などが含まれる。
A typical silver oxide of the present invention includes
The open porosity is 18-25%,
The bulk density is 4 to 7 g / cm 3 ,
Silver oxide and the like having an intensity ratio I 44 / I 33 between the peak intensity I 33 near the diffraction angle 33 ° and the peak intensity I 44 near the diffraction angle 44 ° are 0.05 or less are included.
本発明の酸化銀は、成形品、例えば、粉体成形体（粉体成形品）であってもよい。 The silver oxide of the present invention may be a molded product, for example, a powder molded product (powder molded product).
本発明の酸化銀は、冷却材、電極材及び触媒から選択された少なくとも１種の用途に使用するための酸化銀であってもよい。 The silver oxide of the present invention may be silver oxide for use in at least one selected application from a cooling material, an electrode material and a catalyst.
本発明には、酸化銀（原料酸化銀）を水蒸気の存在下（又は水蒸気中）で熱処理し、酸化銀を製造する方法が含まれる。このような方法で製造される酸化銀は、上記酸化銀（例えば、開気孔率が１７％以上の酸化銀）であってもよい。 The present invention includes a method for producing silver oxide by heat-treating silver oxide (raw material silver oxide) in the presence of steam (or in steam). The silver oxide produced by such a method may be the above-mentioned silver oxide (for example, silver oxide having an open porosity of 17% or more).
このような方法では、酸化銀の成形体［特に、酸化銀の粉体成形体（例えば、酸化銀粉末のシップ（冷間等方圧加圧）成形体）など］を熱処理してもよい。 In such a method, a silver oxide molded product [particularly, a silver oxide powder molded product (for example, a silver oxide powder ship (cold isotropic pressure) molded product)] may be heat-treated.
具体的には、本発明の方法は、原料酸化銀を成形［例えば、酸化銀を粉体成形（シップ成形）］する成形工程、得られた原料酸化銀の成形体を熱処理する熱処理工程とで構成してもよい。 Specifically, the method of the present invention comprises a molding step of molding raw silver oxide [for example, powder molding (ship molding) of silver oxide] and a heat treatment step of heat-treating the obtained raw silver oxide molded body. It may be configured.
本発明の方法において、加圧又は飽和水蒸気圧下、１２０℃以上で熱処理してもよい。 In the method of the present invention, heat treatment may be performed at 120 ° C. or higher under pressure or saturated steam pressure.
本発明には、前記酸化銀（例えば、開気孔率が１７％以上の酸化銀）［又はその還元物（すなわち銀）］を含む材料が含まれる。このような材料は、冷却材、電極材及び触媒材料から選択された少なくとも１種の用途に使用するための材料であってもよい。 The present invention includes a material containing the silver oxide (for example, silver oxide having a porosity of 17% or more) [or a reduced product thereof (that is, silver)]. Such materials may be materials for use in at least one application selected from coolants, electrode materials and catalyst materials.
本発明では、新規な酸化銀（酸化銀（Ｉ）、Ａｇ２Ｏ）を提供できる。
また、本発明では、酸化銀の新規な製造方法を提供できる。
INDUSTRIAL APPLICABILITY The present invention can provide a novel silver oxide (silver oxide (I), Ag 2 O).
Further, the present invention can provide a novel method for producing silver oxide.
［酸化銀］
本発明の酸化銀は、特定の物性（特性）を充足する。本発明の酸化銀が充足する物性は、少なくとも１つであればよく、２以上の物性を充足してもよい。なお、このような物性を充足する酸化銀は、例えば、後述の方法により製造しうる。
[Silver oxide]
The silver oxide of the present invention satisfies specific physical characteristics (characteristics). The silver oxide of the present invention may satisfy at least one physical characteristic, and may satisfy two or more physical characteristics. Silver oxide satisfying such physical characteristics can be produced, for example, by a method described later.
酸化銀は気孔（又は空孔、特に開気孔）を有していてもよい。なお、気孔は、その全部又は一部が貫通孔であってもよい。開気孔を有する酸化銀の開気孔率は、例えば、１０％以上（例えば、１２％以上）の範囲から選択してもよく、１５％以上（例えば、１６％以上、１６．５％以上）、好ましくは１７％以上（例えば、１７．５％以上）、さらに好ましくは１８％以上（例えば、１９％以上、２０％以上など）であってもよい。 Silver oxide may have pores (or pores, especially open pores). The pores may be all or part of the pores. The porosity of silver oxide having open pores may be selected from the range of, for example, 10% or more (for example, 12% or more), and 15% or more (for example, 16% or more, 16.5% or more). It may be preferably 17% or more (for example, 17.5% or more), and more preferably 18% or more (for example, 19% or more, 20% or more, etc.).
