JP3517392B2 - Silicon porous body, method for manufacturing silicon porous body, silicon powder and method for manufacturing the same - Google Patents
Silicon porous body, method for manufacturing silicon porous body, silicon powder and method for manufacturing the sameInfo
- Publication number
- JP3517392B2 JP3517392B2 JP2000260630A JP2000260630A JP3517392B2 JP 3517392 B2 JP3517392 B2 JP 3517392B2 JP 2000260630 A JP2000260630 A JP 2000260630A JP 2000260630 A JP2000260630 A JP 2000260630A JP 3517392 B2 JP3517392 B2 JP 3517392B2
- Authority
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- Prior art keywords
- silicon
- mass
- porous body
- present
- conductive carbon
- Prior art date
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- Filtering Materials (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Powder Metallurgy (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明はケイ素質多孔体、ケ
イ素質粉末に関し、より詳細には半導体特性を有するシ
リコンと、半導体性を有しない金属シリコンとを含む導
電性ケイ素質多孔体、ケイ素質多孔体の製造方法、ケイ
素質粉末およびその製造方法に関する。The invention siliceous porous body BACKGROUND OF THE INVENTION relates to siliceous powder, and silicon having a semiconductor characteristic in more detail, conductive siliceous porous body comprising a metallic silicon having no semiconductor properties, silicaceous The present invention relates to a method for producing a porous body, a silicon powder and a method for producing the same.
【０００２】[0002]
【従来の技術】これまで多孔体は、空気、汚染水などか
ら有害物質を物質を吸着することにより、環境から有害
物質を分離・固定化して、空気、汚染水を浄化するため
に多用されている。多くの場合、これらの多孔体は内部
に形成された微細な細孔へと上述した有害物質を吸着す
ることにより空気、水などを浄化するものである。しか
しながら従来知られている細孔を用いる有害物質の吸着
による分離・浄化は、ある程度有害物質の吸着が進行す
ると、吸着特性が劣化してしまい、長期間にわたる安定
的な浄化作用を維持することができないといった問題が
あった。2. Description of the Related Art Up to now, porous materials have been widely used to purify air and contaminated water by adsorbing harmful substances from air, contaminated water, etc. to separate and immobilize harmful substances from the environment. There is. In many cases, these porous bodies purify air, water, etc. by adsorbing the above-mentioned harmful substances into the fine pores formed inside. However, in the separation / purification by adsorption of harmful substances using the conventionally known pores, if adsorption of harmful substances progresses to some extent, the adsorption characteristics deteriorate and it is possible to maintain a stable purification action for a long period of time. There was a problem that I could not.
【０００３】[0003]
【発明が解決しようとする課題】したがって、これま
で、環境からの汚染物質の除去能力を向上させ、さらに
は向上した除去能力を長期間にわたり維持することが可
能な多孔体が必要とされていた。本発明は、上記問題点
に鑑みなされたものであり、従来の濾過材、フィルター
として用いられている多孔質体の汚染物質除去能力を向
上させ、さらにこの汚染物質除去能力を長期間にわたっ
て維持することが可能なケイ素質多孔体、ケイ素質多孔
体の製造方法、ケイ素質粉末およびその製造方法を提供
することを目的とする。Therefore, there has been a need for a porous body capable of improving the ability to remove pollutants from the environment and maintaining the improved ability for a long period of time. . The present invention has been made in view of the above problems, and improves the pollutant removal ability of a conventional filtration material and a porous body used as a filter, and further maintains this pollutant removal ability for a long period of time. Porous silicon, porous silicon
An object of the present invention is to provide a method for producing a body, a silicon powder and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明者は、鋭意検討し
た結果、多孔体に半導体特性を有する材料を用い、その
内部のキャリアを有効に用いることにより、吸着ではな
く電気化学的に汚染物質を除去することが可能な多孔体
を提供することにより、吸着作用による汚染物質の除去
を用いる従来の濾過材またはフィルターの問題点を解決
し、より良好な特性を有する多孔体を提供できることを
見出し、本発明を完成したものである。Means for Solving the Problems As a result of extensive studies, the present inventor has used a material having semiconductor properties as a porous material and effectively using a carrier therein to electrochemically pollute contaminants rather than adsorb it. It has been found that by providing a porous body capable of removing a porous material, it is possible to solve the problems of the conventional filtering material or filter that uses the removal of pollutants by adsorption action, and provide a porous body having better properties. The present invention has been completed.
【０００５】すなわち、本発明の請求項１の発明によれ
ば、ＰＮドープされた粒状高純度シリコンと、前記粒状
高純度シリコンよりも粒度の粗い金属シリコンとを質量
比で１：２〜１：５で含有し、さらに導電性カーボン
と、トルマリン１〜１０質量％と、酸化チタン１０〜４
０質量％と、無水珪酸ナトリウム０．５〜５質量％とを
含有し、体積抵抗率が０．１Ωｍ〜５００Ωｍであるケ
イ素質多孔体が提供される。That is, according to the first aspect of the present invention, PN-doped granular high-purity silicon and the granular
Mass of metallic silicon with a coarser grain than high-purity silicon
It is contained in the ratio of 1: 2 to 1: 5, and is further made of conductive carbon.
And 1 to 10% by weight of tourmaline and 10 to 4 of titanium oxide
0 mass% and anhydrous sodium silicate 0.5 to 5 mass%
Provided is a siliceous porous body which contains and has a volume resistivity of 0.1 Ωm to 500 Ωm.
