JP2019209247A - Chlorine removing material and chlorine-removed water filtrated thereby - Google Patents
Chlorine removing material and chlorine-removed water filtrated thereby Download PDFInfo
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Abstract
Description
この発明は、塩素除去材、及びこの塩素除去材によって処理された塩素除去水に関し、詳しくは土と草木灰の混合物の焼結粒子からなる塩素除去材、及びこの塩素除去材で処理することにより得られる塩素除去水に関する。 The present invention relates to a chlorine removing material and chlorine removing water treated with the chlorine removing material, and more specifically, a chlorine removing material comprising sintered particles of a mixture of soil and plant ash, and a treatment with the chlorine removing material. Related to chlorine-removed water.
飲料水は、河川、湖沼、地下水等の水を公共の浄水施設で処理されて供されている。この処理としては、凝集・沈降処理、活性炭処理、オゾン処理、塩素等による消毒処理等があげられる。 Drinking water is provided by treating water such as rivers, lakes, and groundwater at public water purification facilities. Examples of this treatment include coagulation / sedimentation treatment, activated carbon treatment, ozone treatment, disinfection treatment with chlorine and the like.
前記の塩素による消毒処理を行うため、処理された水には少量ながら塩素が残留する。この塩素を処理する方法として、特許文献１に記載されているろ過材を用いる方法等が知られている。
そして、この特許文献１には、これに記載のろ過材を用いた場合、処理される前の水は酸性を示すが、処理によってアルカリ性にシフトする、と記載されている。
Since the disinfection treatment with chlorine is performed, a small amount of chlorine remains in the treated water. As a method for treating this chlorine, a method using a filter medium described in Patent Document 1 is known.
And in this patent document 1, when the filter medium described in this is used, although water before processing shows acidity, it is described that it shifts to alkalinity by processing.
ところで、一般に水道水に釘等をつけておくと、錆が生じるが、前記特許文献１に記載のろ過材によって処理された水を用いても、同様に錆が生じる。これは、使用した水に酸化性を有する物質、又は酸化を補助する物質が溶存されているためと考えられる。 By the way, generally, when nails or the like are attached to tap water, rust is generated, but rust is similarly generated even when water treated with the filter medium described in Patent Document 1 is used. This is considered because the substance which has oxidizing property in the used water or the substance which assists oxidation is dissolved.
そこで、この発明は、塩素を除去すると共に、処理された水に抗酸化性を付与することのできる塩素除去材及びその塩素除去材で処理された抗酸化性を有する塩素除去水を提供することを目的とする。 Accordingly, the present invention provides a chlorine removing material capable of removing chlorine and imparting antioxidant properties to the treated water, and chlorine removing water having antioxidant properties treated with the chlorine removing material. With the goal.
この発明は、下記の構成を有する塩素除去材を用いることにより、前記の課題を解決したのである。
［１］泥岩及び泥灰岩から選ばれる少なくとも１種の粉化物とイネ科植物又はショウガ科植物の草木灰との混合物の焼結粒子からなり、前記粉化物と前記草木灰との混合比（重量比）は、粉化物／草木灰で１０／９０以上４５／５５以下である塩素除去材。
［２］［１］に記載の塩素除去材によって処理された塩素除去水。
［３］泥岩及び泥灰岩から選ばれる少なくとも１種の粉化物を乾燥して破砕することにより粉化物を得、イネ科植物又はショウガ科植物を乾燥、燃焼して草木灰を得、前記粉化物及び前記草木灰を、粉化物／草木灰で１０／９０以上４５／５５以下（重量比）となるように、水と共に混合して粒子状物とし、得られた前記粒子状物を１１００℃以上１４００℃以下で燃焼することにより焼結粒子を得、前記焼結粒子を冷却することにより得られる塩素除去材の製造方法。
The present invention solves the above-mentioned problems by using a chlorine removing material having the following configuration.
[1] It is composed of sintered particles of a mixture of at least one powdered material selected from mudstone and marlstone and grass ash of a grass family plant or ginger plant plant, and a mixing ratio (weight ratio) of the powdered material and plant grass ash ) Is a chlorine remover that is 10/90 or more and 45/55 or less in powdered material / plant ash.
