JPH0919680A - Water purifying agent and its production - Google Patents
Water purifying agent and its productionInfo
- Publication number
- JPH0919680A JPH0919680A JP19258795A JP19258795A JPH0919680A JP H0919680 A JPH0919680 A JP H0919680A JP 19258795 A JP19258795 A JP 19258795A JP 19258795 A JP19258795 A JP 19258795A JP H0919680 A JPH0919680 A JP H0919680A
- Authority
- JP
- Japan
- Prior art keywords
- purifying agent
- water purifying
- water
- cao
- compd
- 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
Abstract
Description
【０００１】[0001]
【発明の技術分野】本発明は水質浄化剤、さらに詳細に
は建材等の製造の過程で生ずる廃棄物を利用するととも
に、特にりん・色度・重金属類の除去性に優れた水質浄
化剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water purification agent, and more particularly to a water purification agent which utilizes waste generated in the process of manufacturing building materials and is particularly excellent in removing phosphorus, chromaticity and heavy metals. .
【０００２】[0002]
【従来技術および問題点】水質浄化としてのりんの除去
は、閉鎖性水域における富栄養化防止のため重要であ
る。このようなりんの除去技術には生物学的な除去、凝
集剤を使用した浄化方法、吸着剤を使用した方法などが
ある。一方、海域の環境基準として窒素・りんの濃度が
定められたことにより、これまでの除去方法では対応で
きない低濃度までの除去技術の開発が急務になってい
る。2. Description of the Related Art Removal of phosphorus as water purification is important for preventing eutrophication in closed water areas. Such phosphorus removal techniques include biological removal, purification methods using coagulants, methods using adsorbents, and the like. On the other hand, since the concentration of nitrogen and phosphorus has been set as an environmental standard in the sea area, there is an urgent need to develop a removal technology to a low concentration that cannot be dealt with by conventional removal methods.
【０００３】また、都市用水としての下水処理水の再利
用も行なわれるようになってきており、アオコをはじめ
とした藻類の発生に対する懸念から窒素・りんの除去は
重要な課題となっている。従来このようなりんの除去技
術には、生物学的な除去、凝集剤を用いた浄化方法、吸
着剤を用いた方法などがあるのは前述のとおりである
が、簡易に除去方式を導入できることから、吸着剤を用
いることが多い。Further, since the sewage treatment water for city water is being reused, the removal of nitrogen and phosphorus has become an important issue from the fear of the generation of algae such as water-bloom. As mentioned above, there are conventional methods of removing phosphorus such as biological removal, purification method using coagulant, method using adsorbent, etc., but the removal method can be easily introduced. Therefore, an adsorbent is often used.
【０００４】このような吸着剤としては、アニオンであ
るりん酸イオンを選択的に吸着できる活性アルミナや、
鹿沼土を用いた水質浄化を行なうことが検討されてい
る。しかしながら処理効果、経済性の面から十分とは言
い難いのが現状である。Examples of such an adsorbent include activated alumina capable of selectively adsorbing an anion phosphate ion,
It is considered to carry out water purification using Kanuma soil. However, it is difficult to say that it is sufficient in terms of treatment effect and economic efficiency.
【０００５】本発明は上述の問題点に鑑みなされたもの
であり、経済的にかつ効果的にりん・色度・重金属を除
去できる水質浄化剤を提供することを目的とする。The present invention has been made in view of the above problems, and an object of the present invention is to provide a water purification agent capable of economically and effectively removing phosphorus, chromaticity, and heavy metals.
【０００６】[0006]
【問題点を解決するための手段】上記目的を達成するた
め、本発明による水質浄化剤は、オートクレーブによっ
て水熱合成されたＣａＯ−ＳｉＯ2系の加熱脱水させた
無水物であることを特徴とするものである。In order to achieve the above object, the water purification agent according to the present invention is characterized in that it is a CaO--SiO 2 system heat-dehydrated anhydride hydrothermally synthesized by an autoclave. To do.