酸化銀の開気孔率の上限値は、特に限定されないが、例えば、５０％、４５％、４０％、３５％、３０％、２５％、２３％、２２％などであってもよい。なお、範囲の上限値と下限値とを適宜組み合わせて範囲を設定してもよい（例えば、１８～３０％など。以下同じ）。 The upper limit of the open porosity of silver oxide is not particularly limited, but may be, for example, 50%, 45%, 40%, 35%, 30%, 25%, 23%, 22% and the like. The range may be set by appropriately combining the upper limit value and the lower limit value of the range (for example, 18 to 30%; the same applies hereinafter).
このような開気孔率（比較的多孔質）とすることで、比較的比表面積を大きくできる。このような大きい比表面積により、外部との接触点を増大できる。また、酸化銀（成形体）の内部まで媒体（ガスなど）を拡散や透過しやすくなる。そのため、冷却材、触媒、電極材料などの用途において好適に使用しうる材料となりうる。 By setting such an open porosity (relatively porous), the specific surface area can be relatively large. With such a large specific surface area, the contact point with the outside can be increased. In addition, the medium (gas, etc.) can be easily diffused or permeated into the inside of the silver oxide (molded body). Therefore, it can be a material that can be suitably used in applications such as coolants, catalysts, and electrode materials.
なお、開気孔率の測定方法は特に限定されないが、例えば、開気孔量(Ｐ)は、酸化銀（成形体）の乾燥重量(Ｗ１)、および水中での重量(Ｗ２)、含水させた際の重量(Ｗ３)から、下記の式により求めてもよい。
Ｐ(％)＝１００×(Ｗ３－Ｗ１)／（Ｗ３－Ｗ２）
The method for measuring the open porosity is not particularly limited, but for example, the open porosity (P) includes the dry weight (W 1 ) of silver oxide (molded body), the weight in water (W 2 ), and water content. From the weight (W 3 ) at the time, it may be calculated by the following formula.
P (%) = 100 × (W 3 -W 1 ) / (W 3 -W 2 )
なお、開気孔の大きさは、特に限定されず、例えば、孔径（気孔径）で１～１０μｍ程度であってもよい。 The size of the open pores is not particularly limited, and for example, the pore diameter (pore diameter) may be about 1 to 10 μm.
酸化銀の嵩密度は、例えば、２ｇ／ｃｍ３以上の範囲から選択してもよく、２．５ｇ／ｃｍ３以上（例えば、２．７ｇ／ｃｍ３以上）、好ましくは３ｇ／ｃｍ３以上（例えば、３．５ｇ／ｃｍ３以上）、さらに好ましくは４ｇ／ｃｍ３以上（例えば、４．５ｇ／ｃｍ３以上）であってもよく、５ｇ／ｃｍ３以上（例えば、５．２ｇ／ｃｍ３以上、５．３ｇ／ｃｍ３以上、５．４ｇ／ｃｍ３以上など）であってもよい。 The bulk density of silver oxide may be selected from the range of, for example, 2 g / cm 3 or more, 2.5 g / cm 3 or more (for example, 2.7 g / cm 3 or more), preferably 3 g / cm 3 or more (for example, 2.7 g / cm 3 or more). For example, it may be 3.5 g / cm 3 or more, more preferably 4 g / cm 3 or more (for example, 4.5 g / cm 3 or more), and 5 g / cm 3 or more (for example, 5.2 g / cm 3 or more). It may be 5.3 g / cm 3 or more, 5.4 g / cm 3 or more, and the like).
酸化銀の嵩密度の上限値は、特に限定されないが、例えば、７ｇ／ｃｍ３、６．５ｇ／ｃｍ３、６ｇ／ｃｍ３、５．８ｇ／ｃｍ３、５．７ｇ／ｃｍ３などであってもよい。 The upper limit of the bulk density of silver oxide is not particularly limited, but is, for example, 7 g / cm 3 , 6.5 g / cm 3 , 6 g / cm 3 , 5.8 g / cm 3 , 5.7 g / cm 3 , and the like. You may.
比較的大きい嵩密度とすることで、熱伝導性を上昇させやすくなり、蓄冷材用途等において好適に使用しうる材料となりうる。 By making the bulk density relatively large, it becomes easy to increase the thermal conductivity, and it can be a material that can be suitably used in cold storage material applications and the like.
なお、嵩密度の測定方法は特に限定されないが、例えば、アルキメデス法により測定してもよい。 The method for measuring the bulk density is not particularly limited, but for example, it may be measured by the Archimedes method.