【０００６】本発明の請求項２の発明によれば、さらに
銀ゼオライト２〜１５質量％と、銀０．５〜５質量％と
を含有することを特徴とするケイ素質多孔体が提供され
る。 According to the invention of claim 2 of the present invention,
2 to 15% by mass of silver zeolite and 0.5 to 5% by mass of silver
There is provided a siliceous porous body characterized by containing
It
【０００７】本発明の請求項３の発明によれば、体積抵
抗率が０．１Ωｍ〜２０Ωｍである、ケイ素質多孔体が
提供される。 According to the invention of claim 3 of the present invention,
A silicon-based porous body having a resistance of 0.1 Ωm to 20 Ωm
Provided.
【０００８】本発明の請求項４の発明においては、導電
性カーボンは、竹炭から得られるグラファイトである。 According to the invention of claim 4 of the present invention,
The characteristic carbon is graphite obtained from bamboo charcoal.
【０００９】本発明の請求項５の発明によれば、ＰＮド
ープされた粒状高純度シリコンと、前記粒状高純度シリ
コンよりも粒度の粗い金属シリコンとを質量比で１：２
〜１：５とし、さらにトルマリン１〜１０質量％と、酸
化チタン１０〜４０質量％と、無水珪酸ナトリウム０．
５〜５質量％とを含む組成物を混練りする工程と、該混
練りされた組成物を成形して成形体を形成する工程と、
該成形体を非酸化性雰囲気中で７００℃〜１４００℃の
温度で焼結させる工程と、前記成形体に対して導電性カ
ーボンを含有させる工程と、を含むケイ素質多孔体の製
造方法が提供される。 According to the invention of claim 5 of the present invention,
Granular high-purity silicon and the granular high-purity silicon
Mass ratio of metallic silicon, which is coarser than that of kon, in a mass ratio of 1: 2
˜1: 5, 1 to 10% by weight tourmaline, acid
Titanium iodide 10 to 40 mass% and anhydrous sodium silicate 0.
A step of kneading a composition containing 5 to 5% by mass, and
Molding the kneaded composition to form a molded body,
The molded body was heated at 700 ° C to 1400 ° C in a non-oxidizing atmosphere.
The process of sintering at a temperature
Carbon-containing step, and
A manufacturing method is provided.
【００１０】本発明の請求項６の発明によれば、前記組
成物が、さらに銀ゼオライト２〜１５質量％と、銀０．
５〜５質量％とを含むケイ素質多孔体の製造方法が提供
される。 According to the invention of claim 6 of the present invention, the set
The product further contains 2 to 15% by mass of silver zeolite and 0.
Provided is a method for producing a siliceous porous body containing 5 to 5% by mass.
To be done.
【００１１】本発明の請求項７の発明によれば、前記導
電性カーボンは、竹炭から得られるグラファイトであ
る、ケイ素質多孔体の製造方法が提供される。 According to the invention of claim 7 of the present invention,
Electrolytic carbon is graphite obtained from bamboo charcoal.
A method for manufacturing a porous silicon material is provided.
【００１２】本発明の請求項８の発明によれば、前記非
酸化性雰囲気は、少なくとも二酸化炭素を含む、ケイ素
質多孔体の製造方法が提供される。 According to the invention of claim 8 of the present invention,
The oxidizing atmosphere is silicon containing at least carbon dioxide.
A method for manufacturing a porous material is provided.
【００１３】本発明の請求項９の発明によれば、ＰＮド
ープされた粒状高純度シリコンと、前記粒状高純度シリ
コンよりも粒度の粗い金属シリコンとを質量比で１：２
〜１：５で含有し、さらに導電性カーボンと、トルマリ
ン１〜１０質量％と、酸化チタン１０〜４０質量％と、
無水珪酸ナトリウム０．５〜５質量％とを含有し体積抵
抗率が０．１Ωｍ〜５００Ωｍであるケイ素質焼成多孔
体を粉砕することにより得られるケイ素質粉末が提供さ
れる。 According to the invention of claim 9 of the present invention,
Granular high-purity silicon and the granular high-purity silicon
Mass ratio of metallic silicon, which is coarser than that of kon, in a mass ratio of 1: 2
~ 1: 5, conductive carbon, and tormari
1 to 10% by mass, titanium oxide 10 to 40% by mass,
It contains 0.5 to 5% by mass of anhydrous sodium silicate.
Silicon fired porosity with a resistance of 0.1 Ωm to 500 Ωm
Provided is a siliceous powder obtained by crushing the body
Be done.
【００１４】本発明の請求項１０の発明によれば、さら
に銀ゼオライト２〜１５質量％と、銀０．５〜５質量％
とを含有することを特徴とする、ケイ素質粉末が提供さ
れる。 According to the invention of claim 10 of the present invention,
2 to 15% by mass of silver zeolite and 0.5 to 5% by mass of silver
And a siliceous powder, characterized by containing
Be done.
