JP3595911B2 - Adsorption ceramic - Google Patents

Description

表１の使用例１および使用例２に示すセラミック構造物は、いずれもアルカリ金属およびアルカリ土類金属の酸化物を５重量％以上３５重量％以下混合している。なお、酸化珪素ＳｉＯ_２ および酸化アルミニウムＡｌ_２ Ｏ_３ はセラミック構造物の主体となるもので、これらの存在は不可欠である。
このようなセラミック構造物の原料となる鉱石１…は、平均粒径が５μｍ以上、１０００μｍ以下とし、好ましくは１５０〜５００μｍの範囲がよい。
【００２７】
上記鉱石１に対し、活性炭の粉末２…は安価で入手の容易なヤシ殻活性炭が用いられており、ヤシ殻活性炭はヤシ殻繊維の中に含まれている水分が飛散されることにより、この水分の抜けた跡に多数の気孔が生じた多孔質構造をなしているものである。本例では空隙率が３０〜７０％、比表面積が８００〜１５００ｍ^２ ／ｇの範囲にある活性炭粉末が用いられており、非常に優れた吸着性を有している。上記活性炭粉末の平均粒径は５μｍ以上、１０００μｍ以下とし、好ましくはセラミック構造物を構成する鉱石１の平均粒径と同等がよいが、１０倍以内でセラミック構造物を構成する鉱石１の平均粒径よりも大きくてもよい。
【００２８】
抗菌金属は、銀、銅、亜鉛のいずれであってもよいが、性能、その他の理由から銀粉末が用いられている。なお、銀は硝酸銀から得ることができる。
【００２９】
バインダ４として使用される粘土は、例えば蛙目粘土が使用される。蛙目粘土を使用すれば、焼成された後に蛙目粘土が多孔質構造をもち、吸着作用を奏することができる。
【００３０】
またバインダ４として使用されるフリットガラスは、溶融温度が６５０〜９５０℃のフリットが使用される。
【００３１】
これら鉱石粒１、活性炭の粉末２、銀粉末３、粘土およびフリットガラスの混合割合を下記表２に示す。
【００３２】
【表２】

サンプル１は活性炭の割合が少なくフリットガラスを使用しない場合であり、サンプル２は活性炭の割合が多く、かつフリットガラスを使用した場合である。
【００３３】
このような混合比の材料を用いて吸着セラミック１０、２０、３０を製造する方法を説明する。
サンプル１およびサンプル２のような混合比の材料に水を加えてこれを練り、所定の形を作り易くしかもこの形を維持できる程度の固さを保つ粘土状態にする。この粘土状混合物を、延ばす、切断する、型にはめる、または押し出すなどの成形方法により、図１に示すような造形物１０、２０、３０を成形する。この成形物を焼成炉で焼く。この焼成温度は、セラミック原料の粒子が結晶化し、しかしながら活性炭が灰化しない程度の温度であり、かつ粘土やフリットガラスが焼成され、しかも鉱石粒１、活性炭２および銀粉末３が焼結により相互に付着する温度で焼き上げるものである。具体的には９００〜１０００℃の範囲がよく、特に９４０〜９５０℃が好ましい。
【００３４】
このような方法により製造されたセラミック成形品は、混合したときに用いた水分が焼成工程により飛散されて除去され、粒子間に気孔、すなわち連続気孔の空隙５が形成されることになる。このような焼成により得られた吸着セラミックの諸特性を前記した表２に示す。これら特性は、充填密度、ＪＩＳ法硬度、ＭＳ法硬度、細孔表面積、細孔容積、平均細孔直径である。
【００３５】
このようなサンプル１およびサンプル２の吸着セラミックは以下の作用を奏する。
サンプル１およびサンプル２の諸特性をもつ吸着セラミックは、多孔質セラミック構造物自身が連続気孔の空隙５を備えるから、水などの液体、空気等のガス中に含まれる不純物質、例えば有毒物質、微生物、かび、ウイルス、農薬、重金属などの汚染物質を吸着する。特に、多孔質セラミック構造物に付着されている活性炭が微細な連続細孔を有するので、この活性炭が優れた吸着作用を奏する。この結果、例えば水道水に浸漬する、または水道水を通すと、水道水に含まれる有毒物質、微生物、かび、ウイルス、農薬、重金属などの汚染物質を良好に吸着する。また、かび臭さやカルキ臭さを除去することができる。
【００３６】
そして、活性炭はアンモニアを吸着できないが、多孔性セラミックがアンモニアを吸着するから、塩素とアンモニアとの反応を抑制し、カルキ臭の発生を防止することができる。
【００３７】
さらにこの吸着セラミックは、トリハロメタンおよび残留塩素を取り除く作用がある。
表３はトリハロメタンの測定結果を示す。この試験は、淀川から汲み上げた河川水のトリハロメタン吸着性能を試験したものである。採集した淀川の水はトリハロメタンの濃度が０．０２１ｍｇ／ｌであり、この採集水２００ｍｌの中に５０ｇのサンプル１の吸着セラミックを浸漬し、１分、５分、１０分後のトリハロメタンの量を測定した。
【００３８】
【表３】