酸化銀の理論密度比は、例えば、０．４５以上の範囲から選択してもよく、０．５以上（例えば、０．５５以上）、好ましくは０．６以上（例えば、０．６５以上）、さらに好ましくは０．７以上（例えば、０．７３以上、０．７５以上、０．７６以上、０．７７以上など）であってもよい。 The theoretical density ratio of silver oxide may be selected from the range of, for example, 0.45 or more, 0.5 or more (for example, 0.55 or more), preferably 0.6 or more (for example, 0.65 or more). , More preferably 0.7 or more (for example, 0.73 or more, 0.75 or more, 0.76 or more, 0.77 or more, etc.).
酸化銀の理論密度比の上限値は、例えば、０．９、０．８８、０．８５、０．８４、０．８３、０．８２、０．８１、０．８、０．７９などであってもよい。 The upper limit of the theoretical density ratio of silver oxide is, for example, 0.9, 0.88, 0.85, 0.84, 0.83, 0.82, 0.81, 0.8, 0.79, etc. There may be.
なお、理論密度比は、酸化銀の理論密度（理論最大密度）ｄ（約７．２ｇ／ｃｍ３）に対する嵩密度（実際の密度）ｄ１の比（ｄ１／ｄ）である。すなわち、理論密度比は、嵩密度を理論密度で除することで算出できる。 The theoretical density ratio is the ratio (d1 / d) of the bulk density (actual density) d1 to the theoretical density (theoretical maximum density) d (about 7.2 g / cm 3 ) of silver oxide. That is, the theoretical density ratio can be calculated by dividing the bulk density by the theoretical density.
酸化銀は、銀（不純物としての銀）を含んでいてもよい。このように銀を含む酸化銀において、銀の割合は、酸化銀の用途等において適宜選択できるが、本発明では、比較的銀の割合が低い酸化銀を効率よく提供しうる。 Silver oxide may contain silver (silver as an impurity). As described above, in silver oxide containing silver, the ratio of silver can be appropriately selected depending on the use of silver oxide and the like, but in the present invention, silver oxide having a relatively low ratio of silver can be efficiently provided.
このような銀の割合は、Ｘ線回折（ＸＲＤ）により、酸化銀及び銀に対応するピークの強度比として見積もることができる。例えば、酸化銀のＸ線回折パターンにおいて、酸化銀に対応する回折角３３°付近のピーク強度Ｉ３３と、銀に対応する回折角４４°付近のピーク強度Ｉ４４との強度比Ｉ４４／Ｉ３３は、０．３以下、好ましくは０．２以下、さらに好ましくは０．１以下程度であってもよく、０．０８以下、０．０５以下、０．０３以下、０．０２以下、０．０１以下などであってもよい。 The proportion of such silver can be estimated by X-ray diffraction (XRD) as the intensity ratio of silver oxide and the peak corresponding to silver. For example, in the X-ray diffraction pattern of silver oxide, the intensity ratio I 44 / I of the peak intensity I 33 in the vicinity of the diffraction angle 33 ° corresponding to silver oxide and the peak intensity I 44 in the vicinity of the diffraction angle 44 ° corresponding to silver. 33 may be 0.3 or less, preferably 0.2 or less, more preferably 0.1 or less, and may be 0.08 or less, 0.05 or less, 0.03 or less, 0.02 or less, 0. It may be 0.01 or less.
なお、Ｉ４４／Ｉ３３の下限値は、特に限定されず、０、０．００００１、０．０００１、０．０００３、０．０００５、０．０００７、０．００１、０．００１５などであってもよい。 The lower limit of I 44 / I 33 is not particularly limited, and may be 0, 0.00001, 0.0001, 0.0003, 0.0005, 0.0007, 0.001, 0.0015, or the like. May be good.
後述のように、本発明の酸化銀には、成形体の形態、ひいては比較的大きなサイズを有する形態の酸化銀が含まれるが、一般的に、このような大きなサイズの酸化銀は、酸化銀の熱安定性などに起因してか成形過程において銀が含まれやすい。しかし、本発明では、意外なことに、成形体や大きなサイズの酸化銀であっても、高純度の（さらには高純度と上記のような高気孔率や高嵩密度とを両立しうる）酸化銀を提供しうる。 As will be described later, the silver oxide of the present invention includes silver oxide in the form of a molded product and thus in a form having a relatively large size. Generally, such a large size silver oxide is silver oxide. Due to the thermal stability of silver, silver is likely to be contained in the molding process. However, in the present invention, surprisingly, even if it is a molded product or a large size silver oxide, it has high purity (furthermore, it is possible to achieve both high purity and high porosity and high bulk density as described above). Can provide silver oxide.