【０００７】上記の化合物はゾノトライト（Ｃａ6（Ｓ
ｉ6Ｏ17））・（ＯＨ）2、トバモライト（Ｃａ5（Ｓｉ6
Ｏ18Ｈ2））・（４Ｈ2Ｏ〜８Ｈ2Ｏ）が代表的水和物と
して知られている。また、オートクレーブによって、水
熱合成された工業薬品としては、現在広く建材として使
用されているＡＬＣは、トバモライトを主相とするもの
であり、また、ゾノトライトを主相とする窯業建材、あ
るいは、耐火断熱材料も知られている。The above compounds are zonotolite (Ca 6 (S
i 6 O 17 )). (OH) 2 and tobermorite (Ca 5 (Si 6
O 18 H 2)) · ( 4H 2 O~8H 2 O) has been known as a representative hydrates. As an industrial chemical hydrothermally synthesized by an autoclave, ALC, which is widely used as a building material nowadays, has tobermorite as a main phase, and also has a zonotlite as a main phase. Thermal insulation materials are also known.
【０００８】ＣａＯ−ＳｉＯ2系の水熱合成材料は、６
００℃の温度に加熱することにより、結晶水を放出し
て、結晶度の弱い針状または、リボン状βＣａＯＳｉＯ
2に転移するが、ＤＴＡによる測定によると、結晶水の
多いトバモライトは、７０５℃で脱水し８３５℃でβＣ
ａＯＳｉＯ2に転移するが、ゾノトライトは約１０００
℃付近で脱水が完了して転移するのであった。βＣａＯ
ＳｉＯ2は天然鉱物として珪灰石として知られるもので
密度の高い針状の鉱物であり、吸着などに効果のある気
孔の存在しないものであるが、本発明の処理によるβＣ
ａＯＳｉＯ2は多数の微細気孔を持った綿のような多孔
質のものであることを発見した。The CaO-SiO 2 hydrothermal synthetic material is 6
By heating to a temperature of 00 ° C., water of crystallization is released, and needle-like or ribbon-like βCaOSiO with weak crystallinity is released.
2) , but tobermorite with a large amount of water of crystallization was dehydrated at 705 ° C and βC at 835 ° C as measured by DTA.
Transfers to aOSiO 2 , but xonotlite is about 1000
Dehydration was completed at around ° C and the transfer occurred. βCaO
SiO 2 is known as wollastonite as a natural mineral and is a needle-like mineral having a high density and does not have pores which are effective for adsorption and the like, but βC produced by the treatment of the present invention
It has been discovered that aOSiO 2 is a cotton-like porous material with numerous fine pores.
【０００９】ＣａＯ−ＳｉＯ2系の現成物がオートクレ
ーブによって、ゾル状態となりゲルして固化した履歴を
持つ水和物は、キセロゲルの状態となり、３０〜５０Å
の微細気孔組織を内蔵し、比表面積は２００ｍ2／ｇｖ
という特徴を持つものである。The hydrate, which has a history that the CaO-SiO 2 system existing substance is in a sol state and gels and solidifies by an autoclave, becomes a xerogel state, and is 30 to 50Å.
With a specific surface area of 200 m 2 / gv
It has the characteristics of
【００１０】建材として使用されているＡＬＣは、５０
０μ〜５ｍｍという膨大な気孔を持つ多孔質体であるが
加熱によって結晶水が放出されたときに吸着剤として効
果のある微細気孔が出現することを見いだしたものであ
る。ALC used as a building material is 50
Although it is a porous body having huge pores of 0 μ to 5 mm, it was found that fine pores effective as an adsorbent appear when water of crystallization is released by heating.
【００１１】また、このような材料から生成されるβＣ
ａＯＳｉＯ2はリボン状の薄いハクヘンの重なったよう
な層状の構造を示し、連結された孔隙として存在するた
めに大きな比表面積を持つ吸着剤として特徴を与えてい
るものである。Further, βC produced from such a material
The aOSiO 2 has a layered structure in which ribbon-shaped thin astringent vines are superposed and is present as connected pores, and thus is characterized as an adsorbent having a large specific surface area.
【００１２】特願昭６１−５８４３６号において珪酸カ
ルシウム中のＣａＯを化学処理によって脱出させ、珪酸
カルシウム結晶形態のまま保持した非晶質シリカとし、
吸着剤や脱臭剤として使用する技術が知られているが、
本発明のように加熱脱水させて形成される気孔とは異な
るものである。[0012] In Japanese Patent Application No. 61-58436, CaO in calcium silicate is escaped by a chemical treatment to obtain amorphous silica in which the calcium silicate crystal form is maintained.
Although the technology used as an adsorbent and a deodorant is known,
It is different from the pores formed by heating and dehydration as in the present invention.