上記試験結果から、本例の吸着セラミックは採集水に浸漬して１分後には１４％、５分後には０．５％、１０分後には０．０４％まで減少することが測定され、トリハロメタンの吸着性能がきわめて優れていることを確認することができる。トリハロメタンは活性炭でもある程度まで取り除くことができるが、活性炭でトリハロメタンを取り除く能力は充分でない。本例の吸着セラミックがトリハロメタンの吸着性能に優れている理由は定かでないが以下の点が推測される。
【００３９】
すなわち、上記多孔質セラミック構造物は、ＮａやＫなどのアルカリ金属の酸化物、およびＣａなどのアルカリ土類金属の酸化物を５重量％以上３０重量％以下含有しているから、これらアルカリ金属の酸化物やアルカリ土類金属の酸化物の存在がトリハロメタンの発生を抑止しているものと考えられる。
【００４０】
アルカリ金属の酸化物およびアルカリ土類金属の酸化物の混合割合が５重量％未満の場合はトリハロメタンの吸着作用が小さく、その効果が低いので５重量％以上の混合が必要である。また３５重量％を越えると、多孔質セラミック構造物の主成分であるシリカやアルミナが少なくなり、セラミック強度が低くなる。
【００４１】
そして、本例の吸着セラミックは、抗菌金属として銀を混合しているから、この銀がハロゲンと結びついてハロゲン化銀を生成し、このこともトリハロメタンを少なくするものと考えられる。
【００４２】
表４は残留塩素の測定結果を示す。この試験は、水道水に次亜塩素ナトリウム溶液を加えて残留塩素濃度を２ｍｇ／ｌに調整し、この試験水２００ｍｌの中に５０ｇのサンプル１の吸着セラミックを浸漬し、１分、５分、１０分後の残留塩素の量を測定した。
【００４３】
【表４】

上記試験結果より、残留塩素は吸着セラミックに吸着されてほとんど検出されない。これは主として活性炭が残留塩素を吸着する性質に優れているので、活性炭に吸着されたものと考えられる。
【００４４】
表５は吸着セラミックを水に浸漬した場合、この吸着セラミックから有害といわれている不純物が溶出しないか否かを測定したものである。水道水２リットルの中に５０ｇのサンプル１の吸着セラミックを浸漬し、これを常温で７２時間静置し、得られ浸漬水について、カドミウム、鉛、ヒ素の検出を測定した。
【００４５】
【表５】