[2] Chlorine-removed water treated with the chlorine-removing material according to [1].
[3] Drying and crushing at least one powdered material selected from mudstone and marlstone to obtain a powdered product, drying and burning a grass family plant or ginger plant plant to obtain plant ash, the powdered product And the plant ash is mixed with water so that it becomes 10/90 to 45/55 (weight ratio) as a powdered product / plant ash to form a particulate matter, and the obtained particulate matter is 1100 ° C. to 1400 ° C. The manufacturing method of the chlorine removal material obtained by obtaining sintered particle by burning below and cooling the said sintered particle.
この発明によると、所定の岩石又は土の粉化物と所定の草木灰を所定割合で混合し、焼結した粒子を用いるので、得られる粒子は脱塩素能を有し、この粒子で処理した水の塩素含有量を減少させることができる。また、この粒子により、処理される水の酸化能を除去するため、処理される水に抗酸化性を付与することができる。この処理される水の酸化能を除去する機構は明らかになっていないが、処理される水に含まれる酸化性を有する物質や酸化を補助する物質を除去する、この粒子により、処理される水に含まれる酸化性を有する物質を還元する物質を水に付与して、酸化能を除去する、この粒子により、処理される水に含まれる酸化を補助する物質と反応する物質を水に付与して、酸化補助機能を除去する、等の機構が推測される。 According to the present invention, since a predetermined rock or soil powder and a predetermined plant ash are mixed at a predetermined ratio and sintered particles are used, the obtained particles have dechlorination ability, and water treated with these particles The chlorine content can be reduced. Moreover, since the oxidation ability of the water to be treated is removed by the particles, it is possible to impart an antioxidant property to the water to be treated. Although the mechanism for removing the ability to oxidize the treated water is not clear, the treated water is treated by this particle, which removes the oxidizable substance contained in the treated water and the substance that assists oxidation. By adding to the water a substance that reduces the oxidizing substance contained in the water and removing the oxidizing ability, this particle gives the water a substance that reacts with the substance that assists the oxidation contained in the treated water. Thus, a mechanism such as removal of the oxidation assist function is presumed.
この発明にかかる塩素除去材は、所定の岩石又は土の粉化物と、所定の草木灰との混合物の焼結粒子からなる。
［岩石又は土の粉化物］
前記の粉化物は、岩石又は土を粉化したものである。この岩石としては、泥岩及び泥灰岩があげられ、これらの少なくとも１種が用いられる。また、前記土は、岩石が風化して生成した粗粒をいい、本願においては、泥岩及び泥灰岩が風化して生成した粗粒をいう。
The chlorine removing material according to the present invention is composed of sintered particles of a mixture of a predetermined rock or soil powder and a predetermined plant ash.
[Rock or soil powder]
The above-mentioned powdered product is a powdered rock or soil. Examples of the rock include mudstone and tuff, and at least one of them is used. Moreover, the said soil means the coarse grain produced | generated by the weathering of a rock, and in this application, it means the coarse grain produced | generated by the weathering of a mudstone and a tuff.
前記の粉化は、前記の岩石や土を乾燥し、周知の方法で粉砕したものをいい、粉砕の程度は、前記草木灰との混合が十分に行われる程度の細かさがあれば十分である。 The above-mentioned pulverization refers to a material obtained by drying the above-mentioned rock or soil and pulverizing it by a well-known method. The degree of pulverization is sufficient if it is fine enough to be mixed with the plant ash. .
［草木灰］
前記草木灰とは、草や木の植物を乾燥させ、燃焼させて得られる灰であり、カリウムや石灰分を多く含む。個々で用いられる植物としては、イネ科植物又はショウガ科植物があげられる。このイネ科植物としては、イネ、エリアンサス等があげられ、また、ショウガ科植物としては、月桃等が挙げられる。
これらの植物は、どの部分を使用してもよく、具体的には、葉やもみ殻等をあげることができる。
[Plant ash]
The plant ash is ash obtained by drying and burning grass and tree plants, and contains a large amount of potassium and lime. Plants used individually include gramineous plants or ginger family plants. Examples of the Gramineae plant include rice and Elianthus, and examples of the Gingeraceae plant include moon peach.
