JP4518905B2 - Filter aid comprising easily water disintegrating diatomaceous earth molding and method for producing the same - Google Patents
Filter aid comprising easily water disintegrating diatomaceous earth molding and method for producing the same Download PDFInfo
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本発明は、易水中崩壊性珪藻土成形物からなる濾過助剤及びその製造方法に関し、特に、プール、公衆浴場等に用いられる水の濾過清澄用の濾過助剤として好適な易水中崩壊性珪藻土成形物からなる濾過助剤及びその製造方法に関するものである。 The present invention relates to a filter aid composed of an easily water-disintegrating diatomaceous earth molded product and a method for producing the same, and in particular, an easily water-disintegrating diatomaceous earth molding suitable as a filter aid for filtering and clarifying water used in pools, public baths and the like. The present invention relates to a filter aid comprising a product and a method for producing the same.
珪藻土は、表面が無数の微細な孔に覆われており、濾材の上にプレコートすることにより、不純物が濾材に直接付着することや目詰りすることを防ぎ、また、濾材の目を微細にして濾液の清澄度を高める目的で使用されている。このように濾過助剤として使用される珪藻土は、一般に微粉体状であり、微粉体のまま袋詰めされて販売されているが、かかる微粉体状の珪藻土は、使用時に正確な計量が難しいことに加え、投入時に粉塵が発生しやすく、発生した粉塵が取り扱い者に危害を及ぼしたり、飛散して周辺を汚染したりするおそれがあった。 Diatomaceous earth is covered with countless fine pores, and pre-coating on the filter media prevents impurities from adhering directly to the filter media and clogging, and makes the filter media finer. Used to increase the clarity of the filtrate. Thus, diatomaceous earth used as a filter aid is generally in the form of a fine powder and is sold as a fine powder in a bag. However, it is difficult to accurately measure the fine powdered diatomaceous earth when used. In addition, dust is likely to be generated at the time of charging, and there is a risk that the generated dust may harm the operator or may be scattered and contaminate the surrounding area.
この問題を解決する方法として、粉末状珪藻土に少量のアルギン酸ナトリウム及び水を加え造粒する方法（特許文献１）が提案されているが、接着力及び顆粒状化後の水中崩壊性の問題から、アルギン酸ナトリウムの配合量に制約があるため、乾燥後に得られる造粒物の粒径は、０.６〜２.４ｍｍに過ぎず、使用時の簡便性の観点から、より大きな成形体、並びに任意形状の成形が可能な製造方法が望まれていた。また、この方法では、粉末状珪藻土の粒状化には、珪藻土の総重量に対して３.２〜３.３倍量の水を必要とし、その後の乾燥で大量の水分を除去する必要があるため、経済性に欠けるという問題もあった。更に、この方法で得られる造粒物の密度は、粉末状珪藻土の密度と比較してもさほど高いとは言えず、輸送及び保管効率の点でも不十分であった。 As a method for solving this problem, a method of granulating by adding a small amount of sodium alginate and water to powdered diatomaceous earth (Patent Document 1) has been proposed, but from the problem of adhesive strength and disintegration in water after granulation. Since the blending amount of sodium alginate is limited, the particle size of the granulated product obtained after drying is only 0.6 to 2.4 mm. From the viewpoint of convenience during use, A production method capable of forming an arbitrary shape has been desired. In this method, the granulation of the powdered diatomaceous earth requires 3.2 to 3.3 times the amount of water relative to the total weight of the diatomaceous earth, and it is necessary to remove a large amount of water by subsequent drying. Therefore, there was also a problem of lack of economic efficiency. Furthermore, it cannot be said that the density of the granulated product obtained by this method is so high as compared with the density of the powdered diatomaceous earth, and the transport and storage efficiency is insufficient.
かかる問題点を解決する手段として、珪藻土及びセルロースエーテールからなる易水中崩壊性珪藻土成形物（特許文献２）が提案されているが、該珪藻土成形物は、製品強度が十分でなく、輸送及び保管時の取り扱いに注意を要するという問題があった。 As means for solving such a problem, an easily water disintegrating diatomaceous earth molded product (Patent Document 2) composed of diatomaceous earth and cellulose ether has been proposed. However, the diatomaceous earth molded product does not have sufficient product strength, and can be transported and There was a problem that care should be taken during handling.
以上の状況に鑑み、本発明の目的は、用途に応じて任意の形状及びサイズに成形することが可能で、水中での崩壊性及び濾過性に優れ、更には、輸送及び保管に支障をきたさない十分な強度を有する易水中崩壊性珪藻土成形物からなる濾過助剤及びその製造方法を提供することにある。 In view of the above situation, the object of the present invention is that it can be molded into any shape and size according to the application, is excellent in disintegration and filterability in water, and further hinders transportation and storage. Another object of the present invention is to provide a filter aid comprising an easily water disintegrable diatomaceous earth molded product having no sufficient strength and a method for producing the same.
