【発明の詳細な説明】[Detailed description of the invention]
本発明は、北関東地方を中心に多産される関東
ローム及び大谷石を活用して、富栄養化等の問題
を惹起している河川、海等の汚染を浄化するため
及び畜糞等の悪臭防止を目的とする吸着剤の製法
を提供するものである。
関東ロームはSiO223〜30％、Al2O325〜28％、
Fe2O310〜15％、ig・loss13〜16％の組成をもち
Ｘ線、DTA等の鉱物組成の研究からハロイサイ
トを含有する火山ガラスを多量に伴なう粘土鉱物
であり、地質年代的には数百万年以前（新世代第
４紀）の火山灰風化物であることが知られてい
る。又、大谷石はSiO260〜73％、Al2O310〜15
％、Fe2O30.5〜２％、ig・loss4〜６％の組成で
鉱物学的にゼオライトを主成分としモンモリロナ
イト系の粘土鉱物及び火山ガラスを含む凝塊岩で
数千万年前（新世代第３紀）に生成されたものと
いわれている。
そして両者は共に北関東地方を中心に多産され
る重要な地下資源として注目されるもので、地元
ではその価値的活用が長らく渇望され、種々の試
みがなされてきた。しかしその現状は依然として
前者が土壌剤を、後者が建築材、土木材をその主
用途としている状況で、地方経済活性化の面から
さらなる用途開発が大望されている。
一方、都市及び人口密集地では合成洗剤、下水
等の多用により河・海の汚染が急速に進み、いわ
ゆる富栄養化により魚貝類が生息の危機に瀕して
いる。そして各地方自治体ではその対処策として
法的面及び技術面からの規制を検討中であるが、
経済性をも具備した有効な手段にはきめ手を欠い
ている現状である。又、畜糞等の悪臭も住民を悩
ます原因として多くの規制案が検討されている。
かゝる実情のもとにおいて本発明者は前述の関
東ローム及び大谷石について長年研究に従事して
きた経験及び知見を基に、両者が吸着性に秀れる
構造特性を有することに着目し、これを上記汚染
浄化のための吸着剤として活用する方途を生み出
したものである。
以下、実施例を基にその製造法を説明すると、
まず赤土を主成分とした関東ローム成分と粉状に
破砕した大谷石成分（又は石材としての切削中に
生じた廃粉でも良い）とをその用途に応じて適当
割合で配合する。この混合割合の決定については
（その理由は後述する）リン酸分を多く吸着させ
る場合には関東ローム成分を主とし、アンモニア
成分多吸着の場合はその逆とする。次に、上記２
成分の混合物中に塑性限界以下の範囲内で可及的
に少量の水を添加して、混練機に掛けて、両者を
混合〓和する。こゝで塑性限界以下の範囲内と
は、次行程の成型品作成の際にその形態保持が充
分可能な範囲をいい、混合比にもよるが一般的に
は略20〜40wt％の水分量となる。次いで、混〓
後の塊状物を例えば直径３mmの棒状顆粒体或いは
直径20mmの錠剤に成型する。そうして、この成型
体を350℃〜600℃の温度で約１〜２時間マツフル
炉、或いは電気炉等の加熱炉にて加熱し、関東ロ
ーム成分の熱分解による構造的改質及び大谷石成
分の固結化を促すことによつて本発明吸着剤を得
る。
本発明法はこのように、関東ローム成分と大谷
石成分とを混合するわけであるが、一応両者の構
造的特徴からもたらされる機能を各別に述べれ
ば、関東ロームは内部組織としてハロイサイト構
造を有するためリン酸分の吸着能に秀れ合成洗剤
等に多量に含有されて富栄養化の原因とされるリ
ン酸分を吸着浄化する。他方、大谷石はゼオライ
トに近似の構造を有するもので、アンモニア分の
吸着能に秀れ下水処理等に好適のものである。従
つて、両成分の結合によつて汚染水中のリン酸分
及びアンモニア分が共に浄化されることが、まず
はその併合的効果として言える。
次に、混合両成分中に水分を添加混〓すると関
東ローム中の少量の有機物及び大谷石中のベント
ナイト様物質の水和膨潤性が作用し粘土粒子同志
のすべりをよくして両者を強く密合させる。さら
にこれに加えて両成分の混〓はメカノケミカル的
表面特性の改良を促す事実が判明した。即ち、関
東ローム成分中には粘土分の他に高硬度のシルト
が10〜20％含まれ又大谷石中にもゼオライト及び
石英、長石類の高硬度成分が含まれるため混〓に
より相互に摩擦され、表面上にあるいは破断面に
吸着活性点が露出し、これにより吸着表面積が増
大して吸着能の向上が図られる。このことは、第
１表に示す通り、関東ロームと大谷石が夫々単独
で示す吸着能より混〓後の製品が約10〜20％の吸
着能上昇を示す実験結果からも裏付けられる。
The present invention utilizes Kanto loam and Oya stone, which are abundantly produced mainly in the northern Kanto region, to purify rivers, seas, etc., which are causing problems such as eutrophication, and to purify the odor of livestock feces. The present invention provides a method for producing an adsorbent for the purpose of prevention. Kanto loam has SiO 2 23-30%, Al 2 O 3 25-28%,
It is a clay mineral with a composition of 10-15% Fe 2 O 3 and 13-16% ig loss, and it is a clay mineral with a large amount of volcanic glass containing halloysite, based on mineral composition studies such as X-ray and DTA. It is known to be weathered volcanic ash from several million years ago (new generation Quaternary era). Also, Oya stone contains 60-73% SiO 2 and 10-15% Al 2 O 3
%, Fe 2 O 3 0.5-2%, ig・loss 4-6%. Mineralogically, it is a conglomerate rock whose main component is zeolite and contains montmorillonite clay minerals and volcanic glass. It is said to have been created during the 3rd generation. Both have attracted attention as important underground resources that are abundantly produced mainly in the northern Kanto region, and the local community has long desired to utilize them for their value, and various attempts have been made. However, the current situation is that the former is still mainly used as a soil agent, and the latter as a building material and civil lumber, and there is a strong desire to develop further uses from the perspective of revitalizing the local economy. On the other hand, in cities and densely populated areas, the heavy use of synthetic detergents and sewage has led to rapid pollution of rivers and oceans, and fish and shellfish habitats are under threat due to so-called eutrophication. Local governments are currently considering legal and technical regulations as a countermeasure.
