JPH10337469A - Adsorptive porous sintered compact and its production - Google Patents
Adsorptive porous sintered compact and its productionInfo
- Publication number
- JPH10337469A JPH10337469A JP9165417A JP16541797A JPH10337469A JP H10337469 A JPH10337469 A JP H10337469A JP 9165417 A JP9165417 A JP 9165417A JP 16541797 A JP16541797 A JP 16541797A JP H10337469 A JPH10337469 A JP H10337469A
- Authority
- JP
- Japan
- Prior art keywords
- adsorptive
- muscovite
- activated carbon
- sintered body
- synthetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は汚染物質の吸着除去
を図る多孔質焼結体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous sintered body for removing contaminants by adsorption.
【０００２】[0002]
【従来の技術】空気の浄化や廃水処理等から流体を大量
に浄化処理することが望まれ、従来から活性炭が有効に
利用されている。しかしながら、活性炭の形態は細かい
粉末か又は顆粒なのでカラムに充填した場合、流体の透
過抵抗が高く、効率的な処理が難しかった。また、特性
の面でも、活性炭は湿性ミスト類や水溶性脂肪酸等のよ
うな大きな粒子サイズのものに対して早期に破過する傾
向がある。さらに、流体中に細菌やバクテリアがある場
合、吸着して温存するのでかえって繁殖の場となる問題
点があった。2. Description of the Related Art It is desired to purify a large amount of fluid from air purification and wastewater treatment, and activated carbon has been effectively used. However, since activated carbon is in the form of fine powder or granules, when packed in a column, it has a high fluid permeation resistance and is difficult to treat efficiently. In terms of properties, activated carbon also tends to break through earlier than large particles such as wet mist and water-soluble fatty acids. In addition, when bacteria and bacteria are present in the fluid, they are adsorbed and preserved.
【０００３】こうした活性炭の問題点に対し、まず流体
の透過性の改善については、活性炭を流体透過性の良好
な成形体に造形し、また大きな粒子サイズのものの吸着
の改善には他の吸着材との併用で、さらに細菌類の繁殖
の防止には、抗菌材の添加が試みられている。[0003] In order to improve the fluid permeability, activated carbon is formed into a molded product having good fluid permeability, and other adsorbents are used to improve the adsorption of particles having a large particle size. In addition, antimicrobial materials have been added to prevent the propagation of bacteria.
【０００４】このような改善策のうち、成形体の製造に
ついては、高分子材料を結合材とする方法があるが、樹
脂分が活性炭に含浸して気孔を封じたり、或いは成形体
の気孔率を小さくするので好ましくない。そこで無機質
の粉末を結合材として焼結する方法が採られている。し
かしながら、現状の焼結法は、ガラス粒子や窯業鉱物を
用いていわゆる素焼き状態で活性炭及び添加物を焼結す
るので８００゜Ｃ以上の加熱を必要としている。Among such remedies, there is a method of producing a molded article by using a polymer material as a binder. However, the resin impregnates the activated carbon to seal the pores, or to reduce the porosity of the molded article. Is not preferred because Therefore, a method of sintering using an inorganic powder as a binder has been adopted. However, the current sintering method requires heating at 800 ° C. or more because activated carbon and additives are sintered in a so-called unfired state using glass particles and ceramic minerals.
【０００５】また、この方法は高温でのガラス融着に依
存してするため焼結体の気孔率が小さくなり、また焼結
体に添加した抗菌性付与材、例えば、銀、銅、亜鉛等の
イオン担持物質が６００゜Ｃ以上で焼き付け還元によっ
てイオン化機能を失うことから抗菌作用が期待できなく
なるのである。In addition, this method depends on glass fusion at a high temperature, so that the porosity of the sintered body is reduced, and an antibacterial material added to the sintered body, for example, silver, copper, zinc, etc. Since the ion-bearing substance loses its ionizing function by baking reduction at 600 ° C. or higher, antibacterial action cannot be expected.
【０００６】さらに近年、各種の微生物を粒状活性炭の
気孔に固定した生物活性炭が用いられて、アンモニヤ性
窒素や有機物を吸着生分解除去するものがある。しかし
ながら、前記同様生物活性炭も形態が細粒であるため流
体の透過性が小さく、またその重量により水中で沈積し
て接触面積が小さくなることから充分な効果が得られな
いのである。[0006] In recent years, there has been known a type of bioactive carbon in which various microorganisms are fixed in pores of granular activated carbon to remove and biodegrade ammonia nitrogen and organic substances by adsorption. However, similarly to the above, the biological activated carbon is also in the form of fine granules, so that the fluid permeability is small, and because of its weight, it is deposited in water and the contact area becomes small, so that a sufficient effect cannot be obtained.
【０００７】[0007]
【発明が解決しようとする課題】そこで本発明は、低温
度の焼結マトリックスにより、活性炭、他の吸着材や抗
菌剤等を、夫々の機能を保持した状態で焼結し、気孔率
が大きく、多様な形状で流体透過性の良好な焼結体及び
その製造方法を提供するものである。また、生物活性炭
では水中での浮揚力を付与できて充分な接触面積を確保
でき、吸着生分解除去を効果的にできる焼結体及びその
製造方法を提供するものである。SUMMARY OF THE INVENTION Accordingly, the present invention provides a low-temperature sintering matrix in which activated carbon, other adsorbents, antibacterial agents and the like are sintered while maintaining their respective functions, resulting in a large porosity. Another object of the present invention is to provide a sintered body having various shapes and good fluid permeability, and a method for manufacturing the same. Another object of the present invention is to provide a sintered body capable of imparting buoyancy in water, securing a sufficient contact area, and effectively removing biodegradation by adsorption, and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段】このため本発明の吸着性
多孔質焼結体は、活性炭及び／又は吸着性珪酸塩と、合
成白雲母質物とを含んで成るものである。なお、抗菌剤
や中空質無機物をふくんでもよい。また吸着性珪酸塩
は、カオリナイト、モンモリロナイト、酸性白土、珪藻
土、セピオライト、ゼオライトの少なくとも１種であれ
ばよく、合成白雲母質物は、フッ素マスコバイト又はそ
の原料配合物、或いはフッ素バラゴナイト又はその原料
配合物の少なくとも１種であればよい。さらに、抗菌剤
は、銀、銅又は亜鉛のいずれかを担持したゼオライト、
モンモリロナイト、膨潤性雲母、リン酸カルシウムの少
なくとも１種であればよく、中空質無機物は、シラスバ
ルーン、シリカバルーン、ガラスバルーンの少なくとも
１種であるればよい。Accordingly, the adsorptive porous sintered body of the present invention comprises activated carbon and / or an adsorptive silicate and a synthetic muscovite. Note that an antibacterial agent or a hollow inorganic substance may be included. The adsorptive silicate may be at least one of kaolinite, montmorillonite, acid clay, diatomaceous earth, sepiolite, and zeolite, and synthetic muscovite is a mixture of fluorine muscovite or its raw material, or fluorine balagonite or its raw material It may be at least one of the blends. Further, the antimicrobial agent is a zeolite carrying either silver, copper or zinc,
At least one of montmorillonite, swellable mica, and calcium phosphate may be used, and the hollow inorganic substance may be at least one of shirasu balloon, silica balloon, and glass balloon.