【００１５】本発明の請求項１１の発明によれば、ＰＮ
ドープされた粒状高純度シリコンと、前記粒状高純度シ
リコンよりも粒度の粗い金属シリコンとを質量比で１：
２〜１：５で含有し、さらにトルマリン１〜１０質量％
と、酸化チタン１０〜４０質量％と、無水珪酸ナトリウ
ム０．５〜５質量％とを含む組成物を混練りする工程
と、該混練りされた組成物を成形して成形体を形成する
工程と、該成形体を非酸化性雰囲気中で７００℃〜１４
００℃の温度で焼結させてケイ素質多孔体を形成する工
程と、該ケイ素質多孔体に導電性カーボンを含有させる
工程と、前記導電性カーボンを含有した前記ケイ素質多
孔体を粉砕する工程と、を含むケイ素質粉末の製造方法
が提供される。 According to the eleventh aspect of the present invention, the PN
Doped granular high-purity silicon and the granular high-purity silicon
Mass ratio of metallic silicon, which has a coarser grain size than that of recon, is 1:
2 to 1: 5, and 1 to 10% by weight tourmaline
And 10 to 40% by mass of titanium oxide and anhydrous sodium silicate
Kneading a composition containing 0.5 to 5 mass%
And molding the kneaded composition to form a molded body
Process and the molded body in a non-oxidizing atmosphere at 700 ° C. to 14 ° C.
A process for forming a porous silicon material by sintering at a temperature of 00 ° C.
And the electrically conductive carbon is contained in the porous silicon material.
Process and the silicon-based material containing the conductive carbon.
Pulverizing the pores, and a method for producing a siliceous powder, comprising:
Will be provided.
【００１６】[0016]
【発明の実施の形態】以下本発明を詳細に説明する。本
発明のケイ素質多孔体は、半導体特性を有するシリコン
と、金属シリコンとを含み、体積抵抗率が０．１Ωm〜
５００Ωmとされている。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The silicon-based porous body of the present invention contains silicon having semiconductor characteristics and metallic silicon, and has a volume resistivity of 0.1 Ωm-
It is set to 500 Ωm.
【００１７】半導体性を有するシリコンとしては、種々
のものを挙げることができるが本発明においては、抵抗
値が約０．１Ω〜５００Ωであり、半導体として用いる
ことができる電気抵抗の高純度シリコンを用いることが
好ましい。また、上述した高純度シリコンには、Ｎ型お
よびＰ型それぞれの不純物がドーピングされていて、電
気的特性が調節されていることが必要とされる。また、
本発明においては特に高純度シリコンに対してＰ型およ
びＮ型のドーピングがなされた高純度シリコンを用いる
ことが、電子・ホールを必要とする化学プロセスに対し
て良好な特性を付与することができるため必要である。 Various types of silicon having a semiconducting property can be cited, but in the present invention, high-purity silicon having an electric resistance of about 0.1Ω to 500Ω and having an electric resistance which can be used as a semiconductor is used. It is preferable to use. Further, it is necessary that the above-mentioned high-purity silicon is doped with N-type and P-type impurities to adjust the electrical characteristics . Also,
In the present invention, the use of high-purity silicon in which P-type and N-type doping is applied to high-purity silicon can impart good characteristics to a chemical process requiring electrons and holes. Therefore, it is necessary.
【００１８】上述した半導体性を有するシリコンは、通
常ではシリコンウエハとして市販されているものを用い
ることができ、本発明においては、シリコンウエハを粉
砕して粒状、フレーク状、粉末とし、表面積をできるだ
け大きくすることが好ましい。本発明においてはこの半
導体特性を有するシリコンは単独で用いることも可能で
はあるが、ケイ素質多孔体の質量に対して５〜６０質量
％で金属シリコンと混合して用いると、充分な汚染物質
の除去特性を付与することができることが見出された。
５質量％より少ないと、特性的に劣り、６０質量％を超
えると製造コストが高くなる。As the above-mentioned silicon having semiconducting property, those commercially available as a silicon wafer can be usually used. In the present invention, the silicon wafer is crushed into particles, flakes or powders so that the surface area is as large as possible. It is preferable to make it large. In the present invention, it is possible to use silicon having this semiconductor property alone, but when it is used as a mixture with metallic silicon in an amount of 5 to 60% by mass relative to the mass of the silicon-based porous body, sufficient contamination of contaminants can be obtained. It has been found that removal properties can be imparted.
If it is less than 5% by mass, the properties are inferior, and if it exceeds 60% by mass, the manufacturing cost becomes high.
【００１９】本発明に用いる金属シリコンとは、上述し
た高純度シリコンに対しては純度が低く、製鉄などにお
いて鉄の改質を行うために主として用いられるケイ素約
９８％程度の純度のグレードのシリコンをいう。この金
属シリコンは、本発明のケイ素質多孔体の質量に対して
４０〜９５質量％で添加することができる。４０質量％
より少ないとケイ素質多孔体に対して充分な多孔性を付
与することができず、また９５質量％を超えると汚染物
質の除去特性が低下するためである。また、この金属シ
リコンは、本発明のケイ素質多孔体に対して多孔性を付
与するために用いられるものであり、市販されている金
属シリコンの固まりを粉砕して適切な粒度の粒状体、フ
レーク、粉末として用いることができる。上述した半導
体特性を有するシリコンと、金属シリコンの粒度につい
ては本発明においては特に制限されるものではなく、必
要とされる用途・特性に応じて適宜選択することができ
る。以下、本発明においては、説明の便宜上半導体性を
有するシリコンおよび金属シリコンを粒状として用いた
実施の形態について説明する。半導体性を有する粒状の
シリコンと粒状の金属シリコンとを、質量比で１：１０
〜１：０．５の範囲として用いることが、良好な特性を
付与する点からは好ましいが、特に１：２〜１：５の範
囲とすることが特性と製造コストとをバランスさせる上
で必要である。 The metallic silicon used in the present invention has a low purity with respect to the above-mentioned high-purity silicon, and is mainly used for modifying iron in iron making and the like, and has a purity of about 98%. Say. This metallic silicon can be added at 40 to 95 mass% with respect to the mass of the silicon-based porous body of the present invention. 40 mass%
This is because if it is less than the above range, sufficient porosity cannot be imparted to the porous silicon material, and if it exceeds 95% by mass, the pollutant removal property deteriorates. Further, this metallic silicon is used for imparting porosity to the siliceous porous body of the present invention, and a lump of commercially available metallic silicon is crushed to form a granular body or flakes having an appropriate particle size. , Can be used as a powder. The particle sizes of the above-mentioned silicon having semiconductor characteristics and metallic silicon are not particularly limited in the present invention, and can be appropriately selected according to the required application and characteristics. Hereinafter, in the present invention, an embodiment in which semiconducting silicon and metallic silicon are used in a granular form will be described for convenience of description. Granular silicon having semiconductivity and granular metallic silicon are used in a mass ratio of 1:10.