At present, there is a lack of decision-making on effective means that are also economical. In addition, many regulations are being considered for the odor of livestock feces, etc., which is a cause of concern for residents. Under these circumstances, the inventors of the present invention, based on the experience and knowledge gained through many years of research on the aforementioned Kanto loam and Oya stone, focused on the fact that both have structural characteristics that make them excellent in adsorption. This has created a way to utilize the above-mentioned contamination as an adsorbent for purification. The manufacturing method will be explained below based on examples.
First, a Kanto loam component containing red clay as a main component and a powdered Oya stone component (or waste powder generated during stone cutting may also be used) are mixed in an appropriate ratio depending on the intended use. Regarding the determination of this mixing ratio (the reason will be described later), when a large amount of phosphoric acid is to be adsorbed, the Kanto loam component is used as the main component, and when a large amount of ammonia is to be adsorbed, it is determined to be the opposite. Next, the above 2
A small amount of water is added to the mixture of ingredients within a range below the plasticity limit, and the mixture is mixed with a kneader. In this case, the range below the plasticity limit refers to the range in which the shape can be sufficiently maintained during the next process of forming a molded product, and generally the moisture content is approximately 20 to 40 wt%, although it depends on the mixing ratio. becomes. Next, mix
The resulting mass is then shaped into rod-shaped granules with a diameter of 3 mm or tablets with a diameter of 20 mm, for example. Then, this molded body is heated at a temperature of 350°C to 600°C for about 1 to 2 hours in a heating furnace such as a Matsufuru furnace or an electric furnace, resulting in structural modification by thermal decomposition of Kanto loam components and Oya stone. The adsorbent of the present invention is obtained by promoting solidification of the components. In this way, the method of the present invention mixes the Kanto loam component and the Oya stone component, but if we briefly describe the functions brought about by the structural characteristics of both separately, Kanto loam has a halloysite structure as an internal structure. Therefore, it has excellent adsorption ability for phosphoric acid, and adsorbs and purifies phosphoric acid, which is contained in large amounts in synthetic detergents and is considered to be the cause of eutrophication. On the other hand, Oya stone has a structure similar to that of zeolite, has excellent ammonia adsorption ability, and is suitable for sewage treatment. Therefore, it can be said that the combined effect is that both the phosphoric acid content and the ammonia content in contaminated water are purified by the combination of both components. Next, when water is added to both mixed components, the hydration-swelling properties of a small amount of organic matter in the Kanto loam and the bentonite-like substance in the Oya stone work to improve the slippage between the clay particles and make the two strong and dense. Match. In addition to this, it has been found that mixing both components promotes improvement of mechanochemical surface properties. In other words, the Kanto loam component contains 10 to 20% of high hardness silt in addition to clay, and Oya stone also contains high hardness components such as zeolite, quartz, and feldspars, which cause mutual friction due to mixing. The adsorption active sites are exposed on the surface or on the fractured surface, thereby increasing the adsorption surface area and improving the adsorption capacity. This is also supported by the experimental results shown in Table 1, which show that the adsorption capacity of the product after mixing is about 10 to 20% higher than that of Kanto loam and Oya stone alone.