【００１３】本発明においては対象となる材料は、ＡＬ
Ｃの生産工程から排出されるもの、あるいは長期建材と
して使用された後の廃棄物を使用目的によって、板状、
塊状の形に加工した後、焼成炉内で６００℃以上で加熱
して結晶水を脱出させる等により、経済的に製造するこ
とができるものである。焼成温度は、トバモライト水和
物の場合は８００〜９００℃の焼成温度範囲がよい。さ
らに温度を上げると焼結が促進されて気孔の閉鎖が起こ
り、１１５０℃を越えるとβＣａＯＳｉＯ2はαＣａＯ
ＳｉＯ2となって結晶は粒状化して機能を失うものであ
る。ゾノトライト水和物は、結晶水の脱水が約８００℃
まで続くため、１０００〜１１５０℃の間がよい。ま
た、請求項２に示すように一般の水処理剤としては通常
１〜１０ｖ／ｗ程度の粒状のものが広く使用されてい
る。１ｍｍ未満であると除去効果はよいが、それ自身が
濁りの原因となり、１０ｍｍを越えると表面積が低下す
る。最も好ましい範囲は３〜５ｍｍである。さらに上記
の素材を化学的に見るとＣａＯ−ＳｉＯ2系のオートク
レーブ製品はＣａＯ／ＳｉＯ2比が０．８〜１．３程度
の範囲にあるが製造工程において少量のポルトランドセ
メントとフライアッシュを加えるものであり、Ａｌ2Ｏ3
を４〜５％含むものである。In the present invention, the target material is AL
Depending on the purpose of use, the material discharged from the production process of C, or the waste after being used as a long-term building material,
After being processed into a lump-like shape, it can be economically manufactured by heating at 600 ° C. or higher in a firing furnace to escape crystal water. The firing temperature is preferably 800 to 900 ° C. in the case of tobermorite hydrate. When the temperature is further raised, sintering is promoted and pores are closed, and when the temperature exceeds 1150 ° C, βCaOSiO 2 becomes αCaO.
It becomes SiO 2 and the crystals are granulated and lose their function. Zonotolite hydrate has a dehydration of crystal water of about 800 ° C.
Since it lasts up to 1000 ° C. to 1150 ° C. Further, as shown in claim 2, as a general water treatment agent, granular ones of about 1 to 10 v / w are widely used. If it is less than 1 mm, the removal effect is good, but it itself causes turbidity, and if it exceeds 10 mm, the surface area decreases. The most preferable range is 3 to 5 mm. Further, when the above materials are chemically viewed, CaO-SiO 2 autoclave products have a CaO / SiO 2 ratio in the range of 0.8 to 1.3, but a small amount of Portland cement and fly ash are added in the manufacturing process. Al 2 O 3
4 to 5% is included.
【００１４】浄化剤として作用を考察すると、ＣａＯ−
ＳｉＯ2系水和物が加熱されて結晶水を放出した状態の
βＣａＯＳｉＯ2は、前述のように結合度も極めて弱く
ＣａＯもＳｉＯ2も無定形に近いような反応活性の高い
状態にあり、とくに塩基性のＣａＯは酸性のりん酸化合
物とは容易に反応してＣａ3（ＰＯ4）2となり、さらに
水と長時間接するとＣａ3（ＰＯ4）2・Ｃａ（ＯＨ）2と
なり、不溶性のりん酸カルシウムとして固定するもので
ある。Considering the action as a purifying agent, CaO-
ΒCaOSiO 2 in a state in which SiO 2 hydrate is heated to release water of crystallization has extremely high bonding degree as described above, and CaO and SiO 2 are in a state of high reaction activity such that they are almost amorphous. Basic CaO easily reacts with an acidic phosphoric acid compound to form Ca 3 (PO 4 ) 2 , and when it is in contact with water for a long time, Ca 3 (PO 4 ) 2 · Ca (OH) 2 is formed , which is insoluble. It is fixed as calcium phosphate.
【００１５】ＳｉＯ2は、この反応系において詳細な反
応は確認できないが、活性のＳｉＯ2として存在し、り
ん酸との直接反応は期待できないが、比表面積の拡大に
よる吸着能は、何らかと有効な働きをしてなるものと推
定される。[0015] SiO 2 is not confirmed detailed reaction in the reaction system, present as SiO 2 activity, can not be the direct reaction is expected between the phosphate adsorption capacity by the expansion of specific surface area, effective whether any It is presumed that it will work.