【０００９】また本発明の吸着性多孔質焼結体の製造方
法は、活性炭及び／又は吸着性珪酸塩と、中空質無機物
と、合成白雲母とを含んで成る成形体を、５００〜６５
０゜Ｃで焼成して焼結する方法である。なお、活性炭を
含んだ成形体の外周に、吸着性珪酸塩と合成白雲母質よ
り成る層を形成し、５００〜６５０゜Ｃで焼結すること
で積層体の吸着性多孔質焼結体としてもよい。Further, the method for producing an adsorptive porous sintered body of the present invention is characterized in that a molded article containing activated carbon and / or an adsorptive silicate, a hollow inorganic substance, and synthetic muscovite is provided in a range of 500 to 65.
This is a method of firing at 0 ° C and sintering. In addition, a layer made of adsorbent silicate and synthetic muscovite is formed on the outer periphery of the molded body containing activated carbon, and sintered at 500 to 650 ° C. to form an adsorbent porous sintered body of the laminate. Is also good.
【００１０】ここで活性炭及び／又は吸着性珪酸塩を用
いるのは、それらが汚染物質や不純物の吸着除去に優れ
るためであり、セラミック基体となるものである。この
場合、活性炭単体、吸着性珪酸塩単体、及び活性炭と吸
着性珪酸塩との複合の３形態が実用できるのである。The reason for using activated carbon and / or adsorptive silicate here is that they are excellent in adsorbing and removing contaminants and impurities, and serve as a ceramic substrate. In this case, three forms of activated carbon alone, adsorptive silicate alone, and composite of activated carbon and adsorptive silicate can be used.
【００１１】活性炭は、４００゜Ｃ以上の酸化焼成で酸
化消耗が始まり、また還元焼成でも８００゜Ｃ以上で吸
着特性が劣化する。したがって、吸着性珪酸塩は活性炭
の性能を補完し、焼結マトリックスに参加しうる吸着材
として用いてもよく、活性炭と吸着性珪酸塩との複合使
用が最適である。Activated carbon starts oxidatively depleted when oxidized and fired at 400 ° C. or more, and its adsorption characteristics deteriorate at 800 ° C. or more even when reduced and fired. Therefore, the adsorptive silicate complements the performance of activated carbon and may be used as an adsorbent that can participate in the sintering matrix, and the combined use of activated carbon and adsorptive silicate is optimal.
【００１２】吸着性珪酸塩としては、カオリナイト、モ
ンモリロナイト、酸性白土、珪藻土、セピオライト、ゼ
オライトの少なくとも１種を用いればよい。このうちカ
オリナイト、モンモリロナイト、酸性白土等の層状珪酸
塩は６００゜Ｃ付近より、結晶水を放出し、６５０゜Ｃ
以上で結晶崩壊が始まる。また、セピオライトは、５５
０゜Ｃ以上で結晶水を放出し始め６００゜Ｃ以上ではメ
タセピオライトになって細孔組織を失い、ステアタイト
に転移する。珪藻土は、６５０゜Ｃ以上で気孔率が著し
く低下する。As the adsorptive silicate, at least one of kaolinite, montmorillonite, acid clay, diatomaceous earth, sepiolite and zeolite may be used. Among them, layered silicates such as kaolinite, montmorillonite, and acid clay release water of crystallization from around 600 ° C and 650 ° C.
Thus, the crystal collapse starts. Sepiolite is 55
At 0 ° C. or higher, water of crystallization starts to be released, and at 600 ° C. or higher, it becomes metasepiolite, loses its pore structure, and is transformed into steatite. Diatomaceous earth has a significantly reduced porosity above 650 ° C.
【００１３】合成白雲母質物としては、フッ素マスコバ
イト又はその原料配合物、或いはフッ素バラゴナイト又
はその原料配合物の少なくとも１種を用いればよい。合
成白雲母には、フッ素マスコバイト［ＫＡｌ2（ＡｌＳ
ｉ3Ｏ10）Ｆ2］とフッ素パラゴナイト［ＮａＡｌ2(AlSi
3O10)F2］の２種類がある。また、その組成に見合う原
料配合、例えば、カオリナイト［Al２Si２Ｏ５］、γ−
アルミナ、パイロフィライト［Al2Si4O10(OH)2］等と、
ケイフッ化カリウム（K2SiF6）、ケイフッ化ナトリウム
（Na2SiF6）、氷晶石（Na3AlF6）等のようなフッ化物を
用いて原料配合を行い加圧成型して加熱焼成する。その
焼成は５５０〜７２０゜Ｃで行われ、固相反応により５
００゜Ｃ付近より白雲母が析出し、同時に焼結が進行し
セラミック体となる。さらに、多数の鱗片が重なった状
態となることからその積層部に間隙が生じるため気孔と
なってセラミック体が多孔質となるのである。As the synthetic muscovite, at least one of fluorine muscovite or a raw material blend thereof, or fluorine balagonite or a raw material blend thereof may be used. Fluorine muscovite [KAl 2 (AlS
i 3 O 10 ) F 2 ] and fluorinated paragonite [NaAl 2 (AlSi
3 O 10 ) F 2 ]. In addition, a raw material composition suitable for the composition, for example, kaolinite [Al2Si2O5], γ-
Alumina, pyrophyllite [Al 2 Si 4 O 10 (OH) 2 ], etc.
The raw materials are blended using fluorides such as potassium silicofluoride (K 2 SiF 6 ), sodium silicofluoride (Na 2 SiF 6 ), cryolite (Na 3 AlF 6 ), press-molded and heated and fired. . The calcination is carried out at 550-720 ° C.
At around 00 ° C., muscovite is precipitated, and at the same time, sintering proceeds to form a ceramic body. Further, since a large number of scales are superimposed on each other, a gap is generated in the laminated portion, so that pores are formed and the ceramic body becomes porous.
【００１４】合成白雲母は天然白雲母［KAI2(AlSi3O10)
F2］と同一の結晶構造であり、(OH)基をＦで置換したも
のである。(OH)基を持つ白雲母は、６００゜Ｃ付近より
結晶水(OH)2を放出して分散するのに対して、Ｆ基を持
つ白雲母は５００゜Ｃ付近より微量のフッ化物揮発によ
る焼結作用により焼結する特徴を有する。Synthetic muscovite is natural muscovite [KAI 2 (AlSi 3 O 10 )
F 2 ], and the (OH) group is substituted with F. While muscovite having an (OH) group releases and disperses crystal water (OH) 2 from around 600 ° C, muscovite having an F group is due to volatilization of a small amount of fluoride from around 500 ° C. It has the characteristic of sintering by the sintering action.