To 1: be used as a range of 0.5, is preferred from the viewpoint of imparting good properties, in particular 1: 2 to 1: be in the range of 5 on to balance the properties and manufacturing cost
Needed in.
【００２０】本発明において汚染物質を除去するといっ
た点からは、トルマリン、酸化チタン、銀ゼオライト、
銀といった添加物質を用いてケイ素質多孔体を形成する
ことが必要である。これらの添加物質の本発明のケイ素
質多孔体の汚染物質除去特性における役割は明確ではな
く、あくまで推定の域を出るものではないが、これらの
成分が気体、液体に含まれるイオン成分の存在下で電気
化学的に電池を形成し、本発明のケイ素質多孔体の除去
特性に影響を与えるものと推定している。上述した添加
物質のうち、トルマリンは、ケイ素質多孔体の質量に対
して１〜１０質量％で添加することができ、酸化チタン
は、１０〜４０質量％で添加することができる。From the viewpoint of removing contaminants in the present invention, tourmaline, titanium oxide, silver zeolite,
It is necessary to form a siliceous porous body using an additive substance such as silver. The role of these additive substances in the contaminant removal characteristics of the porous silicon material of the present invention is not clear and is not beyond the scope of estimation, but these components are present in the presence of ionic components contained in gas or liquid. It is presumed that a battery is electrochemically formed by the above method to affect the removal characteristics of the silicon-based porous body of the present invention. Among the above-mentioned added substances, tourmaline can be added in an amount of 1 to 10% by mass, and titanium oxide can be added in an amount of 10 to 40% by mass, based on the mass of the porous silicon material.
【００２１】この酸化チタンは、ルチル型の酸化チタン
とすることもできるし、特に結晶系を定めることなく、
ルチル、アナターゼといった種々の結晶状態を含む酸化
チタンを用いることもできる。また、これらの酸化チタ
ンのそれぞれを適宜混合して用いることができる。これ
らの酸化チタンを混合して用いる場合には、ルチル型の
酸化チタンとそれ以外の酸化チタンとの比を４：３程度
として用いることができる。本発明において添加物質と
して用いられる銀ゼオライトは、２〜１５質量％で含有
されることが良好な除去特性を付与する点から好まし
い。さらに、本発明においては、さらに銀０．５〜５質
量％と、結着性を付与するための無水珪酸ナトリウム
０．５〜５質量％とが含まれていることが好ましい。The titanium oxide may be rutile type titanium oxide, and the crystal system is not particularly defined.
Titanium oxide containing various crystal states such as rutile and anatase can also be used. Further, each of these titanium oxides can be appropriately mixed and used. When these titanium oxides are mixed and used, the ratio of the rutile type titanium oxide to the other titanium oxides can be set to about 4: 3. The silver zeolite used as an additive in the present invention is preferably contained in an amount of 2 to 15 mass% from the viewpoint of providing good removal characteristics. Further, in the present invention, it is preferable that 0.5 to 5% by mass of silver and 0.5 to 5% by mass of anhydrous sodium silicate for imparting binding property are further contained.
【００２２】また、本発明のケイ素質多孔体の体積抵抗
率が０．１Ωｍ〜５００Ωｍとされていることが、汚染
物質の良好な除去特性を付与する点から好ましい。本発
明のケイ素質多孔体の導電性は、さらに、導電性カーボ
ンを浸透または固着させることにより向上させることが
できる。このような、導電性カーボンとしては、導電性
カーボンブラックとして知られている市販品を用いるこ
とができる。また、より効果的には、竹炭を製造する際
に発生する煤を、本発明のケイ素質多孔体の焼結の際に
浸透または固着させることにより、より低価格かつ、よ
り効果的に導電性カーボンとして添加することができ
る。このような導電性カーボンは、その素性によらず、
本発明のケイ素質多孔体の質量に対して１質量％〜３０
質量％で添加することができる。導電性カーボンを含有
させることにより、体積抵抗率を０．１Ωｍ〜２０Ωｍ
程度にまでより効果的に低下させることができる。Further, the volume resistivity of the porous silicon material of the present invention is preferably 0.1 Ωm to 500 Ωm from the viewpoint of providing good contaminant removal characteristics. The conductivity of the silicon-based porous body of the present invention can be further improved by permeating or fixing conductive carbon. As such conductive carbon, commercially available products known as conductive carbon black can be used. In addition, more effectively, the soot generated during the production of bamboo charcoal is permeated or fixed during the sintering of the porous silicon material of the present invention, resulting in a lower cost and more effective conductivity. It can be added as carbon. Such conductive carbon, regardless of its nature,
1% by mass to 30 with respect to the mass of the porous silicon material of the present invention
It can be added by mass%. By containing conductive carbon, the volume resistivity is 0.1Ωm to 20Ωm.