本発明者らは、上記目的を達成するために鋭意検討した結果、珪藻土に対して水溶性多糖類のプルランを配合することで、水中での崩壊性及び濾過性に優れつつ、十分高い強度を有する珪藻土成形物が得られることを見出し、本発明を完成させるに至った。 As a result of diligent studies to achieve the above-mentioned object, the present inventors blended a water-soluble polysaccharide pullulan with diatomaceous earth to provide a sufficiently high strength while being excellent in disintegration and filterability in water. The present inventors have found that a diatomaceous earth molded product having the same can be obtained, and have completed the present invention.
即ち、本発明の易水中崩壊性珪藻土成形物からなる濾過助剤は、珪藻土を主成分とし、バインダーとしてプルランを含むことを特徴とし、該プルランの配合量が前記珪藻土１００質量部に対して２〜３０質量部であり、好ましくは、５〜２０質量部である。ここで、本発明に係わるプルランは、微生物の産生する多糖類の一種であり、デキストランやナタデココの成分のセルロースと同様にブドウ糖の重合物として知られ、一般的には、黒酵母ともよばれる不完全菌Aureobasidium Pullulansにより得られ、この微生物が細胞外に産生する粘性多糖類である。プルランの構造は、下記構造式に示す如く、マルトトリオース（グルコース３分子がα−１，４結合）が規則正しく、α−１，６結合した直鎖状のグルカンである。 That is, the filter aid comprising the easily water-disintegrating diatomaceous earth molding of the present invention is characterized by comprising diatomaceous earth as a main component and pullulan as a binder, and the amount of the pullulan is 2 parts by mass with respect to 100 parts by mass of the diatomaceous earth. a 30 parts by mass, preferably 5 to 20 parts by weight. Here, the pullulan according to the present invention is a kind of polysaccharide produced by microorganisms, and is known as a glucose polymer as well as cellulose as a component of dextran and nata de coco, and is generally incompletely called black yeast. It is a viscous polysaccharide produced by the fungus Aureobasidium Pullulans and produced extracellularly by this microorganism. The structure of pullulan is a linear glucan in which maltotriose (three glucose molecules are α-1,4 bonds) regularly and α-1,6 bonds as shown in the following structural formula.
上記プルランは、澱粉同様、使用制限のない添加物として既存添加物名簿収載品目リスト（別添一）、医薬品添加物規格１９９３、化粧品原料基準外成分規格１９９３に収載されており、増粘剤や接着剤として食品、医薬品、化粧品等に幅広く使用されている。そのため、上記プルランは、人体への悪影響を懸念する必要がなく、プール、公衆浴場等に用いられる水の濾過助剤に含まれていても、問題がない。 Like the starch, the pullulan is listed in the existing additive list listed item list (Appendix 1), the pharmaceutical additive standard 1993, the cosmetic raw material non-standard ingredient standard 1993 as an additive with no restriction on use. As an adhesive, it is widely used in foods, pharmaceuticals, cosmetics, etc. Therefore, the pullulan need not be concerned about adverse effects on the human body, and even if it is contained in water filter aids used in pools, public baths, etc., there is no problem.
なお、上記プルランは、種々の用途への適用が提案されており、具体的に、フィルムへの応用例としては、プルラン及び親水性高分子からなるフィルム、被覆膜、チューブ、カプセル、シート成型物の製造方法（特開昭５１−０１０８５９号公報）が提案されており、また、エアゾール容器の摺動部シール剤への応用例としては、プルラン高含有物に多価アルコールを含有させたコーティング剤、接着剤及び成形物（特開平０６−０６５３０２号公報）が提案されている。 The pullulan has been proposed for various uses. Specifically, as an example of application to a film, a film made of pullulan and a hydrophilic polymer, a coating film, a tube, a capsule, a sheet molding A manufacturing method of a product (Japanese Patent Laid-Open No. 51-010859) has been proposed, and as an application example to a sealant for a sliding part of an aerosol container, a coating containing a polyuranic alcohol in a high pullulan content An agent, an adhesive, and a molded article (Japanese Patent Laid-Open No. 06-066532) have been proposed.
また、水系で徐崩性を有するプルラン含有成形物とその製法としては、ヘテロマンナンを含有させた徐崩性プルラン含有成形物（特開昭６０−２１９２３８号公報）が提案されており、フィルム、種子シート、カプセル、錠剤、肥料杭が具体例として挙げられている。フィルム、種子シート、カプセルに関しては、本発明の主旨と異なるものであり、また、錠剤、肥料杭に関しては、打錠、押し出し機による成形であり、仮に当該方法を珪藻土に適用した場合、加圧操作過程で珪藻土の粒子破壊を生じる結果、濾過助剤として機能しない。加えて、本発明の課題である速崩性が得られないことは言うまでもない。 Further, as a pullulan-containing molded product having a slow disintegration property in an aqueous system and a method for producing the same, a gradually disintegrating pullulan-containing molded product containing a heteromannan (JP-A-60-219238) has been proposed, and a film, Specific examples include seed sheets, capsules, tablets, and fertilizer piles. Regarding the film, seed sheet, and capsule, it is different from the gist of the present invention, and regarding the tablet and the fertilizer pile, it is formed by tableting and extrusion, and if the method is applied to diatomaceous earth, it is pressurized. It does not function as a filter aid as a result of particle breakage of diatomaceous earth during the operation process. In addition, it goes without saying that the rapid collapse that is the subject of the present invention cannot be obtained.