【００１５】抗菌剤としては、銀、銅又は亜鉛のいずれ
かを担持したゼオライト、モンモリロナイト、膨潤性雲
母、リン酸カルシウムの少なくとも１種を用いればよ
く、これらは良好な抗菌作用を果たすものである。な
お、ゼオライト、モンモリロナイト、膨潤性雲母、リン
酸カルシウムを用いるのは、夫々組成上金属イオンを化
学的に担持する機能をもっているからである。しかしな
がら、約６００゜Ｃ以上ではそれらのイオンが担体と焼
結して金属化し抗菌作用を喪失するのである。このため
低温焼結が必要となる。As the antibacterial agent, at least one of zeolite, montmorillonite, swellable mica, and calcium phosphate carrying any one of silver, copper and zinc may be used, and these exhibit a good antibacterial action. The reason for using zeolite, montmorillonite, swelling mica, and calcium phosphate is that each has a function of chemically supporting metal ions in composition. However, above about 600 ° C., those ions sinter and metallize with the carrier and lose their antimicrobial action. For this reason, low-temperature sintering is required.
【００１６】中空質無機物としては、シラスバルーン、
シリカバルーン、ガラスバルーンの少なくとも１種を用
いればよい。これらの微粉末を５〜２０重量部添加する
ことで水中での浮揚力を付与できるのである。これらの
バルーン材料は中空膜の破壊が５５０゜Ｃ以上で始まる
ので低温焼結が必要であり、合成白雲母質マトリックス
による焼結体により達成される。As the hollow inorganic substance, a shirasu balloon,
At least one of a silica balloon and a glass balloon may be used. By adding 5 to 20 parts by weight of these fine powders, buoyancy in water can be imparted. These balloon materials require low temperature sintering since the breakdown of the hollow membrane begins above 550 ° C. and are achieved by sintering with a synthetic muscovite matrix.
【００１７】したがって、活性炭及び／又は吸着性珪酸
塩と、合成白雲母と、必要により添加した中空質無機
物、抗菌剤とを含んで成る成形体を、低温の５００〜６
５０゜Ｃで焼成することにより、活性炭や吸着性珪酸塩
の吸着特性を保持できると共に、気孔率を大きくでき、
抗菌剤による抗菌作用及び中空質無機物による水中浮揚
作用を保持できる吸着性多孔質焼結体が得られるのであ
る。Therefore, a molded article containing activated carbon and / or an adsorbent silicate, synthetic muscovite, and optionally added hollow inorganic substance and antibacterial agent is prepared at a low temperature of 500 to 6%.
By calcination at 50 ° C., it is possible to maintain the adsorption characteristics of activated carbon and adsorptive silicate and to increase the porosity,
Thus, an adsorptive porous sintered body that can maintain the antibacterial action of the antibacterial agent and the floating action in water of the hollow inorganic substance can be obtained.
【００１８】[0018]
【発明の実施の形態】活性炭と合成白雲母質物との焼結
体の配合は、活性炭を６０〜７５重量％、合成白雲母質
粉末（フッ素マスコバイト又はフッ素パラゴナイト、或
いはこれらの原料配合物、２２０メッシュ下）を２５〜
４０重量％、必要に応じて抗菌剤の銀等の金属イオンを
担持したモンモリロナイト等を１〜３重量％がよい。ま
た、水中浮揚性を付与する場合には、シラスバルーンや
シリカバルーン等の中空質無機物粉末の少なくとも１種
を１０〜２０重量％配合してもよい。BEST MODE FOR CARRYING OUT THE INVENTION A sintered body of activated carbon and synthetic muscovite is compounded by adding 60 to 75% by weight of activated carbon, synthetic muscovite powder (fluorine muscovite or fluorine paragonite, or a mixture of these raw materials, 220 mesh below) 25 ~
It is preferably 40% by weight, and if necessary, 1 to 3% by weight of montmorillonite supporting a metal ion such as silver as an antibacterial agent. When imparting water buoyancy, at least one kind of hollow inorganic powder such as a shirasu balloon or a silica balloon may be blended in an amount of 10 to 20% by weight.
【００１９】また、吸着性珪酸塩と合成白雲母質物との
焼結体の配合は、吸着性珪酸塩としてカオリナイト、モ
ンモリロナイト、酸性白土、珪藻土、セピオライト、ゼ
オライトの少なくとも１種又は数種を６０〜８０重量
％、合成白雲母質粉末（フッ素マスコバイト又はフッ素
パラゴナイト、或いはこれらの原料配合物、２２０メッ
シュ下）を２０〜４０重量％、必要に応じて抗菌剤の銀
等の金属イオンを担持したモンモリロナイト等を０〜３
重量％がよい。また、水中浮揚性を付与する場合には、
シラスバルーンやシリカバルーン等の中空質無機物粉末
の少なくとも１種を１０〜２０重量％配合してもよい。The sintered body of the adsorptive silicate and the synthetic muscovite is blended with at least one or several of kaolinite, montmorillonite, acid clay, diatomaceous earth, sepiolite and zeolite as the adsorptive silicate. 20 to 40% by weight of synthetic muscovite powder (fluorine muscovite or fluorine paragonite, or a mixture of these materials, under 220 mesh), and if necessary, metal ions such as silver as an antibacterial agent Montmorillonite etc. from 0 to 3
% By weight is good. Also, when imparting underwater buoyancy,
At least one kind of hollow inorganic powder such as shirasu balloon and silica balloon may be blended in an amount of 10 to 20% by weight.
【００２０】さらに、活性炭及び吸着性珪酸塩と、合成
白雲母質物との焼結体の配合は、活性炭５０〜７０重量
％、吸着性珪酸塩としてカオリナイト、モンモリロナイ
ト、酸性白土、珪藻土、セピオライト、ゼオライトの少
なくとも１種又は数種を２０〜４０重量％、合成白雲母
質粉末（フッ素マスコバイト又はフッ素パラゴナイト、
或いはこれらの原料配合物、２２０メッシュ下）を１０
〜４０重量％、必要に応じて抗菌剤の銀等の金属イオン
を担持したモンモリロナイト等を０〜３重量％がよい。
また、水中浮揚性を付与する場合には、シラスバルーン
やシリカバルーン等の中空質無機物粉末の少なくとも１
種を１０〜２０重量％配合してもよい。Further, the sintered body of the activated carbon and the adsorbent silicate and the synthetic muscovite are blended in an amount of 50 to 70% by weight of the activated carbon and kaolinite, montmorillonite, acid clay, diatomaceous earth, sepiolite as the adsorbent silicate. 20 to 40% by weight of at least one or several zeolites, synthetic muscovite powder (fluorine muscovite or fluorine paragonite,
Alternatively, mix these raw materials, under 220 mesh) with 10
The content is preferably 40 to 40% by weight, and if necessary, 0 to 3% by weight of montmorillonite supporting a metal ion such as silver as an antibacterial agent.
When imparting water buoyancy, at least one hollow inorganic powder such as a shirasu balloon or a silica balloon may be used.
Seeds may be incorporated at 10-20% by weight.