なお、後述するように、本発明の酸化銀を銀に変換（還元）して使用することも可能である。このような場合には、必ずしも酸化銀を上記のような高純度とする必要はない。 As will be described later, it is also possible to convert (reduce) the silver oxide of the present invention into silver before use. In such a case, it is not always necessary to make silver oxide having the above-mentioned high purity.
酸化銀の形態は、特に限定されないが、通常、複数の粒子を含む形態（二次粒子、凝集体、凝集粒子）であってもよい。 The form of silver oxide is not particularly limited, but may be usually a form containing a plurality of particles (secondary particles, aggregates, aggregated particles).
特に、本発明の酸化銀は成形体（酸化銀成形体）の形態であってもよい。例えば、酸化銀は、粉体成形体（粉体成形品）の形態であってもよい。このような成形体は、例えば、酸化銀の粉体（又は粉末）を、加圧下で成形することで得られる。 In particular, the silver oxide of the present invention may be in the form of a molded body (silver oxide molded body). For example, silver oxide may be in the form of a powder molded product (powder molded product). Such a molded product can be obtained, for example, by molding a silver oxide powder (or powder) under pressure.
また、複数の粒子を含む形態や成形体の形態の酸化銀において、各粒子は融着又は焼結されていてもよい。 Further, in the form of silver oxide containing a plurality of particles or in the form of a molded product, each particle may be fused or sintered.
このような成形体の形状は、特に限定されず、用途に応じて適宜選択しうる。例えば、粒状（粒子状）、ペレット状などであってもよい。 The shape of such a molded product is not particularly limited and may be appropriately selected depending on the intended use. For example, it may be granular (particulate), pellet-like, or the like.
なお、成形体の大きさは、用途や成形法などに応じて適宜選択でき、特に限定されないが、例えば、径は３０μｍ以上、４０μｍ以上、５０μｍ以上などであってもよい。より具体的な態様では、粒状の成形体（例えば、冷却材用途の粒状成形体など）の径は、５０μｍ～２ｍｍ程度であってもよい。また、ペレット状の成形体の径（直径、最大径）は、１００μｍ以上（例えば、５００μｍ以上、１ｍｍ以上、１．５ｍｍ以上、２ｍｍ以上など）であってもよい。 The size of the molded product can be appropriately selected depending on the intended use, molding method, etc., and is not particularly limited. For example, the diameter may be 30 μm or more, 40 μm or more, 50 μm or more, and the like. In a more specific embodiment, the diameter of the granular molded body (for example, the granular molded body used as a coolant) may be about 50 μm to 2 mm. Further, the diameter (diameter, maximum diameter) of the pellet-shaped molded product may be 100 μm or more (for example, 500 μm or more, 1 mm or more, 1.5 mm or more, 2 mm or more, etc.).
［酸化銀の製造方法］
本発明には、酸化銀の製造方法も含まれる。このような製造方法により得られる酸化銀は、上記のような物性を充足してもよく、しなくてもよい。特に、本発明の製造方法は、上記のような酸化銀を効率よく製造する方法として好適である。
[Manufacturing method of silver oxide]
The present invention also includes a method for producing silver oxide. The silver oxide obtained by such a production method may or may not satisfy the above physical characteristics. In particular, the production method of the present invention is suitable as a method for efficiently producing silver oxide as described above.
本発明の製造方法は、酸化銀を水蒸気（又は水蒸気の存在下）で熱処理する工程（熱処理工程）を少なくとも含む。 The production method of the present invention includes at least a step (heat treatment step) of heat-treating silver oxide with steam (or in the presence of steam).
熱処理に供する酸化銀（原料酸化銀）としては、特に限定されず、合成したものを使用してもよく、市販品を使用してもよい。 The silver oxide (raw material silver oxide) to be subjected to the heat treatment is not particularly limited, and a synthesized product may be used or a commercially available product may be used.
例えば、原料酸化銀は、金属銀及び／又は銀塩（硝酸銀など）と、アルカリ成分（水酸化ナトリウムなどのアルカリ金属水酸化物など）とを反応させることにより得てもよい。 For example, the raw material silver oxide may be obtained by reacting metallic silver and / or a silver salt (silver nitrate or the like) with an alkaline component (alkali metal hydroxide such as sodium hydroxide).