更に、農薬に徐崩性を付与するために、微生物由来の多糖類をコーティング剤として使用する徐崩性農薬の製造方法（特表２００４−５２５０９４号公報）が提案されているが、コーティングされた粉体を造粒あるいは成形することが記載されておらず、該徐崩性農薬は、粉体のまま使用され、成形物ではない。加えて、特表２００４−５２５０９４号公報に開示の微生物由来の多糖類の添加量は、多孔性担体１ｋｇに対して０.５〜１５ｇの範囲であり、該微生物由来の多糖類は、多孔性担体のコーティング剤として作用して農薬に徐崩性を付与するものの、多孔性担体同士を十分に接着することができないため、輸送及び保管時に十分な製品強度を有する成形物とすることができない。 Furthermore, a method for producing a slow-disintegrating agricultural chemical using a microorganism-derived polysaccharide as a coating agent (Japanese Patent Publication No. 2004-525044) has been proposed in order to impart a slow-disintegrating property to the agricultural chemical. There is no description of granulating or molding the powder, and the slowly disintegrating agricultural chemical is used as it is, not a molded product. In addition, the addition amount of the microorganism-derived polysaccharide disclosed in JP-T-2004-525094 is in the range of 0.5 to 15 g with respect to 1 kg of the porous carrier, and the microorganism-derived polysaccharide is porous. Although acting as a carrier coating agent and imparting gradual disintegration to agricultural chemicals, porous carriers cannot be sufficiently bonded to each other, so that a molded product having sufficient product strength during transportation and storage cannot be obtained.
上記のように、プルランは、種々の用途への適用が提案されているが、輸送及び保管時に十分な製品強度を有し、水中での使用に際しては、速やかに崩壊、分散して粉状となる珪藻土成形物、特に濾過助剤としての珪藻土成形物において、バインダーとしてプルランを適用する技術は知られていない。 As described above, pullulan has been proposed for various uses, but has sufficient product strength during transportation and storage, and when used in water, it quickly disintegrates, disperses and becomes powdery. In a diatomaceous earth molded product, particularly a diatomaceous earth molded product as a filter aid, a technique for applying pullulan as a binder is not known.
本発明の易水中崩壊性珪藻土成形物からなる濾過助剤は、珪藻土に対しバインダーとしてプルランを添加及び混合した後、得られた混合物を水分を介在させながら成形し、更に得られた成形物を乾燥することで製造することができる。ここで、プルランの配合量は、珪藻土１００質量部に対して２〜３０質量部の範囲が好ましく、５〜２０質量部の範囲が更に好ましい。なお、成形に当たっては、目的とする珪藻土成形物の形状に応じた成形方法を適宜選択すれば良い。また、珪藻土へのプルランの配合方法は、特に制限されるものではなく、プルランを粉状のまま珪藻土粉体に配合しても、プルランを水溶液状として珪藻土粉体に配合してもよい。尚、粉末状珪藻土の成形化に際して、介在させる水分の量は、粉末状珪藻土の質量に対して０.８〜２.５倍量の範囲が好ましい。 The filter aid comprising the easily water disintegrating diatomaceous earth molded product of the present invention is obtained by adding and mixing pullulan as a binder to diatomaceous earth, and then molding the resulting mixture while interposing moisture, and further obtaining the molded product. It can be manufactured by drying. Here, the range of 2-30 mass parts is preferable with respect to 100 mass parts of diatomaceous earths, and the range of 5-20 mass parts is still more preferable with respect to 100 mass parts of diatomaceous earth. In molding, a molding method corresponding to the shape of the target diatomaceous earth molded product may be appropriately selected. Moreover, the blending method of pullulan in diatomaceous earth is not particularly limited, and pullulan may be blended in diatomaceous earth powder in powder form or may be blended in diatomaceous earth powder as an aqueous solution. In addition, the amount of water to intervene in forming powdered diatomaceous earth is preferably in the range of 0.8 to 2.5 times the mass of powdered diatomaceous earth.
本発明の易水中崩壊性珪藻土成形物からなる濾過助剤は、取り扱いが簡単で、輸送及び保管に支障をきたさない十分な強度を有し、粉末のような発塵が無く、衛生的で、ひとたび水中に投入すれば容易に崩壊し、ダマを生成することなく、均一な空隙を有する濾過助剤層を形成して、珪藻土本来の機能を発揮した濾過性能が得られる。また、本発明の製造方法によれば、使用方法に応じた任意の形状およびサイズの濾過助剤の製造が可能になる。 The filter aid comprising the easily water disintegrating diatomaceous earth molded product of the present invention is easy to handle, has sufficient strength not to hinder transportation and storage, is free from dust like powder, is hygienic, Once it is put into water, it easily disintegrates and forms a filter aid layer having uniform voids without producing lumps, and a filtration performance that exhibits the original function of diatomaceous earth is obtained. Moreover, according to the manufacturing method of this invention, manufacture of the filter aid of arbitrary shapes and sizes according to the usage method is attained.