【００２１】なお、水中浮揚性を付与する場合として
は、要するに、前記した活性炭及び／又は吸着性珪酸塩
を４０〜７０重量％、前記した合成白雲母質粉末を１０
〜３０重量％と、シラスバルーンやシリカバルーン等の
中空質無機物粉末の少なくとも１種を１０〜２０重量％
を配合するのがよい。In the case of imparting water buoyancy, the above-mentioned activated carbon and / or adsorptive silicate is used in an amount of 40 to 70% by weight, and the above-mentioned synthetic muscovite powder is used in an amount of 10 to 70% by weight.
And 30% by weight, and at least one kind of hollow inorganic powder such as shirasu balloon and silica balloon is 10 to 20% by weight.
Should be blended.
【００２２】これらの配合物は、ミキサーで均質に混合
した後、水又は有機バインダーを加え混合し、水分１〜
３％の状態で型に充填し、加圧、押し出し、マルメライ
ザー成形等により成型する。この成型体を約１００゜Ｃ
で約１時間乾燥した後、耐火物るつぼ中の炭素微粉に埋
設した状態で加熱炉に装入する。加熱は１時間当たり１
００〜１５０゜Ｃの昇温速度で加熱し、到達温度５００
〜６５０゜Ｃで１〜２時間保持して焼結するのである。These compositions are mixed homogeneously with a mixer, and then water or an organic binder is added and mixed to obtain a water content of 1 to 3.
It is filled in a mold in a state of 3%, and is molded by pressurizing, extruding, and mulling processing. Approximately 100 ° C
After drying for about 1 hour in a refractory crucible, it is charged into a heating furnace while being buried in the carbon fine powder in the refractory crucible. Heating 1 per hour
Heat at a heating rate of 00 to 150 ° C and reach an ultimate temperature of 500
The sintering is carried out at a temperature of ６650 ° C. for 1 to 2 hours.
【００２３】活性炭を含んだ成形体の外周に、吸着性珪
酸塩と合成白雲母質より成る積層を形成して成る吸着性
多孔質焼結体は、皮膜層の配合として、前記したモンモ
リナイト等の吸着性珪酸塩を４０〜７０重量％、結合材
として合成白雲母２０〜４０重量％である。The adsorptive porous sintered body formed by forming a laminate composed of an adsorptive silicate and a synthetic muscovite on the outer periphery of a molded body containing activated carbon is made of a mixture of the above-mentioned montmorillonite and the like as a composition of a coating layer. The adsorptive silicate is 40 to 70% by weight, and the binder is 20 to 40% by weight of synthetic muscovite.
【００２４】内芯とする活性炭の造形体は、本発明によ
る焼結体以外を用いてもよく、また焼成していない成型
体を用いて同時に焼成させてもよい。外周皮膜の加工方
法は、プレス又は押し出し成型機による加工、又はマル
メライザーによる粉末被着や配合物のスラリーのディッ
ピング塗装等の方法が使用できる。The shaped body of activated carbon used as the inner core may be other than the sintered body according to the present invention, or may be simultaneously fired using a non-fired molded body. As the processing method of the outer peripheral coating, a method such as processing by a press or an extrusion molding machine, powder coating by a marmellaizer, and dipping coating of a slurry of a compound can be used.
【００２５】成型機による加工は、積層物の配合物を混
合し、水分約３％以下に調整し、成型用型内で活性炭成
型品を浮かしてセットし、外側部に配合物を押圧挿入す
る方法、或いは活性炭成型品が棒体であれば、同芯的な
押し出し成型により配合物を外装する。また、粉末付着
方式は、球形体に適し、常法のマルメライザードラムに
入れ、若干の加湿下で活性炭成型体を入れることで成型
体の外周に積層する。In the processing by the molding machine, the composition of the laminate is mixed, the water content is adjusted to about 3% or less, the activated carbon molding is floated and set in a molding die, and the composition is pressed and inserted into the outer portion. If the method or the activated carbon molded product is a rod, the compound is packaged by concentric extrusion molding. In addition, the powder adhesion method is suitable for a spherical body, and is placed in a conventional malmerizer drum, and the activated carbon molded body is placed under slight humidification so as to be laminated on the outer periphery of the molded body.
【００２６】さらに、チクソトロピーク法は、積層体配
合物を粘性液に調整し、この中に活性炭成型体を浸漬し
て外周に積層体層を付着させる方法である。粘性液は、
モンモリナイトゾル（固型分３％以下）と有機バインダ
ー（濃度２％以下）を混合して調整する。積層体の厚み
は１〜５mmで適宜設定すればよい。Further, the thixotrope peak method is a method in which a laminate composition is adjusted to a viscous liquid, and an activated carbon molded body is immersed in the mixture to adhere a laminate layer to the outer periphery. The viscous liquid is
It is adjusted by mixing a montmorillonite sol (solid content 3% or less) and an organic binder (concentration 2% or less). The thickness of the laminate may be appropriately set at 1 to 5 mm.
【００２７】外周皮膜を形成した成形体は、緩徐に乾燥
させた後、耐火物容器に入れ不活性雰囲気で加熱する。
加熱は毎時８０〜１５０゜Ｃの昇温速度で行い、５５０
〜６５０゜Ｃで１〜２時間保持して焼結する。得られた
積層部の抗圧力は形状、寸法、組成によって異なるが、
少なくとも１００Kg／cm2以上であり、気孔率は成型加
工品で４０〜４５％、粉末付着品で４０〜５０％、チク
ソトロピック塗装品で４５〜６０％である。なお、外周
積層皮膜の形状は問わず、球体被覆の他、平板上面での
平面被覆等でもよい。The formed body having the outer peripheral film formed thereon is slowly dried, and then placed in a refractory container and heated in an inert atmosphere.
Heating is carried out at a heating rate of 80 to 150 ° C./hour and 550
Hold at ６650 ° C. for 1-2 hours and sinter. The coercive pressure of the obtained laminated part depends on the shape, size and composition,
The porosity is at least 100 kg / cm 2 or more, and the porosity is 40 to 45% for a molded product, 40 to 50% for a powder adhered product, and 45 to 60% for a thixotropic painted product. In addition, regardless of the shape of the outer peripheral laminated film, a planar coating on the upper surface of a flat plate or the like may be used instead of the spherical coating.
【００２８】[0028]
【発明の効果】本発明多孔質焼結体の請求項１による
と、活性炭や吸着性珪酸塩により汚染物質等の吸着除去
性に優れると共に、大きな気孔率を保持できて流体透過
性の良好な焼結体となり、合成白雲母質物を含むことで
低温焼成できて容易に成形できるのである。また請求項
２では、良好な抗菌作用を保持でき、請求項３では、水
中での浮揚性によって良好な吸着除去性が図れ、請求項
４では、ミストの選択吸着及び炭素粉の飛散防止の効果
が大きい。さらに請求項５では、良好な吸着除去性を有
する焼結体が容易に得られ、請求項６では、低温焼成を
調整できて容易に得られ、請求項７では、抗菌剤の保持
が良好に図れ、請求項８では、焼結体への水中浮揚性を
容易に付与できるのである。According to the first aspect of the porous sintered body of the present invention, the activated carbon or the adsorptive silicate is excellent in the ability to remove contaminants and the like, can maintain a large porosity, and has good fluid permeability. It becomes a sintered body and can be easily formed by firing at a low temperature by containing a synthetic muscovite substance. In claim 2, good antibacterial action can be maintained, in claim 3, good adsorption and removal properties can be achieved by buoyancy in water, and in claim 4, the effect of selective adsorption of mist and prevention of scattering of carbon powder. Is big. Further, in claim 5, a sintered body having good adsorption and removal properties can be easily obtained, in claim 6, low-temperature sintering can be adjusted and easily obtained, and in claim 7, the antibacterial agent can be easily retained. According to claim 8, it is possible to easily impart underwater buoyancy to the sintered body.