Any part of these plants may be used, and specific examples thereof include leaves and rice husks.
［粒子状物］
前記の粉化物と草木灰とは、水をバインダーとして用いて混合され、粒子状に成形された後に燃焼に供される。
この粒子状物の形状は、この発明にかかる塩素除去材として使用可能であれば、球状（真球状、楕円体を含む）、方形状等、任意の形状とすることができる。
前記の粉化物と草木灰との混合比（重量比）は、粉化物／草木灰で１０／９０以上がよく、１５／８５以上が好ましく、２０／８０以上がより好ましい。１０／９０より小さいと、粉化物が少なくなりすぎ、得られる焼結粒子の表面に細孔が十分に生じず、塩素除去材として使用する場合、十分な塩素除去機能を生じにくくなるおそれがある。一方、混合比の上限は、粉化物／草木灰で４５／５５以下がよく、４０／６０以下が好ましい。４５／５５より大きいと、草木灰が少なくなりすぎ、塩素除去材として使用するとき、抗酸化能付与機能が十分に生せず、これによって処理された塩素除去水に抗酸化能を十分に付与できないおそれが生じる。
[Particulate matter]
The powdered product and plant ash are mixed using water as a binder, formed into particles, and then subjected to combustion.
The shape of the particulate matter can be any shape such as a spherical shape (including a true spherical shape and an ellipsoid), a rectangular shape and the like as long as it can be used as a chlorine removing material according to the present invention.
The mixing ratio (weight ratio) between the powdered product and the plant ash is preferably 10/90 or more, preferably 15/85 or more, and more preferably 20/80 or more in the powdered product / plant ash. If it is less than 10/90, the amount of powdered product will be too small, and there will be insufficient pores on the surface of the resulting sintered particles, which may make it difficult to produce a sufficient chlorine removal function when used as a chlorine removal material. . On the other hand, the upper limit of the mixing ratio is preferably 45/55 or less, preferably 40/60 or less, for powdered material / plant ash. When it is larger than 45/55, the amount of plant ash becomes too small, and when used as a chlorine removing material, the antioxidant ability imparting function does not sufficiently occur, and the treated chlorine removing water cannot sufficiently impart the antioxidant ability. There is a fear.
［焼結粒子］
前記粒子状物を燃焼することにより、焼結粒子が得られる。この燃焼温度は、１０００℃以上がよく、１１００℃以上が好ましく、１２００℃以上がより好ましい。一方、燃焼温度の上限は１４００℃以下がよく、１３００℃以下が好ましい。また、燃焼時間は、１０分間以上３０分間以下がよい。燃焼温度が前記範囲より低かったり、燃焼時間が前記範囲より短かったりすると、十分に焼結せず、得られる粒子がもろくなりやすく、結果として、十分な塩素除去機能を発しえなくなるおそれがある。また、燃焼温度が前記範囲より高かったり、燃焼時間が前記範囲より長かったりすると、得られる焼結粒子の表面に生じた細孔が塞がったり、草木灰の燃焼により、焼結粒子が崩れやすくなったりして、十分な塩素除去機能や抗酸化能付与機能を発揮しえなくなるおそれがある。
この焼結粒子を自然冷却することにより、本願発明の塩素除去材とすることができる。
[Sintered particles]
By burning the particulate matter, sintered particles are obtained. The combustion temperature is preferably 1000 ° C. or higher, preferably 1100 ° C. or higher, and more preferably 1200 ° C. or higher. On the other hand, the upper limit of the combustion temperature is preferably 1400 ° C. or less, and preferably 1300 ° C. or less. The combustion time is preferably 10 minutes or more and 30 minutes or less. If the combustion temperature is lower than the above range or the combustion time is shorter than the above range, the resulting particles are not sufficiently sintered and the resulting particles tend to be brittle, and as a result, there is a possibility that a sufficient chlorine removing function cannot be performed. Also, if the combustion temperature is higher than the above range or the combustion time is longer than the above range, the pores generated on the surface of the obtained sintered particles are blocked, or the sintered particles are liable to collapse due to the burning of plant ash. As a result, there is a possibility that a sufficient chlorine removing function and an antioxidant ability-imparting function cannot be exhibited.