【表】
さらに、混〓後の成型品を350℃〜600℃に加熱
することは２方向に作用する。その一つは、まず
関東ロームの改質に働くもので、当該関東ローム
の組織は前述の通りハロイサイト構造を有するも
のであるが、これが加熱を受けると、組織に随伴
している火山ガラス風化物あるいは鉄ゲルのOH
分の放出及び結晶質の破壊等によりアロフエン構
造へと改質し、その結果アロフエン構造によるよ
り強い吸着性を示すことになる（表２参照）。こ
こでアロフエンとは、関東ロームの成長段階にお
いてハロイサイトの前段階を成す構造体をいう
が、多数の吸着活性点を有することから秀れた吸
着特性を示す。２つ目は大谷石成分の固結化に働
くもので、大谷石はその含有するベントナイト様
鉱物のために水中で膨潤崩壊してそのままではど
のように加圧しても水中での成形体保持が不可能
である。ところが、これに前述の加熱を施すこと
により、ベントナイト層間の水が除去され又水和
膨潤の原因となつているナトリウムの水和イオン
が粘土粒子層間に固着して常温常圧下で膨潤性が
失われるので水中でも強い固結化が保持されるも
のとなる（表３参照）。そして先の混〓時に添加
水分量を塑性限界以下の範囲内で可及的に少量の
ものとしたことは、成形体の加圧成型の際に粒子
表面に水の単分子層を形成せしめて、粒子同志を
至近距離に密接させ且つ充分潤滑的なものとし
て、最密充填の成形体を得られるものとする。
そして加熱温度を350℃〜600℃に設定したの
は、第３表の硬度変化と第２表の吸着能変化との
最良条件を採択したものである。
実施例 １
本発明にかかわる関東ローム（50wt％）：大
谷石粉（50wt％）混合吸着錠剤を用いて屎尿処
理場より採取した排水を使用してNH4 +及びPO３− ４
の吸着実験を行つた。好気性消化処理法（活性汚
泥法）により固形分を除いた放流水はNH＋ ４は
100ppm（mg／）でありPO３− ４は50ppm（mg／
）であつた。この放流排水の一部をとり出し直
径30cm、高さ200cmの充填吸着塔（吸着剤充填高
さ150cm）を用いて図１に示される条件下で吸着
実験を行つた。その結果は表Ａのごとくで、これ
より送液開始から８時間後にはじめてPO３− ４イオ
ンが検出され、10時間後にNH4イオンが出はじめ
るので本方式では８〜10時間で第２の充填吸着塔
にきりかえれば十分に両イオンの除去が行なわれ
ることが判明した。[Table] Furthermore, heating the molded product after mixing to 350°C to 600°C has a two-way effect. One of them is to modify the Kanto loam, which has a halloysite structure as mentioned above, but when this is heated, weathered volcanic glass that accompanies the structure is formed. Or iron gel OH
It is modified into an allofene structure due to the release of components and the destruction of crystalline substances, and as a result, it exhibits stronger adsorption due to the allofuene structure (see Table 2). Here, allofene refers to a structure that is a precursor to halloysite in the growth stage of Kanto loam, and exhibits excellent adsorption properties because it has a large number of adsorption active sites. The second one works to solidify the Oya Stone component. Due to the bentonite-like minerals it contains, Oya Stone swells and collapses in water, and no matter how much pressure is applied, Oya Stone cannot hold its shape in water. It's impossible. However, by heating the clay as described above, the water between the bentonite layers was removed, and the hydrated sodium ions, which are the cause of hydration swelling, stuck between the clay particle layers and lost their swelling properties at room temperature and pressure. Because of this, strong solidification is maintained even in water (see Table 3). In addition, the amount of water added during mixing was kept as small as possible within the range below the plasticity limit to prevent the formation of a monomolecular layer of water on the particle surface during pressure molding of the compact. By bringing the particles into close contact with each other and providing sufficient lubrication, a close-packed compact can be obtained. The heating temperature was set at 350° C. to 600° C. by adopting the best conditions for the change in hardness shown in Table 3 and the change in adsorption capacity shown in Table 2. Example 1 Kanto loam (50 wt%) and Otani stone powder (50 wt%) according to the present invention were used to collect NH 4 + and PO 3-4 using wastewater collected from a human waste treatment plant using a mixed adsorption tablet.