【００２９】本発明の多孔質焼結体の製造方法の請求項
９よると、汚染物質等の吸着除去性に優れると共に、大
きな気孔率を保持できて流体透過性の良好な焼結体が低
温焼成で得られ、請求項１０では、成形体の外周に汚染
物質等の吸着除去性に優れると共に、大きな気孔率を保
持できて流体透過性の良好な積層部が低温焼成で得られ
るのである。According to the ninth aspect of the method for producing a porous sintered body of the present invention, a sintered body which is excellent in adsorption and removal of contaminants and the like, can maintain a large porosity, and has good fluid permeability can be produced at a low temperature. According to the tenth aspect of the present invention, a laminated portion which is excellent in adsorbing and removing contaminants and the like on the outer periphery of the molded body, can maintain a large porosity, and has good fluid permeability can be obtained by low-temperature firing.
【００３０】[0030]
【実施例１〜６】（実施例１）粉末活性炭６０重量％
と、合成白雲母質物としてフッ素マスコバイト［KAI2(A
lSi3O10)F2］３７重量％と、銀イオン担持の抗菌剤３重
量％とを配合する。なお、フッ素マスコバイトは、カオ
リナイト（粘土学会標準品）を77.7重量％、ケイフッ化
カリウム（K2SiF6）を22.3重量％の配合成形体を６２０
゜Ｃで１０時間焼成して合成した結晶焼結体を粉砕して
得た２００メッシュ粉末を用いた。 （実施例２）粉末活性炭７５重量％と、合成白雲母質物
として前記同様のフッ素マスコバイト［KAI2(AlSi3O10)
F2］２４重量％と、抗菌剤１重量％とを配合する。 （実施例３）粉末活性炭６５重量％と、合成白雲母質物
としてフッ素マスコバイトの合成用原料配合物３２重量
％と、抗菌剤３重量％とを配合する。なお、フッ素マス
コバイトの合成用原料配合物は、カオリナイト77.7重量
％及びケイフッ化カリウム22.3重量％の混合粉末であ
る。 （実施例４）粉末活性炭６０重量％と、合成白雲母質物
としてフッ素パラゴライト［NaAI2(AlSi3O10)F2］３７
重量％と、抗菌剤３重量％とを配合する。なお、フッ素
パラゴライトは、パイロフィライト（粘土学会標準品、
関東化学株式会社製）77.4重量％とケイフッ化カリウム
［Na2SiF6、関東化学株式会社製］22.6重量％の配合成
形体を６４０゜Ｃで１５時間焼成して得られた結晶焼結
体を粉砕した２００メッシュ粉末を用いた。 （実施例５）粉末活性炭６５重量％と、合成白雲母質物
としてフッ素パラゴライトの合成用原料配合物３２重量
％と、抗菌剤３重量％とを配合する。なお、フッ素パラ
ゴライトの合成用原料配合物は、パイロフィライト77.4
重量％とケイフッ化カリウム22.6重量％配合の混合粉末
である。なお、粉末活性炭は、武田薬品工業株式会社
製、製品名ＰＨＣ５を用い、また抗菌剤は、いずれも銀
イオンを担持したゼオライトを用いた。Examples 1 to 6 (Example 1) 60% by weight of powdered activated carbon
And fluorinated muscovite [KAI 2 (A
lSi 3 O 10 ) F 2 ] and 3% by weight of an antibacterial agent carrying silver ions. The fluorinated muscovite was prepared by mixing 620 wt.% Of kaolinite (a standard product of the Clay Society of Japan) and 620 wt.% Of potassium silicofluoride (K 2 SiF 6 ).
A 200-mesh powder obtained by pulverizing a crystal sintered body synthesized by firing at ゜ C for 10 hours was used. (Example 2) 75% by weight of powdered activated carbon and the same fluorinated muscovite as synthetic muscovite [KAI 2 (AlSi 3 O 10 )]
F 2 ] 24% by weight and an antibacterial agent 1% by weight. (Example 3) 65% by weight of powdered activated carbon, 32% by weight of a raw material composition for synthesis of fluorine muscovite as a synthetic muscovite, and 3% by weight of an antibacterial agent are blended. The raw material composition for synthesizing fluorine muscovite is a mixed powder of 77.7% by weight of kaolinite and 22.3% by weight of potassium fluorosilicate. (Example 4) 60% by weight of powdered activated carbon and fluorine paragolite [NaAI 2 (AlSi 3 O 10 ) F 2 ] 37 as synthetic muscovite
% By weight and 3% by weight of the antibacterial agent. In addition, fluorinated paragolite is pyrophyllite (Clay Society of Japan standard,
A crystal sintered body obtained by calcining a molded product of 77.4% by weight of 77.4% by weight and potassium silicofluoride [Na 2 SiF 6 , 22.6% by weight of Kanto Chemical Co., Ltd.] at 640 ° C. for 15 hours is used. A crushed 200 mesh powder was used. (Example 5) 65% by weight of powdered activated carbon, 32% by weight of a raw material composition for synthesizing fluorine paragolite as a synthetic muscovite, and 3% by weight of an antibacterial agent are blended. The raw material composition for synthesis of fluorine paragolite was Pyrophyllite 77.4.
% Powder and 22.6% by weight of potassium silicofluoride. The powdered activated carbon used was PHC5 (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.), and the antibacterial used was zeolite carrying silver ions.