By naturally cooling the sintered particles, the chlorine removing material of the present invention can be obtained.
［塩素除去材の製法］
この発明に係る塩素除去材は、次の方法で製造することができる。
まず、泥岩及び泥灰岩から選ばれる少なくとも１種を、自然乾燥等の方法で乾燥する。次いで、周知の方法で破砕して、粉化物を製造する。
また、イネ科植物又はショウガ科植物を自然乾燥等の方法で乾燥する。次いで、これを燃焼して草木灰を得る。
前記の方法で得られた粉化物及び草木灰を、前記した範囲内の割合で、水を加えながら混合する。この際の水の添加量は、混合物のダマができる程度で十分である。これにより、混合物からなる粒子状物を得る。
得られた前記粒子状物を前記の燃焼温度及び燃焼時間の範囲内で燃焼することにより焼結粒子を製造することができる。
そして、得られた焼結粒子を自然冷却することにより塩素除去材を製造することができる。
[Chlorine remover manufacturing method]
The chlorine removing material according to the present invention can be manufactured by the following method.
First, at least one selected from mudstone and tuff is dried by a method such as natural drying. Subsequently, it grind | pulverizes by a known method and manufactures a powdered material.
Further, the grass family or ginger family plant is dried by a method such as natural drying. This is then burned to obtain plant ash.
The powdered material and plant ash obtained by the above method are mixed at a ratio within the above range while adding water. In this case, it is sufficient that the amount of water added is such that the mixture can be lumped. Thereby, the particulate matter which consists of a mixture is obtained.
Sintered particles can be produced by burning the obtained particulate matter within the range of the combustion temperature and combustion time.
And the chlorine removal material can be manufactured by naturally cooling the obtained sintered particle.
［塩素除去水］
前記の焼結粒子は、塩素除去材として使用することができる。この塩素除去材を容器に入れ、この容器に水を入れたり、充填塔などに充填し、これに水を通すことによって、水中の塩素を除去し、塩素除去水を得ることができる。塩素が除去できる理由は、はっきりしないが、塩素除去材の細孔による塩素成分の吸着、塩素除去材の原料に由来する成分による塩素成分の反応、吸着等によることが考えられる。
また、前記塩素除去材は、抗酸化能付与機能を有するので、得られた塩素除去水は、抗酸化能を有する。
[Chlorine-removed water]
The sintered particles can be used as a chlorine removing material. By putting this chlorine removing material into a container, filling the container with water, or filling a packed tower or the like, and passing water therethrough, chlorine in water can be removed, and chlorine-removed water can be obtained. The reason why chlorine can be removed is not clear, but may be due to adsorption of chlorine components by the pores of the chlorine removing material, reaction of chlorine components by components derived from the raw material of the chlorine removing material, adsorption, and the like.
Moreover, since the said chlorine removal material has an antioxidant ability provision function, the obtained chlorine removal water has an antioxidant ability.
次に、本願発明を実施例を用いて詳細に説明する。
［実施例１］
沖縄にある泥岩（クチャ）をビニルシートの上に薄く広げ、３０日間放置し、自然乾燥させた。そして、２つの粉砕機（（株）マゼラー製：マゼラー産業機械６００Ｈと、（株）アイシンナノテクノロジーズ製：ナノジェットマイザーＮＪ−５０）に順番にかけて、細かく粉砕した。
また、イネ科の多年草であるエリアンサスの葉を取り、ビニルシートの上に薄く広げ、３０日間放置し、自然乾燥させた。そして、火をつけて燃やし、草木灰を得た。
次に、クチャの粉砕物２０重量部と草木灰８０重量部を水を加えながら混合し、混合物を球状（真球状か、真球状に近い楕円体）に成形した。なお、このとき加えた水の量は、水や混合物が流れ出ず、混合物の成形を行いやすい量とした。
得られた混合物の粒子状物を１１００℃〜１１５０℃で３０分間焼成し、焼結粒子を得た。次いで、焼結粒子を３日間放置して自然冷却させ、塩素除去材を得た。
Next, the present invention will be described in detail using examples.