上記試験結果から、本例の吸着セラミックは水に浸漬して使用しても、不純物の溶け出しが認められず、安全に使用できることが確認される。
【００４６】
そして、上記吸着セラミックは、多孔質セラミック構造体に抗菌金属としての銀３が付着されているから、銀の殺菌、滅菌、減菌作用により、孔質セラミック構造体の空隙５内および活性炭２の細孔内に吸着した物質より雑菌が繁殖するのを防止する。この場合、銀粉末３が全体に対して０．１重量％未満であると殺菌、滅菌、減菌作用が低く抗菌金属としての役目を果たさず、また５重量％を越えると、溶出が心配され、飲料水や食物への使用が懸念される。
【００４７】
なお、前記したように、銀を使用した場合は、銀がハロゲンと結びついてハロゲン化銀を生成し、トリハロメタンの析出を抑止する。
【００４８】
そして、実施例の多孔質セラミックは、鉱石の粒１と、活性炭の粉末２と、抗菌金属３と、これらを接合するバインダ４としての粘土およびフリットガラスとを混ぜ、これを所定の形に成形して焼成したから、粘土およびフリットガラスがバインダとなって鉱石の粒と活性炭の粒と抗菌金属を結合する。
【００４９】
このため、吸着セラミックが破損したり、活性炭がこぼれ落ちたり、湿潤により剥がれたり、抗菌金属が溶出することがない。
【００５０】
特に、銀３が溶出することは避けなければならないが、この点を実験したところ、表６の結果を得た。表６は水道水１リットルに５０ｇのサンプル１の吸着セラミックを浸漬し、これを常温で２４時間静置した。得られた浸漬水についての銀およびｐＨ値を測定した。
【００５１】
【表６】