以下に、本発明を詳細に説明する。珪藻土本来の濾過性を低下させることなく、水中での崩壊性、並びに保存及び取り扱い時の十分な強度を有する新規な珪藻土成形物を構成するにあたって、本発明では、珪藻土に水溶性多糖類のプルランを配合することを特徴とする。なお、接着性を示す水溶性多糖類としては、種子由来多糖類（グァーガム、タラガム、ローカストビーンガム、タマリンドシードガム、サイリウムシードガム）、樹脂由来多糖類（アラビアガム、カラヤガム）、海藻由来多糖類（寒天、カラギナン、アルギン酸）、微生物由来多糖類（プルラン、キサンタンガム、ジェランガム、カードラン）、植物由来多糖類（ペクチン、セルロース）、甲殻類由来多糖類（キチン、キトサン）など無数に知られているが、珪藻土成形物に求められる要件としては、接着力の他、保存安定性、水中に投入した際の崩壊性及び濾過助剤としての機能を有する必要があることから、本発明者らが鋭意検討した結果、水溶性多糖類の中でもプルランが特に好適であることを見出した。 The present invention is described in detail below. In constructing a novel diatomaceous earth molded product having a disintegration property in water and sufficient strength during storage and handling without reducing the original filterability of diatomaceous earth, in the present invention, a pullulan of a water-soluble polysaccharide is added to diatomaceous earth. It is characterized by blending. In addition, as water-soluble polysaccharides showing adhesiveness, seed-derived polysaccharides (guar gum, tara gum, locust bean gum, tamarind seed gum, psyllium seed gum), resin-derived polysaccharides (arabic gum, karaya gum), seaweed-derived polysaccharides (Agar, carrageenan, alginic acid), microorganism-derived polysaccharides (pullulan, xanthan gum, gellan gum, curdlan), plant-derived polysaccharides (pectin, cellulose), crustacean-derived polysaccharides (chitin, chitosan), etc. However, the requirements for the diatomaceous earth molded product are not only adhesive strength, but also storage stability, disintegration when injected into water, and function as a filter aid. As a result of investigation, it was found that pullulan is particularly suitable among water-soluble polysaccharides.
また、本発明の珪藻土成形物からなる濾過助剤をプール、浴場等の用途に使用する場合、人体に対して無害である必要があるが、プルランは、澱粉同様、使用制限のない添加物として既存添加物名簿収載品目リスト（別添一）、医薬品添加物規格１９９３、化粧品原料基準外成分規格１９９３に収載され、増粘剤や接着剤として食品、医薬品、化粧品等に幅広く使用されており、プール、浴場等の用途で使用する場合においても、人体に対して無害であるという利点がある。 In addition, when the filter aid comprising the diatomaceous earth molded product of the present invention is used for applications such as pools and baths, it must be harmless to the human body. Listed in Existing Additive List (Appendix 1), Pharmaceutical Additive Standard 1993, Cosmetic Raw Material Non-Standard Standard 1993, widely used in foods, pharmaceuticals, cosmetics, etc. as thickeners and adhesives, Even when used for purposes such as pools and baths, there is an advantage that it is harmless to the human body.
このような珪藻土成形物を製造するには、珪藻土にプルランを添加、混合後、水分を介在させながら、珪藻土成形物の目的の形状に応じた成形方法を選択すれば良く、乾燥を経て上記珪藻土成形物が得られる。 In order to produce such a diatomaceous earth molded article, after adding pullulan to the diatomaceous earth and mixing, it is sufficient to select a molding method according to the desired shape of the diatomaceous earth molded article while interposing moisture, and after drying, the above diatomaceous earth is selected. A molding is obtained.
本発明の易水中崩壊性珪藻土成形物からなる濾過助剤において、プルランの配合量は、珪藻土１００質量部に対して２〜３０質量部の範囲であり、５〜２０質量部の範囲が好ましい。プルランの配合量が珪藻土１００質量部に対して２質量部未満の場合、成形後の乾燥過程で形成されるプルランの皮膜形成量が少なく、珪藻土の接着力が不十分であるため、成形物の強度が小さく、輸送及び保管に支障をきたす。また、プルランの配合量が珪藻土１００質量部に対して３０質量部を超えると、強度については問題ないものの、珪藻土成形物に占める珪藻土の割合が低下すると共に、濾過性能が低下する傾向があり好ましくない。 In the filter aid comprising the easily water-disintegrating diatomaceous earth molded product of the present invention, the amount of pullulan is in the range of 2 to 30 parts by mass with respect to 100 parts by mass of diatomaceous earth, and preferably in the range of 5 to 20 parts by mass. When the blending amount of pullulan is less than 2 parts by mass with respect to 100 parts by mass of diatomaceous earth, the amount of pullulan film formed in the drying process after molding is small, and the adhesive strength of diatomaceous earth is insufficient. The strength is low, which hinders transportation and storage. Further, when the blending amount of pullulan exceeds 30 parts by mass with respect to 100 parts by mass of diatomaceous earth, although there is no problem with strength, the ratio of diatomaceous earth in the diatomaceous earth molded product is reduced, and the filtration performance tends to be reduced. Absent.