It can be reduced more effectively to the extent.
【００２３】本発明のケイ素質多孔体の製造方法は、半
導体特性を有する粒状のシリコンと、粒状の金属シリコ
ンとを含む組成物を焼成することにより得ることができ
る。本発明においては、上述したように、２種類のシリ
コンを含む組成物を焼成することにより得ることができ
るが、上述したように製造コスト、性能といった点から
さらに組成範囲および種々の添加剤を加えて焼成を行う
ことが好ましい。The method for producing a porous silicon material of the present invention can be obtained by firing a composition containing granular silicon having semiconductor characteristics and granular metallic silicon. In the present invention, as described above, it can be obtained by firing a composition containing two kinds of silicon. However, as described above, the composition range and various additives are further added from the viewpoint of production cost and performance. It is preferable to perform firing by firing.
【００２４】本発明のケイ素質多孔体の製造方法を詳細
に説明すると、まず、半導体特性を有する粒状のシリコ
ン５〜６０質量％と、粒状の金属シリコン４０〜９５質
量％と、トルマリン１〜１０質量％と、酸化チタン１０
〜４０質量％と、銀ゼオライト２〜１５質量％と、銀
０．５〜５質量％と、無水珪酸ナトリウム０．５〜５質
量％とを含む組成物を混練りする工程と、該混練りされ
た組成物を成形して成形体を形成する工程とを含む。こ
のためにはこれまで知られたいかなる粉砕・混合手段で
も用いることができる。ついで、このようにして得られ
た成形体を非酸化性雰囲気中で７００℃〜１４００℃の
温度で焼結させる。この焼結は、電気炉といった装置を
用い、非酸化性雰囲気中で焼成することもできるが、炭
焼きがま中で炭焼き時に焼成することにより、炭素の浸
透または固着工程と、焼成とを同時に行うことができる
ので特に好ましい。The method for producing the porous silicon material of the present invention will be described in detail. First, 5 to 60 mass% of granular silicon having semiconductor characteristics, 40 to 95 mass% of granular metallic silicon, and 1 to 10 of tourmaline. Mass% and titanium oxide 10
To 40% by mass, silver zeolite 2 to 15% by mass, silver 0.5 to 5% by mass, and anhydrous sodium silicate 0.5 to 5% by mass, and a step of kneading the composition. Molding the formed composition to form a molded body. For this purpose, any of the heretofore known grinding / mixing means can be used. Then, the molded body thus obtained is sintered at a temperature of 700 ° C. to 1400 ° C. in a non-oxidizing atmosphere. This sintering can be performed in a non-oxidizing atmosphere by using an apparatus such as an electric furnace, but by firing in a charcoal grill at the time of charcoal firing, the step of infiltrating or fixing carbon and the firing are performed simultaneously. It is particularly preferable because it can
【００２５】ついで、導電性カーボンを本発明のケイ素
質多孔体に含有させる。この浸透工程は、竹炭を製造す
るための炭焼きがまは、良好なグラファイトからなる煤
を発生させる点で特に好ましい。しかしながら、本発明
においては、電気炉中で同様の雰囲気を発生させ、焼成
を行うことができる。Then, conductive carbon is incorporated into the siliceous porous material of the present invention. This infiltration step is particularly preferable in that a charcoal grill for producing bamboo charcoal generates soot made of good graphite. However, in the present invention, firing can be performed by generating the same atmosphere in the electric furnace.
【００２６】本発明においては、非酸化性雰囲気とは、
少なくとも酸素といった酸化性の気体を含まない雰囲気
をいい、例えば、Ａｒ、Ｎ２、ＣＯ２といった気体を主
に含む環境をいう。In the present invention, the non-oxidizing atmosphere means
At least an atmosphere containing no oxidizing gas such as oxygen, for example, an environment mainly containing a gas such as Ar, N 2 or CO 2 .
【００２７】本発明のケイ素質多孔体は、半導体特性を
有するシリコンを含み、汚染物質を吸着するのではな
く、電気化学的に主として分解し、重金属といった成分
については吸着することにより汚染物質を除去するもの
と考えられる。このため、本発明のケイ素質多孔体の特
性が良好で、かつこの特性が長期間にわたって低下する
ことなく、持続するものである。The silicon-containing porous material of the present invention contains silicon having semiconductor characteristics, and does not adsorb pollutants, but mainly decomposes it electrochemically and removes pollutants by adsorbing components such as heavy metals. It is supposed to do. Therefore, the characteristics of the silicon-based porous body of the present invention are good, and the characteristics are maintained for a long period of time without deterioration.