表６から、銀の溶出は２４時間後に０．０５ｍｇ／ｌが認められたが、これは安全基準内であることが確認されている。
【００５２】
バインダ４として粘土およびフリットガラスを使用することにより、鉱石の粒と活性炭の粒と抗菌金属の異種物質を結合することができるばかりでなく、セラミック構造物を作ることができ、任意形状の吸着セラミックを形成することができる。特に、フリットガラスを混ぜると、ＭＳ法硬度が向上し、破損、欠損、磨耗などに対する機械的強度が向上する。但し、フリットガラスを過剰に使用すると空隙５や活性炭２の目詰まりを起こすのでフリットガラスは２０重量％を越えない分量がよい。
【００５３】
さらに、活性炭粉末の平均粒径とセラミック鉱石の粒径は同等であることが両者を結合するには好都合であるが、活性炭粉末が大きくてもよい。セラミック粒子が活性炭粉末より大きくなると、セラミック粒子が活性炭粉末を掴まえておく機能が低下して焼結形態を保つことができなくなり、破損し易くなる。
【００５４】
活性炭粉末３の平均粒径は、５μｍ未満であると、活性炭粉末が細かくなり過ぎ、セラミック粒子が活性炭粉末の間に形成される気孔を埋めて空隙を無くし、これにより吸着能が低下する。また、活性炭粉末の平均粒径が１０００μｍを越えると、水を吸ったときに湿潤してふやけ、セラミック粒子から外れて崩れる心配がある。
【００５５】
上記実施例の場合、水道水の処理に関して説明したが、本発明の吸着セラミックは水道水の処理に制約されるものではなく、その吸着性能の優秀さから、プールや浴場の水処理、上下水処理、工場の排水処理などを始めとして各種液体処理などの工業的用途、濾過材としての適用、また臭い取りとして気体分野などへの利用も可能であり、広範囲には、食品工業、化学工業、電子工業、環境浄化、医療、農業、林業、水産業その他生活環境への展開が可能である。
【図面の簡単な説明】
【図１】本発明の異なる形状の吸着セラミックを示し、（Ａ）図は球形吸着セラミック、（Ｂ）図は円柱形吸着セラミック、（Ｃ）図は平板形吸着セラミックのそれぞれ斜視図。
【図２】吸着セラミックの結晶構造を模式的に示す構造図。
【符号の説明】
１…セラミック材料の鉱石
２…活性炭粉末
３…銀粉末
４…バインダ
１０、２０、３０…吸着セラミック。[0001]
[Industrial applications]
The present invention relates to an adsorption ceramic excellent in adsorbing and filtering odorous and harmful components and other impurities contained in a fluid such as dirty air and water.
[0002]
[Prior art]
Recently, deterioration of drinking water quality due to contamination of water sources has been raised as a problem, and there is a concern that contaminants such as toxic substances, microorganisms, molds, viruses, pesticides, and heavy metals may be mixed into tap water.
However, tap water is supplied with chlorine as a germicide, thereby disinfecting various germs and the like. It is obligatory to mix such chlorine with tap water, and it has been determined that chlorine must be mixed in the water coming out of the faucet at the end of the water pipe with 0.1 PPM or more. For this reason, chlorine remains in the water discharged from the faucet, thereby maintaining safety against various germs.
However, when chlorine is mixed, chlorine and ammonia combine to generate chlorine odor. The more severe the pollution of the water source, the more ammonia is generated, the more chlorine is used, and the stronger the smell of chlorine.
Also, residual chlorine is combined with a substance called humin to generate trihalomethane, which is known to be a carcinogen.
Furthermore, if the water source becomes heavily contaminated, tap water may have a musty odor.
[0003]
It is said that filtration with activated carbon is effective as such a quality control of tap water. Activated carbon has a large number of fine pores formed in its tissue, and therefore has a porous structure, and therefore has an excellent adsorption action.In these pores, chlorine, pesticides, viruses, detergents, musty odor, It has the effect of capturing water odor, heavy metals such as iron, copper, zinc, lead and manganese and filtering water. Therefore, measures such as installing activated carbon water purifiers and water purifiers have been taken in ordinary households.
[0004]
[Problems to be solved by the invention]
However, although activated carbon is effective in removing residual chlorine, it is said that activated carbon is not perfect for removing trihalomethane. This is thought to be due to the fact that the molecular diameter and water solubility of trihalomethane are smaller than the pore diameter of activated carbon.
That is, trihalomethane means methane in which three halogen elements have been substituted. In the field of water quality, chloroform (CHCl ₃ ), dichlorobromomethane (CHBrCl ₂ ), chlorodibromomethane (CHBr ₂ Cl), and bromoform (CHBr ₃ ) ) Is used as a generic term for the four substances, and since tap water in Japan contains the highest concentration of chloroform and uses little bromine, bromoform is hardly detected. Then, the molecular diameter and the water solubility of chloroform are the smallest, followed by dichlorobromomethane, chlorodibromomethane, and bromoform in this order. For this reason, it is thought that trihalomethane represented by chloroform cannot be completely removed by activated carbon.
Therefore, removal of trihalomethane has been an issue.
[0005]
Activated carbon also has the property of not being able to adsorb ammonia, and cannot prevent the bond between residual chlorine and ammonia, and thus has the problem of not being able to prevent the generation of odor.
[0006]
On the other hand, activated carbon has the property of effectively adsorbing various substances as described above, and such adsorption performance is difficult to dispose of. However, as another problem of activated carbon, adsorbed substances, particularly microorganisms, molds, bacteria, etc., remain in the pores and cause germs to propagate. In other words, it has been pointed out that, for example, when the unused time of a water purifier containing activated carbon is prolonged, various bacteria grow and are unsanitary.
On the other hand, antibacterial activated carbon has been developed. The antibacterial activated carbon is a mixture of activated carbon and an antibacterial metal made of silver, copper or zinc, and the germicidal and sterilizing action of the antibacterial metal prevents the propagation of various germs.
However, conventional antibacterial activated carbon is obtained by applying silver or copper to activated carbon or mixing silver or zinc particles.In such a structure, the problem is that antibacterial metals exceeding the standard value elute into water. There is.
[0007]
Further, most of activated carbon is in the form of granules or powder, and cannot be formed into a predetermined shape. The desired shape requires use in a container of that shape, which leaves the inconvenience of limited use.
[0008]
The present invention has been made based on such circumstances, and the object is to effectively utilize the high adsorption performance of activated carbon, and to excel in the adsorption of ammonia and trihalomethane, and to propagate the germs taken up. It is an object of the present invention to provide an adsorbing ceramic that can be prevented and formed into an arbitrary shape.
[0009]
The adsorptive ceramic of the present invention is not limited to being used for purification of tap water by filtration, but is also intended for liquids such as circulating purification of pools and baths, and wastewater treatment of factories. It can also be used as a filter for gas, such as deodorizing and deodorizing refrigerators and toilet shoeboxes.
[0010]
[Means for Solving the Problems]
The invention according to claim 1 comprises an ore particle containing silicon oxide and aluminum oxide as main components, and at least 5% by weight or more and 30% by weight or less of an oxide of an alkali metal and an alkaline earth metal. The porous ceramic structure is mixed with activated carbon in a proportion of 10% by weight or more and 65% by weight or less and antibacterial metal in a proportion of 0.1% by weight or more and 5% by weight or less based on the whole. An adsorption ceramic characterized by being sintered.
[0012]
According to a second aspect of the present invention , an ore grain serving as a structure of the porous ceramic, an activated carbon grain, an antibacterial metal, and a binder made of clay or frit glass for joining these are mixed and formed into a predetermined shape. The adsorptive ceramic according to claim 1, which is formed and fired.
[0016]
[Action and effect]
According to the present invention, a porous ceramic structure consisting of ore particles, because activated carbon and antibacterial metal is sintered been mixed, it exhibits the adsorption by the pore provided activated carbon inherently good at activated carbon In addition to capturing residual chlorine, pesticides, viruses, detergents, musty odors, moldy odors, other odor components, and heavy metals such as iron, copper, zinc, lead, and manganese, in addition to these, porous ceramic structures It has a void and adsorbs ammonia and the like that the activated carbon is not good at in the void. Therefore, the adsorption action of the activated carbon and the adsorption action of the porous ceramic work together, so that various odor components, harmful substances, and other impurities are satisfactorily adsorbed.
In particular, since the porous ceramic structure contains at least 5% by weight to 30% by weight of an oxide of an alkali metal and an alkaline earth metal, it is effective for trihalomethane adsorption. Although the cause is not clear, it has been experimentally confirmed that the inclusion of an alkali metal and an alkaline earth metal suppresses the generation of trihalomethane. In this case, if the content of the alkali metal and alkaline earth metal oxides is less than 5% by weight, there is no effect on the adsorption of trihalomethane, and if it exceeds 30% by weight, silica or alumina which is the main component of the porous ceramic structure is used. Since the ratio is reduced, the strength is reduced.
In addition, since activated carbon was mixed at a ratio of 10% by weight or more and 65% by weight or less, the physical adsorption effect of the pores inherent in activated carbon was maintained, and residual chlorine, pesticides, viruses, detergents, musty odors, odors, etc. Maintains adsorption performance for odor components, heavy metals such as iron, copper, zinc, lead, and manganese.
Furthermore, since the adsorbed ceramic contains an antibacterial metal, bacteria adsorbed in pores of the porous ceramic structure or the activated carbon are sterilized or sterilized to prevent the propagation of various bacteria. In this case, the antibacterial effect cannot be expected unless the antibacterial metal is mixed with 0.1% by weight or more with respect to the whole. Conversely, if it exceeds 5% by weight, the mixing ratio of the porous ceramic and the activated carbon decreases. If the original adsorptive action is reduced, and if it exceeds 5% by weight, elution is concerned, and it becomes impossible to use it for drinking water or food.
[0018]
According to the invention of claim 2, the ore grains serving as the structure of the porous ceramic, the activated carbon grains, the antibacterial metal, and the binder made of clay or frit glass for joining them are mixed and formed into a predetermined shape. because molded to firing, the binder is bonded to each other and ore particles and activated carbon particle and antimicrobial metal, thus since these grains are firmly bound, there is no Rukoto activated carbon and antibacterial metal is spilled, especially When used in a liquid, elution of the antimicrobial metal can be reliably prevented.
[0023]
【Example】
Hereinafter, the present invention will be described based on one embodiment shown in FIGS. 1A and 1B show examples of adsorption ceramics formed into various shapes. FIG. 1A shows an adsorption ceramic 10 of the present invention formed into spherical small and medium particles, and FIG. 1B shows a columnar shape. FIG. 1 (C) shows the adsorption ceramic 20 of the present invention formed in a flat plate shape. These adsorbing ceramics 10, 20, 30 have the same composition, almost the same manufacturing method, and the same performance and function.
FIG. 2 is a structural diagram schematically showing a sintered crystal structure of the adsorption ceramics 10, 20, and 30. In FIG. 2, reference numeral 1 denotes ore particles serving as a ceramic structure, 2 denotes activated carbon powder formed from, for example, coconut shell, 3 denotes silver powder as an antibacterial metal, 4 denotes a binder, and a mixture of clay and frit glass. State. The ore grains 1 are joined by a binder 4 made of clay or frit glass to form a porous ceramic structure. Activated carbon powder 2 is joined between the ore grains 1. The void 5 is formed of continuous pores that have entered like a gym. Silver powders 3 as antibacterial metals are dispersed and held in the voids 5 formed of the continuous pores. Although not shown, continuous fine pores are formed in the activated carbon powder 2.
[0024]
The ore serving as the ceramic structure has the following composition ratio. That is, the general composition of the ceramic is silicon oxide SiO ₂ and aluminum oxide Al ₂ O ₃ , but the ceramic structure of the present invention has at least an alkali metal and an alkaline earth metal in addition to the main composition. Is mixed in an amount of 5% by weight or more and 30% by weight or less. The alkali metal oxide is sodium oxide Na ₂ O and potassium oxide K ₂ O, and the alkaline earth metal oxide is calcium oxide CaO.
[0025]
Incidentally, the following Table 1 shows an example of the composition ratio of the porous ceramic that can be used.
[0026]
[Table 1]