なお、アルカリ成分の割合は、特に限定されないが、確実に酸化銀（Ａｇ２Ｏ）を形成させるため、金属銀及び／又は銀塩を構成する銀の当量以上［例えば、１モル当量以上（例えば、１．０５モル当量以上、１．１モル当量以上、１．１５モル当量以上など）］としてもよい。 The proportion of the alkaline component is not particularly limited, but is equal to or more than the equivalent of metallic silver and / or silver constituting the silver salt [for example, 1 molar equivalent or more (for example,) in order to surely form silver oxide (Ag 2 O). , 1.05 molar equivalent or more, 1.1 molar equivalent or more, 1.15 molar equivalent or more, etc.)].
原料酸化銀は、銀などの他の成分を含んでいてもよいが、通常、実質的に酸化銀のみで構成してもよい。 The raw material silver oxide may contain other components such as silver, but usually may be composed substantially only of silver oxide.
原料酸化銀の形態（形状）は、特に限定されず、粉末（粉状、粉体状、粒状）であってもよく、成形体（原料成形体）であってもよい。代表的には、原料酸化銀（熱処理に供する酸化銀）は、粉体成形体（粉体成形品）であってもよい。 The form (shape) of the raw material silver oxide is not particularly limited, and may be a powder (powder-like, powder-like, granular) or a molded product (raw material molded product). Typically, the raw material silver oxide (silver oxide to be subjected to heat treatment) may be a powder molded product (powder molded product).
このような原料成形体は、酸化銀（原料酸化銀）を適当な方法により成形することで得ることができる。 Such a raw material molded body can be obtained by molding silver oxide (raw material silver oxide) by an appropriate method.
例えば、粉体成形体は、原料酸化銀の粉末を、加圧成形することにより得てもよい。加圧成形（法）としては、特に限定されないが、シップ（ＣＩＰ）成形（冷間等方圧加圧成形）を好適に使用してもよい。 For example, the powder molded product may be obtained by pressure molding the raw silver oxide powder. The pressure molding (method) is not particularly limited, but ship (CIP) molding (cold isotropic pressure molding) may be preferably used.
なお、加圧成形前に、原料酸化銀の粉末を仮成形してもよい。 The raw silver oxide powder may be temporarily molded before the pressure molding.
粉末状の原料酸化銀の粒径は、特に限定されないが、例えば、平均粒径で１～１０μｍ、好ましくは２～８μｍ、さらに好ましくは３～５μｍ程度であってもよい。 The particle size of the powdered raw material silver oxide is not particularly limited, but may be, for example, an average particle size of 1 to 10 μm, preferably 2 to 8 μm, and more preferably 3 to 5 μm.
また、原料酸化銀［例えば、粉末状の原料酸化銀（又は粉体成形体）］は、適当なバインダー成分を含んでいてもよいが、本発明ではこのようなバインダー成分を含まない原料酸化銀を好適に使用してもよい。 Further, the raw material silver oxide [for example, powdered raw material silver oxide (or powder molded product)] may contain an appropriate binder component, but in the present invention, the raw material silver oxide does not contain such a binder component. May be suitably used.
原料成形体の形状は、特に限定されず、用途に応じて適宜選択しうる。例えば、粒状（粒子状）、ペレット状などであってもよい。 The shape of the raw material molded product is not particularly limited and may be appropriately selected depending on the intended use. For example, it may be granular (particulate), pellet-like, or the like.
熱処理工程では、前記のように、原料酸化銀を水蒸気で熱処理する。このように水蒸気で熱処理することで、前記のような物性（例えば、高開気孔率、高嵩密度など）を有する酸化銀を効率よく得やすい。
また、熱処理工程では、本来、酸化銀が分解して銀へ還元する温度であっても、酸化銀の状態を保持したまま熱処理を行うことができる。
In the heat treatment step, as described above, the raw material silver oxide is heat-treated with steam. By heat-treating with steam in this way, it is easy to efficiently obtain silver oxide having the above-mentioned physical characteristics (for example, high open porosity, high bulk density, etc.).
Further, in the heat treatment step, the heat treatment can be performed while maintaining the state of silver oxide even at a temperature at which silver oxide is originally decomposed and reduced to silver.
熱処理は、水蒸気の存在下で行うことができれば、その温度は特に限定されず、例えば、７０℃以上（例えば、８０℃以上）程度の範囲から選択でき、１００℃以上、好ましくは１２０℃以上、さらに好ましくは１４０℃以上であってもよく、１６０℃以上（例えば、１８０℃以上など）とすることもできる。
なお、温度の上限値は、特に限定されず、例えば、５００℃、４５０℃、４００℃、３５０℃、３００℃、２７０℃、２５０℃、２３０℃などであってもよい。
The temperature of the heat treatment is not particularly limited as long as it can be performed in the presence of steam, and can be selected from a range of, for example, about 70 ° C. or higher (for example, 80 ° C. or higher), 100 ° C. or higher, preferably 120 ° C. or higher. More preferably, it may be 140 ° C. or higher, and 160 ° C. or higher (for example, 180 ° C. or higher).