【００２８】本発明の上述したケイ素質多孔体は、種々
の用途に適用することができ、具体的には例えば、河
川、湖沼、ため池、噴水、工場排水、プール排水、赤
潮、閉鎖海域浄化、水道水浄化、有機塩素化合物などに
より汚染された地下水の浄化、上水浄化、糞尿処理水の
浄化、下水浄化、貯蔵飲料水浄化といった各種水質浄化
に適用することができる。また、本発明のケイ素質多孔
体は、一般海水淡水化、深層水浄化、といった海水浄化
に適用することができる。さらに、本発明のケイ素質多
孔体は、道路沿線、トンネルにおける大気浄化、自動車
エンジンからの排気ガスの浄化、室内、ホール、工場、
病院といった施設における空気浄化、低濃度・高濃度ポ
リ塩化ビフェニール（ＰＣＢ）、ＶＯＣ、ダイオキシ
ン、重金属といった有機物の分解および重金属の吸着、
結露防止、鋼材防錆、鋼材貝殻付着防止、除湿除菌寝
具、底質浄化といった種々の用途に適用することができ
る。The above-mentioned silicon-based porous material of the present invention can be applied to various uses. Specifically, for example, rivers, lakes, reservoirs, fountains, factory drainage, pool drainage, red tide, closed sea area purification, It can be applied to various water quality purifications such as tap water purification, ground water contaminated with organic chlorine compounds, clean water purification, manure treatment water purification, sewage purification, stored drinking water purification. Further, the siliceous porous body of the present invention can be applied to seawater purification such as desalination of general seawater and purification of deep water. Further, the silicon-based porous body of the present invention is used for purifying air along roads, in tunnels, for purifying exhaust gas from automobile engines, indoors, halls, factories,
Air purification in facilities such as hospitals, decomposition of low- and high-concentration polychlorinated biphenyls (PCB), VOCs, dioxins, heavy metals, and adsorption of heavy metals,
It can be applied to various applications such as dew condensation prevention, steel rust prevention, steel shell adhesion prevention, dehumidification and disinfection bedding, and bottom purification.
【００２９】また、本発明のケイ素質多孔体を、クラッ
シャといった適切な粉砕手段により粉砕することにより
得られるケイ素質粉末についても、上述した汚染物質な
どの分解・吸着といった作用を有しており、上述したケ
イ素質多孔体と同様の用途に適用することが可能であ
る。The silicon-based powder obtained by crushing the silicon-based porous material of the present invention by an appropriate crushing means such as a crusher also has an action of decomposing / adsorbing the above-mentioned contaminants, It is possible to apply to the same use as the above-mentioned silicon porous body.
【００３０】以下、本発明を実施例をもって詳細に説明
するが、本発明は下記実施例に限定されるものではな
い。Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.
【００３１】[0031]
【実施例】Ａ ケイ素質多孔体の製造
本発明のケイ素質多孔体を下記のようにして製造した。
以下、％は、特に断らない限り、ケイ素質多孔体の質量
に対する質量％である
＜組 成＞
上述した組成物において、半導体性を有するシリコンお
よび金属シリコンは、粒状として添加した。半導体性を
有するシリコンの粒度は、金属シリコンの粒度よりも小
さくなるようにした。Example A Production of Silicon Porous Body The silicon porous body of the present invention was produced as follows.
Hereinafter,% is% by mass with respect to the mass of the porous silicon material unless otherwise specified. <Composition> In the above-mentioned composition, the semiconducting silicon and metallic silicon were added in the form of particles. The grain size of semiconducting silicon was set smaller than that of metallic silicon.
【００３２】上述の組成物に水を加えて良く混合し、型
枠を用いて成形し、充分乾かした後、竹（孟宗竹）の炭
を製造するための炭焼きがまに配置し、竹を炭にするた
めの熱および非酸化性雰囲気を用いて８日間焼成した。
焼成温度は、約８５０℃であった。Water is added to the above composition, mixed well, molded using a mold, sufficiently dried, and then placed on a charcoal grill for producing charcoal of bamboo (Moso bamboo). Bake for 8 days using heat and a non-oxidizing atmosphere.
The firing temperature was about 850 ° C.
【００３３】この焼成の間、竹の燃焼により生じた導電
性カーボンが浸透または固着して、約５％の質量増加が
見られた。燻煙焼処理が終了し、冷却された後、黒色の
本発明のケイ素質多孔体が得られた。During this firing, the conductive carbon generated by the burning of bamboo was permeated or fixed and a mass increase of about 5% was observed. After the smoky baking treatment was completed and after cooling, a black siliceous porous body of the present invention was obtained.
【００３４】＜体積抵抗率＞
上述のように製造した本発明のケイ素質多孔体の体積抵
抗率を図１に示す装置を用いて４端子法により測定し
た。電流計としては、アドバンテスト株式会社製ＴＲ８
６５２を用い、電圧計としては、アドバンテスト株式会
社製Ｒ６３４１Ｆを用いた。また、直流電源としては、
株式会社高砂製作所製ＧＰ１６０−５Ｒを用いた。<Volume Resistivity> The volume resistivity of the porous silicon material of the present invention produced as described above was measured by the 4-terminal method using the apparatus shown in FIG. As an ammeter, TR8 manufactured by Advantest Corporation
652 was used, and as a voltmeter, R6341F manufactured by Advantest Corporation was used. Also, as a DC power supply,
A Takasago Seisakusho GP160-5R was used.
【００３５】本発明のケイ素質多孔体を縦８．６５ｍ
ｍ、横１５．５ｍｍの棒に形成し、この棒の長手方向の
両端部にエナメル線を銀ペーストにより接着して電流計
および直流電源を接続した。電圧計の測定端子を棒の長
手方向の中央部において１０．９ｍｍの間隔で接触さ
せ、電流を流して体積抵抗率の測定を行った。室温２６
℃、相対湿度（ＲＨ）５５％において、電流計に０．１
Ａの電流が流れたときの電圧は、１１．８Ｖであった。
この結果、体積抵抗率は、１．４５Ωｍであった。体積
抵抗率の算出には、下記式を用いた。The siliceous porous material of the present invention is 8.65 m in length.