[Example 1]
Mudstone (Kucha) in Okinawa was spread thinly on a vinyl sheet, allowed to stand for 30 days and allowed to dry naturally. And it grind | pulverized finely in order in two crushers (Corporation | Co., Ltd. product: Mazeler industrial machine 600H, and Aisin nanotechnology Co., Ltd .: NanoJet Mizer NJ-50).
Elianthus leaves, which are perennials of the grass family, were taken, spread thinly on a vinyl sheet, allowed to stand for 30 days and allowed to dry naturally. Then, it was burned with fire, and plant ash was obtained.
Next, 20 parts by weight of crushed cucumber and 80 parts by weight of plant ash were mixed while adding water, and the mixture was formed into a sphere (true sphere or ellipsoid close to true sphere). The amount of water added at this time was such that water or the mixture did not flow out and the mixture could be easily formed.
The particulate matter of the obtained mixture was baked at 1100 ° C. to 1150 ° C. for 30 minutes to obtain sintered particles. Next, the sintered particles were allowed to stand for 3 days to be naturally cooled to obtain a chlorine removing material.
（塩素除去能測定）
得られた塩素除去材４０ｇを容器に入れ、塩素濃度１．０２ｍｇ／Ｌの水（水道水）６０ｇを温度５０℃にして加え、５〜１０秒ほど放置し、塩素除去材を取り出した。得られた処理水の塩素濃度を測定したところ、検出限界以下（０．０５ｍｇ／Ｌ未満）であった。
なお、塩素濃度は、上水試験方法（２０１１年）ＩＩ−３−３０．２に記載の方法にしたがって行った。
(Chlorine removal ability measurement)
40 g of the obtained chlorine removing material was put in a container, 60 g of water (tap water) having a chlorine concentration of 1.02 mg / L was added at a temperature of 50 ° C., and left for about 5 to 10 seconds to take out the chlorine removing material. When the chlorine concentration of the obtained treated water was measured, it was below the detection limit (less than 0.05 mg / L).
The chlorine concentration was determined according to the method described in Water Supply Test Method (2011) II-3-30.2.
（抗酸化能測定）
また、得られた処理水４５ｇに鉄製のクリップを１ｇ入れ、２０日間放置した。対比実験として、処理前の水に対しても同様の条件で鉄製のクリップ１ｇを入れて２０日間放置した。
そのときの変化の様子を図１に示す。なお、図１の（ａ）はクリップを入れた直後、（ｂ）は１０日目、（ｃ）は２０日目の様子を示す。そして、各図中の「実験水」は前記した処理水を意味し、「水道水」は前記した処理前の水を意味する。さらに、図１（ｂ）（ｃ）の「水道水」においては、グレー度が高くなっているが、これは、赤褐色になったものをグレースケールで示したためである。
その結果、処理水（図中の「実験水」）には変化が見られなかったが、処理前の水（図中の「水道水」）は赤褐色となり、クリップ表面に赤錆がでて、水不溶物が生じていることが確認された。さらに、１０日後処理前の水（図１（ｂ）の「水道水」）より、２０日後処理前の水（図１（ｃ）の「水道水」）の方が、赤褐色がより濃かった。
(Measurement of antioxidant capacity)
Further, 1 g of an iron clip was put into 45 g of the obtained treated water and left for 20 days. As a comparison experiment, 1 g of an iron clip was added to water before treatment under the same conditions and left for 20 days.
The state of the change at that time is shown in FIG. 1A shows a state immediately after inserting a clip, FIG. 1B shows a state on the 10th day, and FIG. 1C shows a state on the 20th day. “Experimental water” in each figure means treated water as described above, and “tap water” means water before treatment as described above. Furthermore, in the “tap water” of FIGS. 1B and 1C, the gray level is high, because the reddish brown color is shown in gray scale.