【００３１】各実施例共、配合物を約２時間混合した
後、PVA（１０％水溶液）を配合物に対し固型分換算で
１重量部添加し、30Kg／cm2で紐状（３mmΦ）に押し出
し成型し、これを裁断して３mmΦ×２〜３mmの粒体とし
た。これを夫々各実施例の配合物粉末を入れたドラム式
マルメライザーに装入し、配合物粉末を付着させ肥大化
させて直径８mmΦの球体を成型する。この球体を乾燥器
で乾燥した後、ムライト質るつぼに入れ黒鉛粉末を充填
して空気と遮断した状態で電気炉に入れ加熱する。毎時
１５０゜Ｃの昇温速度で加熱し、実施例２は６００゜
Ｃ、その他の実施例は５５０゜Ｃで２時間保持して焼結
体を得た。夫々焼結体のかさ比重、比表面積、高度を表
１に示す。In each of the examples, after mixing the composition for about 2 hours, 1 part by weight of PVA (10% aqueous solution) was added to the composition in terms of solid content, and a string (30 mmΦ) was formed at 30 kg / cm 2. , And then cut into 3 mmΦ × 2 to 3 mm granules. Each of them is charged into a drum-type marmalizer containing the compound powder of each example, and the compound powder is adhered and enlarged to form a sphere having a diameter of 8 mmΦ. After the spheres are dried in a dryer, they are placed in a mullite crucible, filled with graphite powder, and heated in an electric furnace in a state of being cut off from air. The sintered body was heated at a heating rate of 150 ° C./hour, and kept at 600 ° C. in Example 2 and 550 ° C. in other Examples for 2 hours. Table 1 shows the bulk specific gravity, specific surface area, and altitude of each sintered body.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【実施例６〜１１】実施例１〜５までと同じ活性炭粉
末、フッ素マスコバイト、フッ素マスコバイト合成用組
成物、フッ素パラゴナイト及びフッ素マスコバイト合成
用組成物を用い、他に、カオリナイト（粘土学会標準
品）、モンモリロナイト（國峯鉱業名、山形産）、酸性
白土（山形産、SiO2：60.1重量％、Al2O3：16.7重量
％）、セビオライト（水沢化学工業株式会社製）、珪藻
土（宮城産、SiO2：84重量％、Al2O3：3重量％、２０〜
３０μｍ）、ゼオライト（水沢化学工業株式会社製）、
抗菌剤として銀イオンを担持したゼオライト、シリカ
（１００メッシュ下）、長石（Ｋ−長石、K2O：11.1重
量％、Na2O：3.6重量％、２００メッシュ）、フッ化物
（Na2AlF6）を用いて表２のように配合し、実施例１〜
５までと同様に焼結した。夫々焼結体のかさ比重、比表
面積、高度を表２に示す。Examples 6 to 11 Using the same activated carbon powder, fluorinated muscovite, fluorinated muscovite synthesizing composition, fluorinated paragonite and fluorinated muscovite synthesizing composition as in Examples 1 to 5, other than kaolinite (clay) Montmorillonite (Kunimine mining name, Yamagata product), acid clay (Yamagata product, SiO 2 : 60.1% by weight, Al 2 O 3 : 16.7% by weight), sebiolite (manufactured by Mizusawa Chemical Industry Co., Ltd.), diatomaceous earth (Miyagi produced, SiO 2: 84 wt%, Al 2 O 3: 3 wt%, 20 to
30 μm), zeolite (manufactured by Mizusawa Chemical Industry Co., Ltd.),
Zeolite carrying a silver ion as an antimicrobial agent, silica (100 mesh under), feldspar (K-feldspar, K 2 O: 11.1 wt%, Na 2 O: 3.6 wt%, 200 mesh), fluoride (Na 2 AlF 6 ) And blended as shown in Table 2, and
Sintering was performed in the same manner as before. Table 2 shows the bulk specific gravity, specific surface area, and altitude of each of the sintered bodies.
【００３４】[0034]
【表２】 [Table 2]
【００３５】[0035]
【実施例１２〜１７：別材で外周皮膜した吸着性多孔質
焼結体】外周皮膜を形成する実施例であり、その積層す
る外周皮膜原料の配合を実施例１２〜１７として表３に
示す。夫々原料をボールミルにより２時間混合し、夫々
実施例１〜５と同一の配合及び製造法で製作した径５mm
の球体をドラム式マルメライザーに装入し、実施例１２
〜１７の配合物粉末を霧と共に吹き込みながらドラムを
回転させて球体に付着させ肥大化させて直径９mmの積層
成形体を得る。この球体を乾燥器で乾燥した後、ムライ
ト質るつぼに入れ蓋をして空気を遮断した状態で電気炉
に入れ加熱する。毎時１５０゜Ｃの昇温速度で加熱し、
５８０゜Ｃで２時間保持して積層焼結体を得た。夫々外
周の皮膜層の焼結体のかさ比重、比表面積、高度を表３
に合わせて示す。Examples 12 to 17: Adsorbent porous sintered body having outer peripheral film coated with another material This is an example of forming an outer peripheral film, and the blending of the outer peripheral film material to be laminated is shown in Table 3 as Examples 12 to 17. . Each raw material was mixed by a ball mill for 2 hours, and each was manufactured by the same blending and manufacturing method as in Examples 1 to 5 to a diameter of 5 mm.
Was charged into a drum-type marmalizer, and Example 12
While the compound powder of Nos. 1 to 17 is being blown together with a mist, the drum is rotated to adhere to the sphere and enlarge, thereby obtaining a laminated molded article having a diameter of 9 mm. After the spheres are dried in a drier, they are placed in a mullite crucible and heated in an electric furnace with the lid closed and the air shut off. Heat at a heating rate of 150 ° C per hour,
It was kept at 580 ° C. for 2 hours to obtain a laminated sintered body. Table 3 shows the bulk specific gravity, specific surface area and altitude of the sintered body of the outer coating layer.
Shown along with.
【００３６】[0036]
【表３】 [Table 3]
【００３７】なお、BETによる細孔分布測定及び電子顕
微鏡写真（SEM×10000倍）による観察によれば、実施例
１２、実施例１４及び実施例１６の気孔性において、セ
ピオライト細孔は保たれており、粒子間の二次気孔径は
7000〜10000オングストロームに分布していた。また、
実施例１３及び実施例１５も珪酸塩の構造は保存されて
おり、粒子間気孔径は8000〜12000オングストロームに
分布していた。According to the pore distribution measurement by BET and the observation by an electron micrograph (SEM × 10,000), sepiolite pores were retained in the porosity of Examples 12, 14 and 16. And the secondary pore size between the particles is
It was distributed in the range of 7000 to 10,000 angstroms. Also,
In Examples 13 and 15, the structure of the silicate was also preserved, and the interparticle pore size was distributed at 8000 to 12000 angstroms.
【００３８】[0038]
【実施例１８：水中浮揚性多孔質焼結体】実施例１〜５
までと同じ活性炭粉末６０重量％、フッ素マスコバイト
合成用組成物２５重量％を用い、これにシラスバルーン
（平均粒径５０μｍ）１５重量％を実施例１〜５と同様
に混合、芯材形成、マルメライザー成型し、温度５００
゜Ｃで３時間焼結し、径８mmの球状焼結体を得た。これ
によると、かさ比重0.41、全気孔率６５％、吸水率４８
％で水に浸漬させても沈降しないで水中で浮遊していた
のである。Embodiment 18: Underwater buoyant porous sintered body Examples 1 to 5
Activated carbon powder 60% by weight and a composition for synthesizing fluorine muscovite 25% by weight were used. Molded with marmellaizer, temperature 500
Sintering was performed at 球状 C for 3 hours to obtain a spherical sintered body having a diameter of 8 mm. According to this, bulk specific gravity 0.41, total porosity 65%, water absorption 48
Even if it was immersed in water, it did not settle and floated in water.