The bar was formed into a rod having a length of m and a width of 15.5 mm, and an enameled wire was adhered to both ends in the longitudinal direction of the rod with silver paste to connect an ammeter and a DC power source. The measurement terminal of the voltmeter was brought into contact with the center of the rod in the longitudinal direction at an interval of 10.9 mm, and a current was passed to measure the volume resistivity. Room temperature 26
0.1 ° C at 55 ° C and 55% relative humidity (RH)
The voltage when the current of A flowed was 11.8V.
As a result, the volume resistivity was 1.45 Ωm. The following formula was used to calculate the volume resistivity.
【００３６】[0036]
【数１】
（上式中、Ｖは、電圧であり、Ｉは、電流値であり、Ｓ
は、断面積（ａ×ｂ）であり、ｌは、電圧計の端子間距
離ｃである。）[Equation 1] (In the above formula, V is a voltage, I is a current value, S
Is the cross-sectional area (a × b), and l is the terminal distance c of the voltmeter. )
【００３７】Ｂ 汚染物質除去特性
上述のようにして製造した本発明のケイ素質多孔体に、
東京都江東区横十間川親水公園あひるの池から採取した
原水を循環させてその汚染度の改善について試験した。
試験項目としたデータは、ｐＨ（ＪＩＳ Ｋ ０１０２
１２．１、ガラス電極法）、ＣＯＤＭｎ（ＪＩＳ Ｋ
０１０２ １７．、滴定法）、ＢＯＤ（ＪＩＳ Ｋ
０１０２ ２１．および３２．１ ウインクラアジ化ナ
トリウム変法）、ＳＳ（昭和４６年環境庁報告第５９号
付表６、ろ過質量法）、濁度（上水試験方法 ＶＩ−１
３．３．１）、クロロフィルａ（上水試験方法 ＶＩ
−４ ２０．２ アセチルアセトンによる吸光光度法）
である。表１にその結果を示す。B Pollutant Removal Property The silicon-based porous body of the present invention produced as described above,
The raw water sampled from Ahiru-no-ike, Yokojukkengawa Water Park, Koto-ku, Tokyo was circulated to test the improvement of pollution degree.
The data used as test items are pH (JIS K 0102
12.1, glass electrode method), COD Mn (JIS K
0102 17. , Titration method), BOD (JIS K
0102 21. And 32.1 Wincla sodium azide modified method), SS (Environmental Agency report No. 59 Appendix Table 6, filtration mass method), turbidity (clean water test method VI-1)
3.3.1), chlorophyll a (clean water test method VI
-4 20.2 absorptiometry by acetylacetone)
Is. The results are shown in Table 1.
【００３８】[0038]
【表１】 [Table 1]
【００３９】表１に示されるように、本発明のケイ素質
多孔体は、汚染された水を循環させることにより、著し
く水質を改善することができることが確認された。As shown in Table 1, it was confirmed that the siliceous porous material of the present invention can remarkably improve the water quality by circulating the contaminated water.
【００４０】[0040]
【発明の効果】これまで説明したように、本発明によれ
ば、従来の濾過材、フィルターとして用いられている多
孔体の汚染物質除去能力を向上させ、さらにこの汚染物
質除去能力を長期間にわたって維持することが可能なケ
イ素質多孔体、ケイ素質多孔体の製造方法、ケイ素質粉
末およびその製造方法を提供することが可能となる。As described above, according to the present invention, it is possible to improve the pollutant removal ability of the conventional filter media and porous bodies used as filters, and to further improve this pollutant removal ability for a long period of time. It is possible to provide a silicon-based porous body that can be maintained, a method for producing a silicon-based porous body, a silicon-based powder, and a method for producing the same.
【図１】本発明における体積抵抗率測定装置を示した
図。FIG. 1 is a diagram showing a volume resistivity measuring device according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平11−104422（ＪＰ，Ａ) 特開2001−205024（ＪＰ，Ａ) 特開 平11−179117（ＪＰ，Ａ) 特開 平９−192425（ＪＰ，Ａ) 特開 平11−323475（ＪＰ，Ａ) 特開 平８−217568（ＪＰ，Ａ) 特開 昭59−145087（ＪＰ，Ａ) 特開 平11−509（ＪＰ，Ａ) 特開 平10−287937（ＪＰ，Ａ) 特開 平９−268085（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 20/00 - 20/34 B01D 39/00 - 39/20 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-11-104422 (JP, A) JP-A-2001-205024 (JP, A) JP-A-11-179117 (JP, A) JP-A-9-192425 (JP, A) JP 11-323475 (JP, A) JP 8-217568 (JP, A) JP 59-145087 (JP, A) JP 11-509 (JP, A) Kaihei 10-287937 (JP, A) JP-A-9-268085 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B01J 20/00-20/34 B01D 39/00- 39/20
Claims (11)
と、前記粒状高純度シリコンよりも粒度の粗い金属シリ
コンとを質量比で１：２〜１：５で含有し、さらに導電
性カーボンと、トルマリン１〜１０質量％と、酸化チタ
ン１０〜４０質量％と、無水珪酸ナトリウム０．５〜５
質量％とを含有し、体積抵抗率が０．１Ωｍ〜５００Ω
ｍであるケイ素質多孔体。1. PN-doped granular high-purity silicon
And a metal particle that is coarser than the granular high-purity silicon.
Containing 1 to 2 to 1: 5 by mass ratio, and further conductive
Carbon, tourmaline 1-10% by mass, titanium oxide
10 to 40 mass% and anhydrous sodium silicate 0.5 to 5
%, And has a volume resistivity of 0.1 Ωm to 500 Ω.
m is a silicon-based porous body.