上記珪藻土へのプルランの添加方法は、珪藻土成形物の形状あるいは成形方法に応じて形態が異なる。例えば、珪藻土成形物の形状が球状の場合は、プルランを粉状のまま珪藻土粉体と混合した後、パン型成形機等を使用して、水噴霧しながら転動造粒し、乾燥工程を経ることで、粒径が３〜１０ｍｍ程度の球状珪藻土成形物が得られる。また、珪藻土成形物の形状が直方体の場合は、プルランを水溶液状で使用し、珪藻土粉体と混練後、型枠に入れ成形した後、乾燥工程を経ることで、型枠に応じた任意サイズの直方体珪藻土成形物が得られる。ここで、プルランを粉状のまま使用し、珪藻土粉体及び水と混練することも可能であり、また、型枠は直方体に限定されず、任意の形状に出来ることは言うまでもない。 The method for adding pullulan to the diatomaceous earth differs depending on the shape of the diatomaceous earth molded product or the molding method. For example, if the shape of the diatomaceous earth molded product is spherical, after pullulan is mixed with diatomaceous earth powder in powder form, it is rolled and granulated while spraying with water using a bread mold molding machine, etc. By passing, a spherical diatomaceous earth molded product having a particle size of about 3 to 10 mm is obtained. In addition, when the shape of the diatomaceous earth molded product is a rectangular parallelepiped, use pullulan in the form of an aqueous solution, knead with diatomaceous earth powder, mold into a mold, and then go through a drying process to give an arbitrary size according to the mold A cuboid diatomaceous earth molded product is obtained. Here, it is possible to use pullulan in powder form and knead it with diatomaceous earth powder and water, and it is needless to say that the formwork is not limited to a rectangular parallelepiped and can be formed in any shape.
尚、粉末状珪藻土の成形化に際して、必要とされる水の量は、粉末状珪藻土の質量に対して０.８〜２.５倍量の範囲が好ましい。使用する水の量が粉末状珪藻土の質量に対して０.８倍量未満の場合、プルランの均一被膜形成が不十分で、成形物の強度が低下する。また、使用する水の量が粉末状珪藻土の質量に対して２.５倍を超えた場合、成形化に際しては、何等支障はないが、成形後の乾燥工程で除去する水の量が増える為、経済的でない。 In addition, the amount of water required for forming powdered diatomaceous earth is preferably in the range of 0.8 to 2.5 times the amount of powdered diatomaceous earth. When the amount of water to be used is less than 0.8 times the mass of the powdered diatomaceous earth, the formation of a uniform film of pullulan is insufficient and the strength of the molded product is reduced. If the amount of water used exceeds 2.5 times the mass of the powdered diatomaceous earth, there will be no problem during molding, but the amount of water removed in the drying process after molding will increase. Not economical.
上記のようにして得られた水及びプルラン含有珪藻土成形物を乾燥して、輸送及び保管に支障をきたさない十分な強度を有する珪藻土成形物が得られる。具体的には、造粒された成形物や、成形型に入れて形を整えた後、取り出された成形物を３０〜１５０℃の温度で熱風乾燥することが好ましい。なお、乾燥温度及び乾燥時間は、成形物の含水率及びプルランによって形成される皮膜の皮膜分布等に影響を与える為、所定の物性を要する成形物を得るには、乾燥温度及び乾燥時間を適宜調整すれば良い。 The water and pullulan-containing diatomaceous earth molded product obtained as described above is dried to obtain a diatomaceous earth molded product having sufficient strength that does not hinder transportation and storage. Specifically, it is preferable that the granulated molded product or the molded product taken out after being put in a mold and dried is hot-air dried at a temperature of 30 to 150 ° C. The drying temperature and drying time affect the moisture content of the molded product and the film distribution of the film formed by pullulan. Therefore, in order to obtain a molded product that requires predetermined physical properties, the drying temperature and the drying time are appropriately set. Adjust it.
このように構成した珪藻土成形物において、成形物の表面は、主としてプルランの皮膜で覆われており、乾燥条件によって、成形物内部に水分及び皮膜が分散して残る。その結果、表面を覆う皮膜によって成形物の形状が維持される。このプルランの皮膜は、水中に投下した際、容易に溶解する為、成形物は直ちに崩壊して本来の濾過助剤としての機能を十分に発揮することが可能となる。 In the diatomaceous earth molding thus configured, the surface of the molding is mainly covered with a pullulan film, and moisture and the film remain dispersed inside the molding depending on the drying conditions. As a result, the shape of the molded product is maintained by the film covering the surface. This pullulan film dissolves easily when dropped in water, so that the molded product immediately disintegrates and can fully function as an original filter aid.
また、珪藻土、水、プルランを配合、混練して得られる成形物は過剰の水分を含有する結果、強度あるいは形状維持の問題の他、保存時の自然乾燥による水分蒸発等によって、成形物の組成が変化するため、本発明の製造方法では、混練、成形後の成形物を３０〜１５０℃の温度で熱風乾燥し、過剰水分を除去してプルランの皮膜形成を促進させ、成形物中の皮膜分布を調整する。その結果、保存期間中における安定性が高く、且つ強度が十分に維持された珪藻土成形物を得る事が出来る。 In addition, the molded product obtained by blending and kneading diatomaceous earth, water, and pullulan contains excess moisture, resulting in strength or shape maintenance problems, as well as moisture evaporation due to natural drying during storage, etc. Therefore, in the production method of the present invention, the molded product after kneading and molding is dried with hot air at a temperature of 30 to 150 ° C. to remove excess moisture and promote film formation of pullulan. Adjust the distribution. As a result, it is possible to obtain a diatomaceous earth molded product having high stability during the storage period and sufficient strength.