The upper limit of the temperature is not particularly limited and may be, for example, 500 ° C., 450 ° C., 400 ° C., 350 ° C., 300 ° C., 270 ° C., 250 ° C., 230 ° C. or the like.
また、熱処理は、常圧下又は加圧下で行ってもよく、特に加圧下（加圧水蒸気、過熱水蒸気、水熱条件下）で行ってもよい。加圧下で行う場合、圧力（反応器内圧力、内圧）としては、温度にもよるが、例えば、０．１２ＭＰａ以上、好ましくは０．１５ＭＰａ以上、さらに好ましくは０．２ＭＰａ以上であってもよく、０．３ＭＰａ以上などであってもよい。 Further, the heat treatment may be performed under normal pressure or under pressure, and may be performed particularly under pressure (pressurized steam, superheated steam, hydrothermal conditions). When the pressure is applied, the pressure (reactor internal pressure, internal pressure) may be, for example, 0.12 MPa or more, preferably 0.15 MPa or more, and more preferably 0.2 MPa or more, although it depends on the temperature. , 0.3 MPa or more may be used.
加圧下で行う場合、圧力の上限値は、特に限定されないが、例えば、２２ＭＰａ、２０ＭＰａなどであってもよい。前記のように比較的高い開気孔率や嵩密度を有する酸化銀を効率良く得るためには、極端な高圧を作用させることなく熱処理してもよい。 When the pressure is applied, the upper limit of the pressure is not particularly limited, but may be, for example, 22 MPa, 20 MPa, or the like. In order to efficiently obtain silver oxide having a relatively high porosity and bulk density as described above, heat treatment may be performed without applying an extremely high pressure.
熱処理は、加圧又は飽和水蒸気圧下で行ってもよく、非飽和水蒸気圧下で行ってもよい。 The heat treatment may be performed under pressure or saturated steam pressure, or may be performed under unsaturated steam pressure.
なお、熱処理は、水蒸気の存在下で行うことができれば、水以外の成分の存在下で行ってもよい。例えば、水以外の成分（他の成分）を含む水溶液の蒸気中で、熱処理を行うこともできる。
このような他の成分としては、例えば、アルカリ成分（例えば、水酸化ナトリウム、水酸化カリウムなどの水酸化物など）などが含まれる。
The heat treatment may be performed in the presence of components other than water as long as it can be performed in the presence of steam. For example, the heat treatment can be performed in the steam of an aqueous solution containing a component other than water (other components).
Such other components include, for example, an alkaline component (for example, a hydroxide such as sodium hydroxide and potassium hydroxide) and the like.
ただし、このような他の成分の存在下で熱処理することで、酸化銀（特に酸化銀成形体）を不均一化しやすい傾向があるようである（例えば、部位によって組織が密に成長するなど）。そのため、他の成分（例えば、アルカリ成分）の存在下で熱処理する場合でも、このような影響が生じない程度で他の成分を存在させるのが好ましく、特に、実質的に水蒸気のみで熱処理を行うのが好ましい。 However, it seems that heat treatment in the presence of such other components tends to make silver oxide (particularly silver oxide molded product) non-uniform (for example, the tissue grows densely depending on the site). .. Therefore, even when the heat treatment is performed in the presence of other components (for example, an alkaline component), it is preferable that the other components are present to the extent that such an effect does not occur, and in particular, the heat treatment is performed substantially only with steam. Is preferable.
熱処理（工程）を行う容器（反応器）は、特に限定されず、例えば、オートクレーブなどの加熱（及び加圧）可能な容器を使用してもよい。 The container (reactor) for performing the heat treatment (process) is not particularly limited, and for example, a container capable of heating (and pressurizing) such as an autoclave may be used.
熱処理において、水蒸気の量は、特に限定されず、飽和状態又は非飽和状態であるか等に応じて適宜選択でき、例えば、水として容器内体積（系内の体積）の０．５体積％以上、好ましくは１体積％以上、さらに好ましくは２体積％以上などであってもよく、５体積％以上、１０体積％以上、１５体積％以上、２０体積％以上、２５体積％以上、３０体積％以上などであってもよい。
なお、上限値としては、特に限定されないが、例えば、水として容器内体積（系内の体積）の９０体積％、８０体積％、７０体積％、６０体積％、５０体積％などであってもよい。
In the heat treatment, the amount of water vapor is not particularly limited and can be appropriately selected depending on whether it is in a saturated state or an unsaturated state, for example, 0.5% by volume or more of the volume in the container (volume in the system) as water. It may be preferably 1% by volume or more, more preferably 2% by volume or more, 5% by volume or more, 10% by volume or more, 15% by volume or more, 20% by volume or more, 25% by volume or more, 30% by volume. It may be the above.