Each of the ceramic structures shown in Use Example 1 and Use Example 2 in Table 1 contains 5% by weight or more and 35% by weight or less of an oxide of an alkali metal and an alkaline earth metal. Note that silicon oxide SiO ₂ and aluminum oxide Al ₂ O ₃ are the main components of the ceramic structure, and their presence is indispensable.
The ore 1 as a raw material of such a ceramic structure has an average particle size of 5 μm or more and 1000 μm or less, and preferably in the range of 150 to 500 μm.
[0027]
For the ore 1, activated carbon powder 2 is made of inexpensive and easily available coconut shell activated carbon, and the coconut shell activated carbon emits water contained in coconut shell fibers, and this is used as the activated carbon powder. It has a porous structure in which a large number of pores are formed in the trace of moisture. In this example, activated carbon powder having a porosity in the range of 30 to 70% and a specific surface area in the range of 800 to 1500 m ² / g is used, and has extremely excellent adsorptivity. The average particle size of the activated carbon powder is 5 μm or more and 1000 μm or less, preferably the same as the average particle size of the ore 1 constituting the ceramic structure, but within 10 times the average particle size of the ore 1 constituting the ceramic structure. It may be larger than the diameter.
[0028]
The antimicrobial metal may be any of silver, copper, and zinc, but silver powder is used for performance and other reasons. In addition, silver can be obtained from silver nitrate.
[0029]
As the clay used as the binder 4, for example, Frog-eyed clay is used. The use of the frog eye clay allows the frog eye clay to have a porous structure after being fired and exhibit an adsorption action.
[0030]
As the frit glass used as the binder 4, a frit having a melting temperature of 650 to 950 ° C is used.
[0031]
Table 2 below shows the mixing ratio of these ore grains 1, activated carbon powder 2, silver powder 3, clay and frit glass.
[0032]
[Table 2]