尚、本発明の珪藻土成形物からなる濾過助剤には、珪藻土の濾過性能、並びにプルランの接着力及び安定性等を阻害しない範囲内で、例えば、識別の為の着色剤、抗菌・殺菌剤あるいは臭気成分の捕集剤等を配合することが出来る。これらの薬剤は珪藻土成形物製造時の混合過程で、珪藻土及びプルランと共に配合すれば良い。また、本発明の珪藻土成形物からなる濾過助剤には、水中での崩壊性、並びに保存及び取り扱い時の強度を損なわない範囲において、プルラン（必須成分）と共に、接着性を示す他の水溶性多糖類を併用することが出来る。
The filter aid comprising the diatomaceous earth molded product of the present invention includes, for example, a colorant, an antibacterial and bactericidal agent for identification within a range that does not impair the filtration performance of diatomaceous earth and the adhesion and stability of pullulan. Alternatively, an odor component scavenger or the like can be blended. These chemicals may be blended together with diatomaceous earth and pullulan in the mixing process at the time of diatomaceous earth molding production. In addition, the filter aid comprising the diatomaceous earth molded product of the present invention has other water-solubility that exhibits adhesiveness together with pullulan (essential component) within a range that does not impair disintegration in water and strength during storage and handling. Polysaccharides can be used in combination.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。また、珪藻土成形物の強度、耐摩耗性、沈降性、崩壊性、濾過性、ケーク嵩密度、平均粒子径を評価するにあたっては、以下の試験方法を用いた。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. Moreover, in evaluating the strength, abrasion resistance, sedimentation, disintegration, filterability, cake bulk density, and average particle diameter of the diatomaceous earth molded product, the following test methods were used.
［試験方法］
・強度 ：成形物を平面上に静置し、指触により破壊されるまで圧力を加え、その程度を比較した。
・耐摩耗性 ：定形の容器に一定量の粒を入れて容器ごと回転させ、粉化の程度を比較した。
・沈降性 ：珪藻土成形物を水温３０℃に調整した水の表面に静かに投入し、ビーカー底部まで沈降するのに要した時間を比較した。
・崩壊性 ：珪藻土成形物を水温３０℃に調整した水に浸漬し、崩壊により当初の形状が消失するまでの時間を比較した。
[Test method]
・ Strength: The molded product was allowed to stand on a flat surface, and pressure was applied until it was destroyed by finger touching.
-Abrasion resistance: A fixed amount of particles were put into a regular container, and the whole container was rotated to compare the degree of powdering.
-Sedimentability: The diatomaceous earth molded product was gently put on the surface of water adjusted to a water temperature of 30 ° C, and the time required to settle to the bottom of the beaker was compared.
-Disintegration property: The diatomaceous earth molded product was immersed in water adjusted to a water temperature of 30 ° C, and the time until the original shape disappeared due to the collapse was compared.
・濾過性 ：珪藻土成形物を水中で崩壊させ、濾過助剤を含んだ懸濁液を作製した後、定圧濾過試験装置を用いてケークを形成させた。これに一定量の水を透過させ、下記のダルシー（Darcy）の透過式より透過率を求め、その数値にて濾過性を評価した。ここで、透過率とは、下記ダルシーの透過式に基づく係数ｋであり、助剤のみで形成されたケーク内を清澄な流体が透過する速度の指標である。 Filterability: The diatomaceous earth molded product was disintegrated in water to prepare a suspension containing a filter aid, and then a cake was formed using a constant pressure filtration test apparatus. A certain amount of water was allowed to permeate this, and the transmittance was determined from the Darcy permeation method described below, and the filterability was evaluated based on the numerical value. Here, the transmittance is a coefficient k based on the following Darcy transmission equation, and is an index of the speed at which a clear fluid permeates through a cake formed only with an auxiliary agent.
式中、
Ａ：透過層断面積〔m2〕
Ｖ：透過量〔m3〕
θ：透過時間〔s〕
ｋ：透過率〔m2〕
ｐ：透過層の圧力損失〔Pa〕
μ：透過流体の粘度〔Pa・s〕
Ｌ：透過層厚さ〔m〕
であり、透過率はケーク平均濾過比抵抗の逆数に相当し、数値が大きいほど透過速度が大きいことを示す。
Where
A: Transmission layer cross-sectional area [m 2 ]
V: Permeation amount [m 3 ]
θ: Transmission time [s]
k: Transmittance [m 2 ]
p: Pressure loss of transmission layer [Pa]
μ: Permeable fluid viscosity [Pa · s]
L: Transmission layer thickness [m]
The transmittance corresponds to the reciprocal of the cake average filtration specific resistance, and the larger the value, the higher the permeation rate.