The upper limit value is not particularly limited, but may be, for example, 90% by volume, 80% by volume, 70% by volume, 60% by volume, 50% by volume, etc. of the volume inside the container (volume in the system) as water. good.
熱処理時間は、原料酸化銀の形状や熱処理条件などに応じて適宜選択でき、特に限定されないが、例えば、１０分以上（例えば、３０分以上）、好ましくは１時間以上（例えば、１．５時間以上）、さらに好ましくは２時間以上（例えば、２．５時間以上）などであってもよい。 The heat treatment time can be appropriately selected depending on the shape of the raw silver oxide, the heat treatment conditions, and the like, and is not particularly limited, but is, for example, 10 minutes or more (for example, 30 minutes or more), preferably 1 hour or more (for example, 1.5 hours). More than that), more preferably 2 hours or more (for example, 2.5 hours or more).
なお、熱処理後の酸化銀は、必要に応じて、洗浄処理してもよい。 The silver oxide after the heat treatment may be washed if necessary.
上記のようにして、酸化銀が得られる。特に、原料酸化銀が成形体である場合、当該成形体の形態（形状）を反映した酸化銀が得られる。 As described above, silver oxide is obtained. In particular, when the raw material silver oxide is a molded product, silver oxide that reflects the form (shape) of the molded product can be obtained.
［酸化銀の用途］
本発明の酸化銀の用途は、特に限定されず、種々の用途［例えば、蓄冷材又は冷却材（冷凍機用の蓄冷材など）、電極材、触媒など］に使用できる。
[Use of silver oxide]
The use of the silver oxide of the present invention is not particularly limited, and can be used for various uses [for example, a cold storage material or a cooling material (such as a cold storage material for a refrigerator), an electrode material, a catalyst, etc.].
特に、本発明の酸化銀は、比較的大きい開気孔率や嵩密度を有している（さらには高純度で酸化銀を含んでいる）場合が多く、このような物性を生かした用途に好適に使用しうる。 In particular, the silver oxide of the present invention often has a relatively large porosity and bulk density (further contains silver oxide with high purity), and is suitable for applications that make use of such physical characteristics. Can be used for.
また、本発明の酸化銀は、そのまま使用する場合のみならず、銀に還元することで使用することもできる。 Further, the silver oxide of the present invention can be used not only when it is used as it is, but also when it is reduced to silver.
例えば、触媒用途などでは、本発明の酸化銀をそのままないし酸化銀を還元させた銀の状態で触媒として使用することもできる。 For example, in catalyst applications, the silver oxide of the present invention can be used as a catalyst as it is or in the state of silver obtained by reducing silver oxide.
銀に還元しても、元の物性（比較的大きい開気孔率や嵩密度）や形状を保持しているため、このような物性や形状を有する銀原料として、本発明の酸化銀を使用することもできる。 Even if it is reduced to silver, it retains its original physical properties (relatively large porosity and bulk density) and shape. Therefore, the silver oxide of the present invention is used as a silver raw material having such physical properties and shape. You can also do it.
次に、実験例、実施例を挙げて本発明をさらに具体的に説明するが、本発明はこれらの実施例により何ら限定されるものではなく、多くの変形が本発明の技術的思想内で当分野において通常の知識を有する者により可能である。 Next, the present invention will be described in more detail with reference to experimental examples and examples, but the present invention is not limited to these examples, and many modifications are made within the technical idea of the present invention. It is possible by a person who has ordinary knowledge in this field.
なお、各種物性・特性は以下のように測定又は評価した。 Various physical properties and characteristics were measured or evaluated as follows.