An adsorption experiment was conducted. The effluent from which the solid content has been removed by the aerobic digestion treatment method (activated sludge method) is NH + 4 .
100ppm (mg/) and PO 3-4 is 50ppm (mg /
). A portion of this discharged wastewater was taken out and an adsorption experiment was conducted under the conditions shown in Figure 1 using a packed adsorption tower with a diameter of 30 cm and a height of 200 cm (adsorbent filling height: 150 cm). The results are shown in Table A. From this, PO 3-4 ions are detected for the first time 8 hours after the start of liquid feeding , and NH 4 ions begin to appear after 10 hours, so in this method, the second filling is completed in 8 to 10 hours. It was found that both ions could be sufficiently removed by switching to an adsorption tower.
【表】
実施例 ２
本発明にかかわる関東ローム（50wt％）：大
谷石粉（50wt％）混合顆粒を散布して鶏舎の除
臭あるいは鶏糞運搬肥料化の脱臭のための実験を
行つた。水平型リボン混合機（約400内容積）
を用い、まづ鶏糞10Kgを平均に収納し10分間撹拌
し静置10分後に北川式ガス検知器を用い機内のア
ンモニアガス濃度を測定したところ120ppmであ
つた。次に本顆粒３Kgを混合機へ送入し10分間撹
拌混合し、静置10分後に測定したところアンモニ
アガス濃度70ppmとなり、除去率42％（１２０−７０／
１２０
＝0.42）であつた。更に２Kgの顆粒を追加し（合
計５Kg添加）混合撹拌した後上記同様な測定をし
た場合50ppmで除去率58％（１２０−５０／１２０＝0.5
8）で
あつた。悪臭の主なるものはアンモニア臭である
が、硫黄化合物系の悪臭にも効果あるため全体の
臭は著しく緩和され作業環境の改善は勿論鶏の発
育にも良好な結果を与えることが判明した。
本発明は以上のようで、関東ローム及び大谷石
の吸着性を利用して単に両者の併合的効果に止ま
らず、両者の保有する特性の有機的結合及びそれ
ら特性の物理化学的改質とにより、吸着性の改善
及び水中での固形保持性を具備させ、特にリン酸
及びアンモニア吸着の著効性により富栄養化等の
汚染問題の解消に資することができる。又、畜糞
等の悪臭及び廃液、廃ガス等の公害を惹起する物
質の吸着剤としての使用も可能である。もとより
これが地下資源の活用により地域経済振興の期待
に応え得ることはいうまでもない。[Table] Example 2 An experiment was conducted for deodorizing a chicken house or transporting chicken manure for use as fertilizer by spraying mixed granules of Kanto loam (50 wt%) and Otani stone powder (50 wt%) according to the present invention. Horizontal ribbon mixer (approximately 400 internal volume)
First, 10 kg of chicken manure was stored on average, stirred for 10 minutes, and after 10 minutes of standing, the ammonia gas concentration inside the machine was measured using a Kitagawa gas detector and found to be 120 ppm. Next, 3 kg of the present granules were sent to a mixer and stirred and mixed for 10 minutes, and after 10 minutes of standing, the ammonia gas concentration was 70 ppm, and the removal rate was 42% (120-70/
120 = 0.42). When 2 kg of granules were added (total of 5 kg added), mixed and stirred, and the same measurement as above was performed, the removal rate was 58% (120-50/120 = 0.5) at 50 ppm.
8) It was. Although the main odor is ammonia odor, it has been found that it is also effective against sulfur compound odor, so the overall odor is significantly alleviated, which not only improves the working environment but also has good results for the growth of chickens. As described above, the present invention utilizes the adsorption properties of Kanto loam and Oya stone, and is not limited to simply combining the two, but also organically combines the properties of both and physicochemically modifies those properties. It has improved adsorption properties and solid retention properties in water, and can contribute to solving pollution problems such as eutrophication due to its particularly effective adsorption of phosphoric acid and ammonia. Furthermore, it can also be used as an adsorbent for substances that cause pollution such as foul odors such as livestock feces, waste liquids, and waste gases. Needless to say, this can meet expectations for regional economic development by utilizing underground resources.