・ケーク嵩密度：濾過性評価試験時に、試験装置内に形成されたケークの厚みよりケーク全体の体積を算出し、当該ケークの乾燥重量をこれで除したものをケーク嵩密度とした。
・平均粒子径 ：珪藻土成形物を水に懸濁させた後、得られた珪藻土粒子の平均粒子径をレーザー式粒度分布測定装置で測定した。
-Cake bulk density: During the filterability evaluation test, the volume of the entire cake was calculated from the thickness of the cake formed in the test apparatus, and the cake weight density was obtained by dividing the dry weight of the cake by this.
-Average particle diameter: After suspending the diatomaceous earth molding in water, the average particle diameter of the obtained diatomaceous earth particles was measured with a laser-type particle size distribution measuring device.
（実施例１）
粉末状精製珪藻土［昭和化学工業（株）製］３５ｋｇとプルラン［（株）林原製］０．７ｋｇとを混合した後、水を噴霧しながら転動造粒した。造粒に際して使用した水の量は約５５ｋｇであった。造粒後の湿潤状態の珪藻土成形物を８０℃で４８時間乾燥して、粒径が３〜１０ｍｍの球状珪藻土成形物を３２.８ｋｇ得た。得られた珪藻土成形物の嵩密度は０.３３２ｇ／ｃｍ3であった。
Example 1
After mixing 35 kg of powdery refined diatomaceous earth [manufactured by Showa Chemical Industry Co., Ltd.] and 0.7 kg of pullulan [manufactured by Hayashibara Co., Ltd.], rolling granulation was performed while spraying water. The amount of water used for granulation was about 55 kg. The wet diatomaceous earth molded product after granulation was dried at 80 ° C. for 48 hours to obtain 32.8 kg of spherical diatomaceous earth molded product having a particle size of 3 to 10 mm. The bulk density of the obtained diatomaceous earth molded product was 0.332 g / cm 3 .
（実施例２）
粉末状精製珪藻土３５ｋｇとプルラン１.７５ｋｇとを混合した後、水を噴霧しながら転動造粒した。造粒に際して使用した水の量は約５７ｋｇであった。造粒直後の湿潤状態の珪藻土成形物を８０℃で４８時間乾燥して、粒径が３〜１０ｍｍの球状珪藻土成形物を３３.６ｋｇ得た。得られた珪藻土成形物の嵩密度は０.３６８ｇ／ｃｍ3であった。
(Example 2)
After mixing 35 kg of powdered purified diatomaceous earth and 1.75 kg of pullulan, rolling granulation was performed while spraying water. The amount of water used for granulation was about 57 kg. The wet diatomaceous earth molded product immediately after granulation was dried at 80 ° C. for 48 hours to obtain 33.6 kg of spherical diatomaceous earth molded product having a particle size of 3 to 10 mm. The bulk density of the obtained diatomaceous earth molded product was 0.368 g / cm 3 .
（実施例３）
粉末状精製珪藻土３.５ｋｇとプルラン０.７ｋｇ及び水４.２ｋｇをモルタルミキサーで混合した後、５×５×１０ｃｍの型枠に入れ成形した。成形後の湿潤状態の珪藻土成形物を１０５℃で４８時間乾燥して直方体の珪藻土成形物３８個（３.８ｋｇ）を得た。得られた珪藻土成形物の嵩密度は０.４１９ｇ／ｃｍ3であった。
(Example 3)
Powdered refined diatomaceous earth (3.5 kg), pullulan (0.7 kg) and water (4.2 kg) were mixed with a mortar mixer, and then placed in a 5 × 5 × 10 cm mold and molded. The wet diatomaceous earth moldings after molding were dried at 105 ° C. for 48 hours to obtain 38 cuboid diatomaceous earth moldings (3.8 kg). The bulk density of the obtained diatomaceous earth molded product was 0.419 g / cm 3 .
（実施例４）
粉末状精製珪藻土３.５ｋｇとプルラン１.０５ｋｇ及び水５.１ｋｇをモルタルミキサーで混合した後、５×５×１０ｃｍの型枠に入れ成形した。成形後の湿潤状態の珪藻土成形物を１０５℃で４８時間乾燥して直方体の珪藻土成形物３８個（４.１ｋｇ）を得た。得られた珪藻土成形物の嵩密度は０.４３２ｇ／ｃｍ3であった。
Example 4
Powdered refined diatomaceous earth (3.5 kg), pullulan (1.05 kg) and water (5.1 kg) were mixed with a mortar mixer, and then put into a 5 × 5 × 10 cm mold and molded. The wet diatomaceous earth moldings after molding were dried at 105 ° C. for 48 hours to obtain 38 cuboid diatomaceous earth moldings (4.1 kg). The bulk density of the obtained diatomaceous earth molded product was 0.432 g / cm 3 .