【００１６】本発明による水質浄化剤に藻類の繁殖を防
止するために金属イオンと焼結固着することができる。
このような金属イオンには、チタン、銀、銅等の一種類
以上を使用する。これらの金属イオンは、塩化物、硫酸
塩、硝酸塩等に形となった水溶液を乾燥粒子に吸着させ
た後、脱水乾燥し、さらに焼成して酸化物の形として粒
子表面積に焼結反応によって固着させるものである。ま
た、これらの金属塩の付着量は、処理対象となる水中の
除去物質の含有量によって調整し、過剰の重金属イオン
が逆に水中に再溶解して害を与えないような限度量とな
る。また、銅等の重金属の焼結付着量が少ないと藻類の
繁殖防止効果を発揮できない恐れが生じる。The water purification agent according to the present invention may be sinter-fixed with metal ions in order to prevent the growth of algae.
For such metal ions, one or more kinds of titanium, silver, copper and the like are used. These metal ions are adsorbed on the dry particles by an aqueous solution in the form of chloride, sulfate, nitrate, etc., dehydrated and dried, and further baked to be fixed in the form of oxides on the surface area of the particles by a sintering reaction. It is what makes me. Further, the amount of these metal salts attached is adjusted by the content of the substance to be removed in the water to be treated, and is a limit amount in which excess heavy metal ions are not redissolved in water and do harm. Further, if the amount of heavy metal such as copper that is sintered and adhered is small, the effect of preventing the growth of algae may not be exhibited.
【００１７】水中におけるりん等の除去効果について
は、請求項１に示したものと金属イオンを固着させたも
のとはほとんど差は認められないが、硫化水素の除去に
著しい効果があったものであり、銅、銀等の酸化物が無
定形の形として存在し、多数の気体分子を吸着する親和
性の強い状態にあると考えられる。Regarding the effect of removing phosphorus and the like in water, there is almost no difference between the one described in claim 1 and the one in which metal ions are fixed, but there was a remarkable effect in removing hydrogen sulfide. It is considered that copper, silver, and other oxides exist in an amorphous form and have a strong affinity for adsorbing a large number of gas molecules.
【００１８】以下、本発明の実施例について説明する。Examples of the present invention will be described below.
【００１９】[0019]
【実施例１】ＡＬＣ粒（商品名：ヘーベル、旭化成建材
（株）製）３〜５ｗ／ｗに整粒した後、８００℃の温度
で焼成した無水和物で、かさ比重０．４〜０．４５、Ｘ
線回折による結晶相はβＣａＯＳｉＯ2であった。Example 1 ALC granules (trade name: Hebel, manufactured by Asahi Kasei Construction Materials Co., Ltd.) 3-5 w / w sized, and then calcined at a temperature of 800 ° C. Anhydrous anhydride having a bulk specific gravity of 0.4-0. .45, X
The crystal phase by line diffraction was βCaOSiO 2 .
【００２０】また、上記ＡＬＣ粒を３〜５ｍｍに整粒
し、約１００℃で乾燥した後、温度２０〜２２℃の１０
％硫酸銅水溶液中に５分間浸漬した後、１００℃での乾
燥工程を経て８００℃で焼成したＣｕＯ付着量は１．５
〜２ｇ／ｋｇであった。Further, the above ALC particles are sized to 3 to 5 mm, dried at about 100 ° C., and then 10 at a temperature of 20 to 22 ° C.
% Copper sulphate aqueous solution was dipped in a 5% copper sulfate aqueous solution for 5 minutes, then dried at 100 ° C. and baked at 800 ° C.
Was ~ 2 g / kg.
【００２１】[0021]
【実施例２】前記水質浄化剤を５ｇを３００ｍｌの三角
フラスコに加えた後、標準液２００ｍｌを注入して撹拌
し、２時間後に試験水を採取して水質分析を実施した結
果を表１に示す。また、表２には、同様の操作で求めた
りんの等の温吸着量を示す。その比較例として従来の活
性アルミナによる水質浄化剤の値も同表に示した。Example 2 After adding 5 g of the water purification agent to a 300 ml Erlenmeyer flask, 200 ml of the standard solution was poured and stirred, and after 2 hours, test water was collected and water quality analysis was performed. Show. In addition, Table 2 shows the amount of phosphorus adsorbed at a temperature determined by the same operation. As a comparative example, the value of the conventional water purification agent using activated alumina is also shown in the same table.