Sample 1 is a case where the ratio of activated carbon is small and no frit glass is used, and Sample 2 is a case where the ratio of activated carbon is large and frit glass is used.
[0033]
A method for manufacturing the adsorbing ceramics 10, 20, 30 using the materials having such a mixing ratio will be described.
Water is added to a material having a mixing ratio such as Sample 1 and Sample 2, and the mixture is kneaded to obtain a clay state which is easy to form a predetermined shape and which has a hardness sufficient to maintain the shape. The moldings 10, 20, 30 as shown in FIG. 1 are molded by a molding method such as stretching, cutting, molding, or extruding the clay-like mixture. This molded product is baked in a firing furnace. The firing temperature is such that the particles of the ceramic raw material are crystallized, but the activated carbon is not ashed, and the clay or frit glass is fired, and the ore particles 1, the activated carbon 2 and the silver powder 3 are mutually sintered. It is baked at the temperature at which it adheres. Specifically, the temperature is preferably in the range of 900 to 1000C, and particularly preferably 940 to 950C.
[0034]
In the ceramic molded article manufactured by such a method, the water used at the time of mixing is scattered and removed in the firing step, and pores, that is, voids 5 of continuous pores are formed between the particles. Table 2 shows various characteristics of the adsorption ceramic obtained by such firing. These characteristics are packing density, JIS hardness, MS hardness, pore surface area, pore volume, and average pore diameter.
[0035]
The adsorption ceramics of Sample 1 and Sample 2 have the following effects.
Since the porous ceramic structure itself has the pores 5 of continuous pores, the adsorptive ceramic having the properties of the samples 1 and 2 has impurities 5 contained in a liquid such as water and a gas such as air, for example, a toxic substance. Adsorb contaminants such as microorganisms, molds, viruses, pesticides, heavy metals, etc. In particular, since the activated carbon attached to the porous ceramic structure has fine continuous pores, the activated carbon exhibits an excellent adsorption action. As a result, for example, when immersed in or passed through tap water, contaminants such as toxic substances, microorganisms, fungi, viruses, pesticides, and heavy metals contained in the tap water are satisfactorily adsorbed. In addition, it is possible to remove moldy odor and odor of mold.
[0036]
Activated carbon cannot adsorb ammonia, but porous ceramics adsorb ammonia. Therefore, it is possible to suppress the reaction between chlorine and ammonia and prevent the generation of odor.
[0037]
Further, the adsorbed ceramic has an action of removing trihalomethane and residual chlorine.
Table 3 shows the measurement results of trihalomethane. In this test, the trihalomethane adsorption performance of river water pumped from the Yodo River was tested. The collected Yodogawa water had a trihalomethane concentration of 0.021 mg / l, and 50 g of the sample 1 adsorption ceramic was immersed in 200 ml of the collected water, and the amount of trihalomethane after 1 minute, 5 minutes, and 10 minutes was measured. It was measured.
[0038]
[Table 3]