（比較例１）
粉末状精製珪藻土３５ｋｇとプルラン０.１７５ｋｇとを混合した後、水を噴霧しながら転動造粒した。造粒に際して使用した水の量は約５４ｋｇであった。造粒直後の湿潤状態の珪藻土成形物を８０℃で４８時間乾燥して、粒径が３〜１０ｍｍの球状珪藻土成形物を３２ｋｇ得た。得られた珪藻土成形物の嵩密度は０.２７７ｇ／ｃｍ3であった。
(Comparative Example 1)
After mixing 35 kg of powdered purified diatomaceous earth and 0.175 kg of pullulan, rolling granulation was performed while spraying water. The amount of water used for granulation was about 54 kg. The wet diatomaceous earth molded product immediately after granulation was dried at 80 ° C. for 48 hours to obtain 32 kg of spherical diatomaceous earth molded product having a particle size of 3 to 10 mm. The bulk density of the obtained diatomaceous earth molded product was 0.277 g / cm 3 .
（比較例２）
珪藻土３.５ｋｇとプルラン１.２２５ｋｇ及び水５.６ｋｇをモルタルミキサーで混合した後、５×５×１０ｃｍの型枠に入れ成形した。成形後の湿潤状態の珪藻土成形物を１０５℃で４８時間乾燥して直方体の珪藻土成形物３８個（４.３ｋｇ）を得た。得られた珪藻土成形物の嵩密度は０.４３７ｇ／ｃｍ3であった。
(Comparative Example 2)
The diatomaceous earth (3.5 kg), the pullulan (1.225 kg) and the water (5.6 kg) were mixed with a mortar mixer, and then put into a 5 × 5 × 10 cm mold and molded. The wet diatomaceous earth moldings after molding were dried at 105 ° C. for 48 hours to obtain 38 cuboid diatomaceous earth moldings (4.3 kg). The bulk density of the obtained diatomaceous earth molded product was 0.437 g / cm 3 .
（比較例３）
珪藻土成形物が濾過助剤として使用される時に、濾過助剤としての特性が維持されているかを確認するために、一般的な濾過助剤として使用される粉末状精製珪藻土と比較した。使用した粉末状精製珪藻土の嵩密度は０.２ｇ／ｃｍ3である。以上の結果を表１に示す。
(Comparative Example 3)
When the diatomaceous earth molded product was used as a filter aid, it was compared with powdered purified diatomaceous earth used as a general filter aid in order to confirm whether the properties as a filter aid were maintained. The bulk density of the powdered refined diatomaceous earth used is 0.2 g / cm 3 . The results are shown in Table 1.
＊１ 強度 ： 低い ← × △ ○ ◎ → 高い
＊２ 耐摩耗性： 低い ← × △ ○ ◎ → 高い
＊３ 沈降性 ： 低い ← × △ ○ ◎ → 高い
＊４ 崩壊性 ： 低い ← × △ ○ ◎ → 高い
* 1 Strength: Low ← × △ ○ ◎ → High * 2 Abrasion resistance: Low ← × △ ○ ◎ → High * 3 Sedimentation: Low ← × △ ○ ◎ → High * 4 Disintegration: Low ← × △ ○ ◎ → expensive
表１に示したように、珪藻土１００質量部に対して加えたプルランの配合量が２〜３０質量部の範囲であれば（実施例１〜４）、ハンドリング等に必要な強度や耐摩耗性が得られ、また、該成形物は、水に投入すると良好な沈降性を示し、沈降後まもなく自然に崩壊した。更に、これら成形物が水中で分散された粉末の濾過助剤としての特性は、濾過助剤として一般的に使用される粉末状精製珪藻土の特性と同等であった。なお、プルランの配合量は、強度及び耐摩耗性の観点から、珪藻土１００質量部に対して５質量部以上の範囲が好ましく（実施例２）、崩壊性及び濾過性能の観点から、２０質量部以下の範囲が好ましかった（実施例３）。 As shown in Table 1, if the amount of pullulan added to 100 parts by mass of diatomaceous earth is in the range of 2 to 30 parts by mass (Examples 1 to 4), the strength and wear resistance required for handling and the like. In addition, the molded product showed good sedimentation when poured into water, and spontaneously disintegrated shortly after settling. Furthermore, the properties of the powder in which these moldings are dispersed in water as a filter aid were equivalent to those of powdered purified diatomaceous earth generally used as a filter aid. In addition, the blending amount of pullulan is preferably in the range of 5 parts by mass or more with respect to 100 parts by mass of diatomaceous earth from the viewpoint of strength and wear resistance (Example 2). The following ranges were preferred (Example 3).
一方、プルランの配合量が珪藻土１００質量部に対し２質量部に満たない場合（比較例１）には、必要な強度や耐摩耗性が得られず、逆に３０質量部を超える場合（比較例２）には、崩壊性や濾過性が不良であった。
On the other hand, when the blending amount of pullulan is less than 2 parts by mass with respect to 100 parts by mass of diatomaceous earth (Comparative Example 1), necessary strength and wear resistance cannot be obtained, and conversely, when it exceeds 30 parts by mass (comparison) In Example 2), disintegration and filterability were poor.
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| JPH0665302A (en) * | 1992-08-20 | 1994-03-08 | Hayashibara Biochem Lab Inc | Pullulan concentrate, and its production and use |
| JP2004243180A (en) * | 2003-02-12 | 2004-09-02 | Taimei Chemicals Co Ltd | Diatomaceous earth molding and its production method |
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| JPH0665302A (en) * | 1992-08-20 | 1994-03-08 | Hayashibara Biochem Lab Inc | Pullulan concentrate, and its production and use |
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