【００２２】 [0022]
【００２３】 [0023]
【００２４】[0024]
【発明の効果】以上説明したように、本発明による水質
浄化剤は、りん・色度・重金属等の除去ならびに臭気成
分の除去に効果がある。しかも原料は未利用資源のリサ
イクルによるため経済性も優れた素材であり、なおかつ
素材の製造時に有害物質の混入の恐れがないために、材
料に使用に伴う安全性も確保される利点がある。As described above, the water purification agent according to the present invention is effective in removing phosphorus, chromaticity, heavy metals, etc. and odorous components. Moreover, the raw material is a material that is highly economical because it is recycled from unused resources, and since there is no fear of harmful substances being mixed in during the production of the material, there is an advantage that the safety associated with the use of the material is secured.
【００２５】さらに本発明による水質浄化剤は、水のｐ
Ｈが中性域でも吸着能が大きく、従来の活性アルミナ
（りんの吸着能が高まるｐＨが４以下で使用する必要が
ある）に比較して広いｐＨ領域で使用できる。また、本
発明による材料は、独特の微細な気孔組織を有し、水処
理以外の有害ガス成分の除去等にも効果的なため、水処
理以外の用途の拡大も期待できるものである。Furthermore, the water purification agent according to the present invention is
Even when H is in the neutral range, it has a large adsorptive capacity and can be used in a wider pH range than conventional activated alumina (which must be used at a pH of 4 or less to increase the adsorptivity of phosphorus). Further, since the material according to the present invention has a unique fine pore structure and is effective for removing harmful gas components other than water treatment, it can be expected to expand applications other than water treatment.
Claims (3)
ａＯ−ＳｉＯ2系の水和化合物を粒状あるいは塊状に成
形し、６００〜１２００℃に温度範囲に焼成されたβＣ
ａＯＳｉＯ2を主結晶相とする水質浄化剤。1. C hydrothermally synthesized by an autoclave
βC formed by molding an aO-SiO 2 hydrated compound into a granular or lump form and firing it at a temperature range of 600 to 1200 ° C.
A water purification agent whose main crystalline phase is aOSiO 2 .
〜２０ｍｍに整粒した後、６００〜１２００℃の温度で
焼成させたものである水質浄化剤。2. The water purification agent has a particle size of 1 for ALC building material products.
A water purification agent obtained by sizing the particles to -20 mm and then firing at a temperature of 600 to 1200 ° C.
が焼結被覆されていることを特徴とする請求項１または
２記載の水質浄化剤。3. The water purification agent according to claim 1, wherein the particle surface of the water purification agent is sintered and coated with a metal compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19258795A JPH0919680A (en) | 1995-07-05 | 1995-07-05 | Water purifying agent and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19258795A JPH0919680A (en) | 1995-07-05 | 1995-07-05 | Water purifying agent and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0919680A true JPH0919680A (en) | 1997-01-21 |
Family
ID=16293766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19258795A Pending JPH0919680A (en) | 1995-07-05 | 1995-07-05 | Water purifying agent and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0919680A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100293536B1 (en) * | 1998-10-23 | 2001-09-17 | 전용진 | Removal method of phosphorus in wastewater by using lightweight foam concrete |
| JP2001521441A (en) * | 1997-04-18 | 2001-11-06 | カボット、コーポレーション | Use of airgel as adsorbent |
| KR20020070923A (en) * | 2002-08-06 | 2002-09-11 | 홍영호 | Method for Removal of Heavymetals in wastewater using ALC |
| KR102002775B1 (en) * | 2019-03-14 | 2019-07-23 | 최병윤 | Manufacturing method of ceramic ball for water treatment |
-
1995
- 1995-07-05 JP JP19258795A patent/JPH0919680A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001521441A (en) * | 1997-04-18 | 2001-11-06 | カボット、コーポレーション | Use of airgel as adsorbent |
| KR100293536B1 (en) * | 1998-10-23 | 2001-09-17 | 전용진 | Removal method of phosphorus in wastewater by using lightweight foam concrete |
| KR20020070923A (en) * | 2002-08-06 | 2002-09-11 | 홍영호 | Method for Removal of Heavymetals in wastewater using ALC |
| KR102002775B1 (en) * | 2019-03-14 | 2019-07-23 | 최병윤 | Manufacturing method of ceramic ball for water treatment |
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