From the above test results, it was measured that the adsorbed ceramic of this example decreased to 14% after 1 minute of immersion in the collected water, to 0.5% after 5 minutes, and to 0.04% after 10 minutes. It can be confirmed that the adsorption performance is extremely excellent. Activated carbon can remove trihalomethane to some extent, but activated carbon does not have sufficient ability to remove trihalomethane. The reason why the adsorption ceramic of this example is excellent in trihalomethane adsorption performance is not clear, but the following points are presumed.
[0039]
That is, the porous ceramic structure contains 5% by weight to 30% by weight of an oxide of an alkali metal such as Na or K and an oxide of an alkaline earth metal such as Ca. It is considered that the presence of an oxide of, or an oxide of an alkaline earth metal suppresses the generation of trihalomethane.
[0040]
When the mixing ratio of the alkali metal oxide and the alkaline earth metal oxide is less than 5% by weight, the adsorbing action of trihalomethane is small, and the effect is low. Therefore, the mixing of 5% by weight or more is necessary. If it exceeds 35% by weight, silica and alumina, which are the main components of the porous ceramic structure, decrease, and the ceramic strength decreases.
[0041]
And since the adsorption ceramic of this example mixes silver as an antibacterial metal, this silver combines with halogen to generate silver halide, which is also considered to reduce trihalomethane.
[0042]
Table 4 shows the measurement results of residual chlorine. In this test, the residual chlorine concentration was adjusted to 2 mg / l by adding sodium hypochlorite solution to tap water, and 50 g of the adsorption ceramic of Sample 1 was immersed in 200 ml of the test water, and the test was performed for 1 minute, 5 minutes, After 10 minutes, the amount of residual chlorine was measured.
[0043]
[Table 4]

From the above test results, the residual chlorine is hardly detected by being adsorbed by the adsorbed ceramic. This is probably because activated carbon is excellent in the property of adsorbing residual chlorine, and thus is adsorbed on activated carbon.
[0044]
Table 5 shows whether the harmful impurities do not elute from the adsorbed ceramic when the adsorbed ceramic is immersed in water. 50 g of the adsorption ceramic of sample 1 was immersed in 2 liters of tap water, allowed to stand at room temperature for 72 hours, and the immersion water was measured for the detection of cadmium, lead and arsenic.
[0045]
[Table 5]