銀０．５〜５質量％とを含有することを特徴とする、請
求項１に記載のケイ素質多孔体。2. Further, 2 to 15 mass% of silver zeolite,
The siliceous porous body according to claim 1 , which contains 0.5 to 5% by mass of silver .
る、請求項１または２に記載のケイ素質多孔体。3. The silicon-based porous body according to claim 1 , which has a volume resistivity of 0.1 Ωm to 20 Ωm.
ラファイトである、請求項１に記載のケイ素質多孔体。4. The siliceous porous body according to claim 1 , wherein the conductive carbon is graphite obtained from bamboo charcoal.
と、前記粒状高純度シリコンよりも粒度の粗い金属シリ
コンとを質量比で１：２〜１：５とし、さらにトルマリ
ン１〜１０質量％と、酸化チタン１０〜４０質量％と、
無水珪酸ナトリウム０．５〜５質量％とを含む組成物を
混練りする工程と、 該混練りされた組成物を成形して成形体を形成する工程
と、 該成形体を非酸化性雰囲気中で７００℃〜１４００℃の
温度で焼結させる工程と、前記成形体に対して 導電性カーボンを含有させる工程
と、を含むケイ素質多孔体の製造方法。5. PN-doped granular high-purity silicon
And metal silicon having a particle size coarser than that of the granular high-purity silicon in a mass ratio of 1: 2 to 1: 5,
1 to 10% by mass, titanium oxide 10 to 40% by mass,
A step of kneading a composition containing 0.5 to 5% by mass of anhydrous sodium silicate, a step of molding the kneaded composition to form a molded body, and the molded body in a non-oxidizing atmosphere And a step of sintering the molded body at a temperature of 700 ° C. to 1400 ° C. and a step of incorporating conductive carbon into the molded body .
１５質量％と、銀０．５〜５質量％とを含む請求項５に
記載のケイ素質多孔体の製造方法。6. The composition further comprises 2 to 3 of silver zeolite.
The method for producing a siliceous porous body according to claim 5, comprising 15% by mass and 0.5 to 5% by mass of silver .
るグラファイトである、請求項５または６に記載のケイ
素質多孔体の製造方法。7. The method for producing a siliceous porous body according to claim 5 , wherein the conductive carbon is graphite obtained from bamboo charcoal.
化炭素を含む、請求項５〜７のいずれか１項に記載のケ
イ素質多孔体の製造方法。8. The method for producing a silicon-based porous body according to claim 5 , wherein the non-oxidizing atmosphere contains at least carbon dioxide.
と、前記粒状高純度シリコンよりも粒度の粗い金属シリ
コンとを質量比で１：２〜１：５で含有し、さらに導電
性カーボンと、トルマリン１〜１０質量％と、酸化チタ
ン１０〜４０質量％と、無水珪酸ナトリウム０．５〜５
質量％とを含有し体積抵抗率が０．１Ωｍ〜５００Ωｍ
であるケイ素質焼成多孔体を粉砕することにより得られ
るケイ素質粉末。9. PN-doped granular high-purity silicon
And metal silicon having a particle size coarser than that of the granular high-purity silicon in a mass ratio of 1: 2 to 1: 5, and further containing conductive
Carbon, tourmaline 1-10% by mass, titanium oxide
10 to 40 mass% and anhydrous sodium silicate 0.5 to 5
%, And has a volume resistivity of 0.1 Ωm to 500 Ωm
The silicon-based powder obtained by crushing the silicon-based fired porous body as described above.
と、銀０．５〜５質量％とを含有することを特徴とす
る、請求項９に記載のケイ素質粉末。10. Further, 2 to 15% by mass of silver zeolite
And 0.5 to 5% by mass of silver, The siliceous powder according to claim 9, characterized in that
と、前記粒状高純度シリコンよりも粒度の粗い金属シリ
コンとを質量比で１：２〜１：５で含有し、さらにトル
マリン１〜１０質量％と、酸化チタン１０〜４０質量％
と、無水珪酸ナトリウム０．５〜５質量％とを含む組成
物を混練りする工程と、 該混練りされた組成物を成形して成形体を形成する工程
と、 該成形体を非酸化性雰囲気中で７００℃〜１４００℃の
温度で焼結させてケイ素質多孔体を形成する工程と、 該ケイ素質多孔体に導電性カーボンを含有させる工程
と、 前記導電性カーボンを含有した前記ケイ素質多孔体を粉
砕する工程と、を含むケイ素質粉末の製造方法。11. PN-doped granular high-purity silicon
And metallic silicon having a grain size coarser than that of the granular high-purity silicon in a mass ratio of 1: 2 to 1: 5.
1-10% by weight of marine and 10-40% by weight of titanium oxide
And a step of kneading a composition containing 0.5 to 5% by mass of anhydrous sodium silicate, a step of molding the kneaded composition to form a molded body, and a non-oxidizing property of the molded body. A step of sintering at a temperature of 700 ° C. to 1400 ° C. in an atmosphere to form a porous silicon material, a step of containing conductive carbon in the porous silicon material, and the silicon material containing conductive carbon And a step of pulverizing the porous body, the method for producing a silicon powder.
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| US7564027B2 (en) * | 2003-02-10 | 2009-07-21 | Waters Investments Limited | Adsorption, detection and identification of components of ambient air with desorption/ionization on silicon mass spectrometry (DIOS-MS) |
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