【００３９】（実験例）実施例１２及び実施例１５を用
いて臭気成分とミストの混合水溶液により吸着テストを
行った。水１００ml中に、アニリン１ml、ホルマリン
（８０％）１ml、メチルエチルケトン１mlを分散させた
溶液を三角フラスコ（５００ml）に入れた。この液中に
空気導入管を挿入し、液面上空間部から外部に出る流出
管を取り付け、空気導入管から空気を送り入れ、流出管
より各臭気成分の揮発湿性ガス（湿度７０〜７５％）を
放出させた。流出管の途中に実施例１２及び実施例１５
の積層多孔質焼結体（９mm球）を各２０ケ装入したカラ
ムを取り付けて測定すると、両実施例とも流出ガスから
臭気が消失しており、湿度も約実施例１２のもので２０
％、実施例１５のもので２６％以下となっていた。(Experimental Example) Using Examples 12 and 15, an adsorption test was conducted using a mixed aqueous solution of an odor component and a mist. A solution in which 1 ml of aniline, 1 ml of formalin (80%) and 1 ml of methyl ethyl ketone were dispersed in 100 ml of water was placed in an Erlenmeyer flask (500 ml). An air introduction pipe is inserted into this liquid, an outflow pipe that goes out of the space above the liquid surface to the outside is attached, air is sent in from the air introduction pipe, and volatile humid gas (humidity 70 to 75%) of each odor component is passed through the outflow pipe. ) Was released. Example 12 and Example 15 in the middle of the outflow pipe
When the measurement was carried out by attaching a column in which 20 pieces of the laminated porous sintered body (9 mm sphere) were mounted, the odor was eliminated from the effluent gas and the humidity was about 20 in both Examples.
% And 26% or less in Example 15.
【００４０】流出管の途中に実施例１２及び実施例１５
の積層多孔質焼結体（９mm球）を各２０ケ装入したカラ
ムを取り付けて測定すると、両実施例とも流出ガスから
臭気が消失しており、湿度も約実施例１２のもので２０
％、実施例１５のもので２６％以下となっていた。Example 12 and Example 15 in the middle of the outflow pipe
When the measurement was carried out by attaching a column in which 20 pieces of the laminated porous sintered body (9 mm sphere) were mounted, the odor was eliminated from the effluent gas and the humidity was about 20 in both Examples.
% And 26% or less in Example 15.
【００４１】また、カラム内の球体を取り出し、破砕し
て内芯活性端部と外周積層部に分けて測定したところ夫
々外周積層部に湿分を先行吸着すると共に、アニリン、
ホルマリンを一部吸着しており、内芯活性端部ではメチ
ルエトンが吸着されていた。Further, the spheres in the column were taken out, crushed, and measured separately for the inner core active end portion and the outer peripheral laminated portion.
Formalin was partially adsorbed, and methyl ethone was adsorbed at the inner core active end.
【００４２】さらに、実施例４及び実施例１２の外周積
層部を１mm以下に粉砕してガラス皿（径７０mm、深さ１
０mm）に採取し、ガラス皿１個につき大腸菌が１０4〜
１０5個のレベルで菌液を調整して添加した。２５゜Ｃ
で３時間保持し、菌数測定用培地（SCDLP培地）でガラ
ス皿内の含有菌を洗い出して、この洗液を菌数測定培地
による平板培養法（３７゜Ｃ、４８時間）により生残菌
数を測定した。その結果、実施例４では１．２×１０2
以下であり、実施例１２では０．９×１０2以下であっ
た。Further, the outer peripheral laminated portion of Example 4 and Example 12 was crushed to 1 mm or less and crushed into a glass dish (diameter 70 mm, depth 1).
Were taken to 0mm), E. coli per one glass dish 10 4 ~
The bacterial solution was adjusted and added at 10 5 levels. 25 ゜ C
For 3 hours, and the bacteria contained in the glass dish are washed out with a culture medium for cell count (SCDLP medium). The number was measured. As a result, in Example 4, 1.2 × 10 2
In Example 12, the value was 0.9 × 10 2 or less.
Claims (10)
白雲母質物とを含んで成る吸着性多孔質焼結体。1. An adsorptive porous sintered body comprising activated carbon and / or an adsorptive silicate and a synthetic muscovite substance.
剤と、合成白雲母質物とを含んで成る吸着性多孔質焼結
体。2. An adsorptive porous sintered body comprising activated carbon and / or an adsorptive silicate, an antibacterial agent, and a synthetic muscovite.
質無機物と、合成白雲母とを含んで成る吸着性多孔質焼
結体。3. An adsorptive porous sintered body comprising activated carbon and / or adsorptive silicate, a hollow inorganic substance, and synthetic muscovite.
珪酸塩と合成白雲母質より成る積層を形成して成る吸着
性多孔質焼結体。4. An adsorptive porous sintered body formed by forming a laminate comprising an adsorptive silicate and a synthetic muscovite on the outer periphery of a molded body containing activated carbon.
リロナイト、酸性白土、珪藻土、セピオライト、ゼオラ
イトの少なくとも１種である請求項１又は請求項２又は
請求項３又は請求項４の吸着性多孔質焼結体。5. The adsorptive porous material according to claim 1, wherein the adsorptive silicate is at least one of kaolinite, montmorillonite, acid clay, diatomaceous earth, sepiolite, and zeolite. Sintered body.
又はその原料配合物、或いはフッ素バラゴナイト又はそ
の原料配合物の少なくとも１種である請求項１又は請求
項２又は請求項３又は請求項４の吸着性多孔質焼結体。6. The synthetic muscovite substance according to claim 1, wherein the synthetic muscovite is at least one of fluorine muscovite or a raw material blend thereof, or fluorine balagonite or a raw material blend thereof. Adsorbent porous sintered body.
担持したゼオライト、モンモリロナイト、膨潤性雲母、
リン酸カルシウムの少なくとも１種である請求項２の吸
着性多孔質焼結体。7. An antibacterial agent comprising a zeolite, montmorillonite, swellable mica, carrying either silver, copper or zinc;
3. The adsorptive porous sintered body according to claim 2, which is at least one kind of calcium phosphate.
カバルーン、ガラスバルーンの少なくとも１種である請
求項３の吸着性多孔質焼結体。8. The adsorptive porous sintered body according to claim 3, wherein the hollow inorganic substance is at least one of a shirasu balloon, a silica balloon, and a glass balloon.
質無機物と、合成白雲母とを含んで成る成形体を、５０
０〜６５０゜Ｃで焼成して焼結することを特徴とする吸
着性多孔質焼結体の製造方法。9. A molded article comprising activated carbon and / or adsorptive silicate, a hollow inorganic substance, and synthetic muscovite,
A method for producing an adsorptive porous sintered body, characterized by firing at 0 to 650 ° C and sintering.