From the above test results, it is confirmed that even when the adsorbed ceramic of this example is immersed in water and used, no leaching of impurities is observed, and it can be used safely.
[0046]
Since the adsorption ceramic has silver 3 as an antibacterial metal adhered to the porous ceramic structure, the silver is sterilized, sterilized, and sterilized by the action of silver 3 in the pores 5 of the porous ceramic structure and the activated carbon 2. Prevents the propagation of various bacteria from the substance adsorbed in the pores. In this case, if the silver powder 3 is less than 0.1% by weight of the whole, the sterilizing, sterilizing and sterilizing effects are low, and the silver powder 3 does not serve as an antibacterial metal. , There is concern about use in drinking water and food.
[0047]
As described above, when silver is used, silver is combined with halogen to form silver halide, thereby suppressing the precipitation of trihalomethane.
[0048]
The porous ceramic of the embodiment is obtained by mixing ore grains 1, activated carbon powder 2, antibacterial metal 3, clay and frit glass as a binder 4 for joining them, and molding this into a predetermined shape. After firing, the clay and frit glass serve as a binder to bind the ore grains, activated carbon grains and antimicrobial metal.
[0049]
Therefore, the adsorbed ceramic is not damaged, the activated carbon is not spilled, peeled off by wetting, and the antibacterial metal is not eluted.
[0050]
In particular, elution of silver 3 must be avoided. When this point was tested, the results shown in Table 6 were obtained. Table 6 shows that 50 g of the adsorption ceramic of sample 1 was immersed in 1 liter of tap water and allowed to stand at room temperature for 24 hours. Silver and pH values of the obtained immersion water were measured.
[0051]
[Table 6]

From Table 6, it was confirmed that the elution of silver was 0.05 mg / l after 24 hours, but this was within the safety standards.
[0052]
By using clay and frit glass as the binder 4, it is possible to combine not only the ore grains, the activated carbon grains and the dissimilar substances of the antibacterial metal, but also to form a ceramic structure, and to form an adsorbed ceramic of any shape. Can be formed. In particular, when frit glass is mixed, the MS method hardness is improved, and the mechanical strength against breakage, chipping, abrasion, and the like is improved. However, if the frit glass is excessively used, the voids 5 and the activated carbon 2 are clogged. Therefore, the amount of the frit glass should not exceed 20% by weight.
[0053]
Furthermore, it is convenient to combine the activated carbon powder with the average particle diameter of the activated carbon powder and the particle diameter of the ceramic ore, but the activated carbon powder may be large. When the ceramic particles are larger than the activated carbon powder, the function of the ceramic particles to hold the activated carbon powder is reduced, so that the sintered particles cannot be maintained in a sintered form and are easily damaged.
[0054]
If the average particle size of the activated carbon powder 3 is less than 5 μm, the activated carbon powder becomes too fine, and the ceramic particles fill pores formed between the activated carbon powder to eliminate voids, thereby lowering the adsorption ability. When the average particle size of the activated carbon powder exceeds 1000 μm, there is a concern that the activated carbon powder may become wet and swell when absorbing water, and may fall off the ceramic particles and collapse.
[0055]
In the case of the above embodiment, the description has been made with respect to the treatment of tap water. However, the adsorption ceramic of the present invention is not limited to the treatment of tap water, and because of its excellent adsorption performance, water treatment of pools and baths, water supply and sewage. It can be used for industrial applications such as various liquid treatments, such as water treatment, factory wastewater treatment, etc., as a filter material, and as a odor remover for gaseous fields. It can be applied to the electronics industry, environmental purification, medical care, agriculture, forestry, fisheries and other living environments.
[Brief description of the drawings]
1A and 1B are perspective views of adsorption ceramics having different shapes according to the present invention, wherein FIG. 1A is a spherical adsorption ceramic, FIG. 1B is a columnar adsorption ceramic, and FIG.
FIG. 2 is a structural diagram schematically showing a crystal structure of an adsorption ceramic.
[Explanation of symbols]
1 ore of ceramic material 2 ... activated carbon powder 3 ... silver powder 4 ... binder 10, 20, 30 ... adsorption ceramic.

Claims (2)

A porous ceramic structure composed of ore grains containing silicon oxide and aluminum oxide as main components, and at least 5% by weight or more and 30% by weight or less of an oxide of an alkali metal and an alkaline earth metal , 10% by weight or more and 65% by weight or less of activated carbon and 0.1% by weight or more and 5% by weight or less of antibacterial metal are mixed and sintered. Adsorption ceramic characterized. The ore grains serving as the structure of the porous ceramic, the activated carbon grains, the antibacterial metal, and a binder made of clay or frit glass for joining them are mixed, formed into a predetermined shape, and fired. The adsorption ceramic according to claim 1 , wherein:

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