（開気孔率）
開気孔量（Ｐ）は酸化銀（成形体）の乾燥重量（Ｗ１）、および水中での重量（Ｗ２）、含水させた際の重量（Ｗ３）から、下記の式により求めた。
Ｐ（％）＝１００×（Ｗ３－Ｗ１）／（Ｗ３－Ｗ２）
（嵩密度）
アルキメデス法により測定した。
（理論密度比）
アルキメデス法により測定した嵩密度と、酸化銀の理論密度から計算した。
（銀量及び結晶相）
Ｘ線回折（ＸＲＤ）により、酸化銀の主ピーク（３３°付近）強度Ｉ３３と、銀の２番目に高いピーク（４４°付近）強度Ｉ４４との強度比Ｉ４４／Ｉ３３を測定した。
結晶相は、Ｉ４４／Ｉ３３の値が０．１以下であるとき、酸化銀の単一相と、０．１超であるとき酸化銀及び銀を含む相と決定した。
(Open porosity)
The amount of open pores (P) was calculated by the following formula from the dry weight (W 1 ) of silver oxide (molded body), the weight in water (W 2 ), and the weight when impregnated with water (W 3 ).
P (%) = 100 × (W 3 -W 1 ) / (W 3 -W 2 )
(The bulk density)
It was measured by the Archimedes method.
(Theoretical density ratio)
It was calculated from the bulk density measured by the Archimedes method and the theoretical density of silver oxide.
(Silver amount and crystal phase)
By X-ray diffraction (XRD), the intensity ratio I 44 / I 33 of the silver oxide main peak (near 33 °) intensity I 33 and the silver second highest peak (near 44 °) intensity I 44 was measured. ..
The crystalline phase was determined to be a single phase of silver oxide when the value of I 44 / I 33 was 0.1 or less, and a phase containing silver oxide and silver when the value was more than 0.1.
（実施例１～５、参考例１）
濃度５．０質量％硝酸銀水溶液２００ｇに、濃度０．４質量％の水酸化ナトリウム水溶液７０７．５ｇ（反応当量の１．２モル倍）を約５分かけて混合し、１５分間放置（エージング）した。得られた混合物をデカンテーションにより中性になるまで洗浄後、得られたスラリーを１００℃で５時間処理（エージング）し、酸化銀の粉末（平均粒径約４μｍ）を得た。
(Examples 1 to 5, Reference Example 1)
707.5 g of a 0.4% by mass sodium hydroxide aqueous solution (1.2 mol times the reaction equivalent) was mixed with 200 g of a 5.0 mass% silver nitrate aqueous solution over about 5 minutes and left for 15 minutes (aging). did. The obtained mixture was washed by decantation until it became neutral, and then the obtained slurry was treated (aged) at 100 ° C. for 5 hours to obtain a silver oxide powder (average particle size of about 4 μm).
得られた酸化銀粉末を、一軸加圧により仮成形した後、冷間等方圧加圧（ＣＩＰ、圧力１５０ＭＰａ、時間４分）により、ペレット状（直径約１６ｍｍ、厚さ約３ｍｍ）に成形した。 The obtained silver oxide powder is temporarily molded by uniaxial pressure, and then molded into pellets (diameter: about 16 mm, thickness: about 3 mm) by cold isotropic pressure (CIP, pressure: 150 MPa, time: 4 minutes). did.
得られたペレットを、溶液と接しないように試料台を設けたテフロン内張オートクレーブに入れ、表１に示した条件で熱処理を行った。熱処理後、希硝酸（濃度３．０質量％）にて３０秒間洗浄し、ペレット状の酸化銀を得た。なお、実施例１～５で得られた酸化銀（の表面）には、４～５μｍ程度の空孔を確認できた。 The obtained pellets were placed in a Teflon-lined autoclave provided with a sample table so as not to come into contact with the solution, and heat-treated under the conditions shown in Table 1. After the heat treatment, it was washed with dilute nitric acid (concentration: 3.0% by mass) for 30 seconds to obtain pelletized silver oxide. In addition, pores of about 4 to 5 μm could be confirmed in (the surface of) the silver oxide obtained in Examples 1 to 5.
下記表に条件及び熱処理後の酸化銀の物性をまとめたものを示す。 The table below summarizes the conditions and the physical properties of silver oxide after heat treatment.
また、熱処理前のペレット、実施例１～５及び参考例１で得られた酸化銀の微細構造を、走査型電子顕微鏡（ＳＥＭ）により確認した。ＳＥＭ写真（５０００倍）を図１～７に示す。 In addition, the pellets before heat treatment and the fine structures of silver oxide obtained in Examples 1 to 5 and Reference Example 1 were confirmed by a scanning electron microscope (SEM). SEM photographs (5000x) are shown in FIGS. 1-7.
表１の結果及び図からも明らかなように、実施例では、高い開気孔率等を有する酸化銀が得られた。 As is clear from the results in Table 1 and the figures, in the examples, silver oxide having a high porosity and the like was obtained.
本発明によれば、新規な酸化銀を提供できる。 According to the present invention, a novel silver oxide can be provided.
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