As a result, there was no change in the treated water (“experimental water” in the figure), but the water before treatment (“tap water” in the figure) became reddish brown, red rust appeared on the clip surface, It was confirmed that insoluble matter was generated. Further, the water before 20 days after treatment ("tap water" in FIG. 1 (c)) was darker in reddish brown than the water before treatment after 10 days ("tap water" in FIG. 1 (b)).
［実施例２］
エリアンサスの代わりにイネのもみ殻を用いた以外は、実施例１と同様にして塩素除去材を得た。
実施例１に記載の方法と同様にして塩素除去能測定を行ったところ、１．０２ｍｇ／Ｌの塩素濃度を有する水が、検出限界以下となった。
また、実施例１に記載の方法と同様にして抗酸化能測定を行ったところ、実施例１の場合と同様に、処理水には変化が見られなかったが、処理前の水は赤褐色となり、クリップ表面に赤錆がでていることが確認された。
[Example 2]
A chlorine removing material was obtained in the same manner as in Example 1 except that rice chaff was used instead of Eliansus.
When the chlorine removal ability was measured in the same manner as in the method described in Example 1, water having a chlorine concentration of 1.02 mg / L was below the detection limit.
Further, when the antioxidant ability was measured in the same manner as described in Example 1, no change was observed in the treated water as in Example 1, but the water before treatment became reddish brown. It was confirmed that red rust appeared on the clip surface.
［実施例３］
エリアンサスの代わりにショウガ科月桃の葉を用いた以外は、実施例１と同様にして塩素除去材を得た。
実施例１に記載の方法と同様にして塩素除去能測定を行ったところ、１．０２ｍｇ／Ｌの塩素濃度を有する水が、検出限界以下となった。
また、実施例１に記載の方法と同様にして抗酸化能測定を行ったところ、実施例１の場合と同様に、処理水には変化が見られなかったが、処理前の水は赤褐色となり、クリップ表面に赤錆がでていることが確認された。
[Example 3]
A chlorine removing material was obtained in the same manner as in Example 1 except that ginger peach leaves were used instead of Elianthus.
When the chlorine removal ability was measured in the same manner as in the method described in Example 1, water having a chlorine concentration of 1.02 mg / L was below the detection limit.
Further, when the antioxidant ability was measured in the same manner as described in Example 1, no change was observed in the treated water as in Example 1, but the water before treatment became reddish brown. It was confirmed that red rust appeared on the clip surface.
Claims (3)
前記粉化物と前記草木灰との混合比（重量比）は、粉化物／草木灰で１０／９０以上４５／５５以下である塩素除去材。 Comprising sintered particles of a mixture of at least one powdered material selected from mudstone and marlstone and grass ash of a grass family plant or ginger plant plant,
The mixing ratio (weight ratio) of the pulverized product and the plant ash is 10/90 or more and 45/55 or less of the pulverized product / plant ash.
イネ科植物又はショウガ科植物を乾燥、燃焼して草木灰を得、
前記粉化物及び前記草木灰を、粉化物／草木灰で１０／９０以上４５／５５以下（重量比）となるように、水と共に混合して粒子状物とし、
得られた前記粒子状物を１１００℃以上１４００℃以下で燃焼することにより焼結粒子を得、
前記焼結粒子を冷却することにより得られる塩素除去材の製造方法。 A powdered product is obtained by drying and crushing at least one selected from mudstone and marlstone,
Dry and burn grasses or ginger plants to obtain plant ash,
The powdered product and the plant ash are mixed with water so as to be 10/90 or more and 45/55 or less (weight ratio) of the powdered product / plant ash to form a particulate material,
By burning the obtained particulate matter at 1100 ° C. or higher and 1400 ° C. or lower to obtain sintered particles,
A method for producing a chlorine removing material obtained by cooling the sintered particles.
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| JP2005335969A (en) | 2004-05-24 | 2005-12-08 | Suminoe Textile Co Ltd | Lightweight porous material, its producing method, carrier and water cleaning material |
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