性珪酸塩と合成白雲母質より成る層を形成し、５００〜
６５０゜Ｃで焼成して焼結することを特徴とする吸着性
多孔質焼結体の製造方法。10. A layer comprising an adsorptive silicate and synthetic muscovite is formed on the outer periphery of a molded body containing activated carbon,
A method for producing an adsorptive porous sintered body, characterized by firing at 650 ° C. and sintering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9165417A JPH10337469A (en) | 1997-06-05 | 1997-06-05 | Adsorptive porous sintered compact and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9165417A JPH10337469A (en) | 1997-06-05 | 1997-06-05 | Adsorptive porous sintered compact and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10337469A true JPH10337469A (en) | 1998-12-22 |
Family
ID=15812031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9165417A Pending JPH10337469A (en) | 1997-06-05 | 1997-06-05 | Adsorptive porous sintered compact and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10337469A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002062710A1 (en) * | 2001-02-07 | 2002-08-15 | Bmt Bio Mineral Technologies Ab | Filter equipment and process for the treatment of waste water containing inorganic, organic pollution and/or pathogens |
| JP2006160692A (en) * | 2004-12-09 | 2006-06-22 | Masayoshi Mori | Method for producing antimicrobial agent and antimicrobial agent |
| KR100895867B1 (en) | 2007-11-28 | 2009-04-30 | (주)동화라이징 | Method for preparing of porous sintered bodies |
| WO2009157681A3 (en) * | 2008-06-24 | 2010-03-11 | Lumilite Co., Ltd. | Water quality improvement composition containing eco-friendly active natural minerals and method of manufacturing the same |
| JP2016010749A (en) * | 2014-06-27 | 2016-01-21 | 株式会社タカギ | Method for producing molded adsorbent, molded adsorbent and water purifier using the same |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5446210A (en) * | 1977-09-21 | 1979-04-12 | Osaka Sanso Kougiyou Kk | Method of making halffburnt body comprising active carbon* zeolite blended mixture |
| JPS62155935A (en) * | 1985-12-28 | 1987-07-10 | Topy Ind Ltd | Deodorant |
| JPS63147858A (en) * | 1986-07-28 | 1988-06-20 | オオタケセラム株式会社 | Active inorganic material and manufacture |
| JPH01278408A (en) * | 1988-04-28 | 1989-11-08 | Matsushita Electric Ind Co Ltd | Bacteriostatic activated carbon |
| JPH03208870A (en) * | 1990-01-09 | 1991-09-12 | Oriental Sangyo Kk | Production of porous ceramic body |
| JPH04108537A (en) * | 1990-08-27 | 1992-04-09 | Babcock Hitachi Kk | Preparation of catalyst carrier and catalyst |
| JPH05345703A (en) * | 1992-06-12 | 1993-12-27 | Taihei Kagaku Sangyo Kk | Antibacterial activated carbon |
| JPH07148434A (en) * | 1993-07-12 | 1995-06-13 | Ishihara Sangyo Kaisha Ltd | Photocatalyst and water cleaning method using the same |
| JPH0970806A (en) * | 1995-09-04 | 1997-03-18 | Sekisui Chem Co Ltd | Manufacture of inorganic cured body |
-
1997
- 1997-06-05 JP JP9165417A patent/JPH10337469A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5446210A (en) * | 1977-09-21 | 1979-04-12 | Osaka Sanso Kougiyou Kk | Method of making halffburnt body comprising active carbon* zeolite blended mixture |
| JPS62155935A (en) * | 1985-12-28 | 1987-07-10 | Topy Ind Ltd | Deodorant |
| JPS63147858A (en) * | 1986-07-28 | 1988-06-20 | オオタケセラム株式会社 | Active inorganic material and manufacture |
| JPH01278408A (en) * | 1988-04-28 | 1989-11-08 | Matsushita Electric Ind Co Ltd | Bacteriostatic activated carbon |
| JPH03208870A (en) * | 1990-01-09 | 1991-09-12 | Oriental Sangyo Kk | Production of porous ceramic body |
| JPH04108537A (en) * | 1990-08-27 | 1992-04-09 | Babcock Hitachi Kk | Preparation of catalyst carrier and catalyst |
| JPH05345703A (en) * | 1992-06-12 | 1993-12-27 | Taihei Kagaku Sangyo Kk | Antibacterial activated carbon |
| JPH07148434A (en) * | 1993-07-12 | 1995-06-13 | Ishihara Sangyo Kaisha Ltd | Photocatalyst and water cleaning method using the same |
| JPH0970806A (en) * | 1995-09-04 | 1997-03-18 | Sekisui Chem Co Ltd | Manufacture of inorganic cured body |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002062710A1 (en) * | 2001-02-07 | 2002-08-15 | Bmt Bio Mineral Technologies Ab | Filter equipment and process for the treatment of waste water containing inorganic, organic pollution and/or pathogens |
| JP2006160692A (en) * | 2004-12-09 | 2006-06-22 | Masayoshi Mori | Method for producing antimicrobial agent and antimicrobial agent |
| KR100895867B1 (en) | 2007-11-28 | 2009-04-30 | (주)동화라이징 | Method for preparing of porous sintered bodies |
| WO2009157681A3 (en) * | 2008-06-24 | 2010-03-11 | Lumilite Co., Ltd. | Water quality improvement composition containing eco-friendly active natural minerals and method of manufacturing the same |
| JP2016010749A (en) * | 2014-06-27 | 2016-01-21 | 株式会社タカギ | Method for producing molded adsorbent, molded adsorbent and water purifier using the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102285816A (en) | Tourmaline integral honeycomb ceramic and preparation method thereof | |
| JP2005015276A (en) | Ceramic fired body and antibacterial ceramic and microorganism immobilization support using the same | |
| JPH10337469A (en) | Adsorptive porous sintered compact and its production | |
| US3116131A (en) | Method and materials for disposing of radioactive waste | |
| CN110668606B (en) | Composite active carbon filter element and preparation method thereof | |
| JPH08310881A (en) | Porous sintered body and its production | |
| KR101111536B1 (en) | Manufacturing method of heavy metal adsorbent | |
| JPH10258228A (en) | Granular sintered body and its manufacture | |
| JPH08141589A (en) | Ceramics porous element and treatment of waste water using the same | |
| JP2007063085A (en) | Calcium carbonate composition | |
| CN106396628A (en) | Spherical sepiolite lightweight through-hole ceramsite with air purifying functions | |
| KR101227802B1 (en) | Porous ceramic media for microbes by sawdust and method of manufacturing the same | |
| CN106431463A (en) | Light cylindrical attapulgite through-hole ceramsite with air purification function | |
| JPH11322469A (en) | Production of porous tourmaline ceramics | |
| JPS5969146A (en) | Production of filter-like adsorbent using powdery activated carbon as raw material | |
| KR100481973B1 (en) | Organic and Inorganic Hybrid Media for Microbe Immobilization and Its Producing Method | |
| JP2008074648A (en) | Method for producing porous material | |
| CN106431284A (en) | Spherical zeolite light through-hole ceramsite with air purification function | |
| JPH07330527A (en) | Antimicrobial ceramic | |
| CN106631149A (en) | Gravel-shaped light ceramsite with air purification function and volcaniclastic rock | |
| CN113398884B (en) | Floating adsorbent and proportioning and metering method thereof | |
| JP2003103285A (en) | Water cleaning porous body | |
| JPH10211428A (en) | Adsorptive ceramic | |
| KR20240042702A (en) | A method for manufacturing an absorbent for phosphorus removal based on granular red mud and its absorbent | |
| JPH0375256A (en) | Functional ceramics and production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040604 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20051130 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051213 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20060425 |