JP5964195B2 - Microbial carrier - Google Patents
Microbial carrier Download PDFInfo
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- JP5964195B2 JP5964195B2 JP2012223365A JP2012223365A JP5964195B2 JP 5964195 B2 JP5964195 B2 JP 5964195B2 JP 2012223365 A JP2012223365 A JP 2012223365A JP 2012223365 A JP2012223365 A JP 2012223365A JP 5964195 B2 JP5964195 B2 JP 5964195B2
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- 230000000813 microbial effect Effects 0.000 title claims description 30
- 244000005700 microbiome Species 0.000 claims description 36
- 229920005672 polyolefin resin Polymers 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 10
- 230000002093 peripheral effect Effects 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 48
- 238000004062 sedimentation Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000006260 foam Substances 0.000 description 7
- 229920013716 polyethylene resin Polymers 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000005446 dissolved organic matter Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Biological Treatment Of Waste Water (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、水中沈降性及び嫌気性微生物の付着性に優れると共に、長時間使用しても水中汚染を生じない微生物担体に関する。 The present invention relates to a microbial carrier that is excellent in sedimentation in water and adherence to anaerobic microorganisms and that does not cause water contamination even when used for a long time.
従来、排水等に対する水処理には、嫌気性微生物による働きで溶存有機物を分解させる嫌気性処理がある。嫌気性処理においては、汚水浄化槽における反応槽(嫌気濾床層)に流動性の微生物担体を投入または充填して汚水(有機性排水)を通水させることで、微生物担体に付着した嫌気性微生物による働きで汚水中の溶存有機物を分解している(特許文献1、特許文献2)。
Conventionally, water treatment for waste water or the like includes anaerobic treatment in which dissolved organic matter is decomposed by the action of anaerobic microorganisms. In anaerobic treatment, anaerobic microorganisms attached to the microbial carrier by introducing or filling a fluid microbial carrier into the reaction tank (anaerobic filter bed layer) in the sewage septic tank and passing the sewage (organic wastewater) through The dissolved organic matter in the sewage is decomposed by the action of (
嫌気性処理では、嫌気性雰囲気で微生物が働くため、反応槽等内に投入された流動性の微生物担体は速やかに水中に沈降して水面に長く浮き上がっていない事が、水処理能力向上に必要となる。特に有機性排水を上向流通水して高速処理を行う場合、水沈降性が高いことが求められる。
水沈降性の向上を図った嫌気性処理用の微生物担体として、オレフィン系樹脂とセルロース系粉末を含むオレフィン系樹脂発泡体からなり、あるいはさらに無機粉末を含むオレフィン系樹脂発泡体からなり、発泡体の表面にメルトフラクチャー状態を有するものがある(特許文献2、特許文献3)。
In anaerobic treatment, since microorganisms work in an anaerobic atmosphere, it is necessary to improve the water treatment capacity that the fluid microbial carrier introduced into the reaction tank etc. quickly settles in the water and does not float on the surface for a long time. It becomes. In particular, when organic wastewater is circulated upward and high-speed treatment is performed, water sedimentation is required to be high.
As a microbial carrier for anaerobic treatment with improved water sedimentation, it is made of an olefin resin foam containing an olefin resin and a cellulose powder, or further comprising an olefin resin foam containing an inorganic powder. Some have a melt fractured state on the surface (Patent Document 2, Patent Document 3).
しかしながら、オレフィン系樹脂とセルロース系粉末を含むオレフィン系樹脂発泡体、あるいはさらに無機粉末を含むオレフィン系樹脂発泡体からなり、発泡体の表面にメルトフラクチャー状態を有する微生物担体は、発泡剤を使用することで表面の凹凸状態を発現させているものの、発泡体で中空状態からなるため、依然として水沈降性が良好ではなく、水処理能力も充分ではなく、さらに含有されている木粉等のセルロース系粉末が微生物担体自体を脆くさせるため、水中で長時間使用されると微生物担体の破片が水中に流れ出し、水中汚染を生じる問題がある。また、微生物担体の発泡体のセル内部に、微生物から発生するガスが溜まることによって浮力が増加して水沈降性が低下する問題がある。 However, a microbial carrier comprising an olefin resin foam containing an olefin resin and a cellulose powder, or an olefin resin foam containing an inorganic powder, and having a melt fractured state on the surface of the foam uses a foaming agent. Although the surface unevenness state is expressed by this, since it is in a hollow state with a foam, the water sedimentation property is still not good, the water treatment capacity is not sufficient, and further the cellulose type such as wood flour contained Since the powder makes the microbial carrier itself brittle, there is a problem in that if it is used in water for a long time, fragments of the microbial carrier will flow out into the water and cause contamination in the water. In addition, there is a problem that buoyancy is increased due to accumulation of gas generated from microorganisms inside the cell of the foam of the microbial carrier and water sedimentation is reduced.
本発明は前記の点に鑑みなされたものであって、水沈降性及び水処理能力に優れ、かつ水中で長時間使用しても水中汚染を生じない、嫌気性処理に好適な流動性の微生物担体の提供を目的とする。 The present invention has been made in view of the foregoing points, and is a fluid microorganism suitable for anaerobic treatment that is excellent in water sedimentation and water treatment capacity and does not cause underwater contamination even when used in water for a long time. The purpose is to provide a carrier.
請求項1の発明は、微生物を表面に保持する微生物担体において、前記微生物担体は非多孔質体からなり、前記非多孔質体は、該非多孔質体の100質量%中にメルトマスフローレイト(JIS K7210:1999)が0.01(g/10min)以上5(g/10min)未満であるポリオレフィン系樹脂30〜90質量%と無機粉末10〜70質量%を含み、比重が1より大で、外周面に相対的に外径の大きい大径部と相対的に外径の小さい小径部とが前記非多孔質体の長さ方向に交互に存在する波形状の凹凸を有し、前記非多孔質体の長さが、1〜10mmであり、前記大径部の平均外径が、2.5〜5.0mmであり、前記小径部の平均外径が、2.0〜4.5mmであり、前記大径部の平均外径と前記小径部の平均外径の比(大径部の平均外径/小径部の平均外径)が、1.02〜1.50であり、隣り合う前記大径部の間隔が0.8〜2.5mmであることを特徴とする。
According to the first aspect of the present invention, there is provided a microorganism carrier for holding microorganisms on the surface, wherein the microorganism carrier comprises a non-porous body, and the non-porous body comprises a melt mass flow rate (JIS) in 100% by mass of the non-porous body. K7210: 1999) contains 30 to 90% by weight of polyolefin resin and 0.01 to 70% by weight of inorganic powder with 0.01 (g / 10 min) or more and less than 5 (g / 10 min). have a wave-like irregularities larger large diameter portion of the relatively outer diameter surface and a small diameter portion having a relatively outer diameter are present alternately in the longitudinal direction of the non-porous body, wherein the non-porous The length of the body is 1 to 10 mm, the average outer diameter of the large diameter portion is 2.5 to 5.0 mm, and the average outer diameter of the small diameter portion is 2.0 to 4.5 mm The ratio of the average outer diameter of the large diameter portion to the average outer diameter of the small diameter portion (large The average outer diameter of the diameter portion / the average outer diameter of the small diameter portion) is 1.02 to 1.50, and the interval between the adjacent large diameter portions is 0.8 to 2.5 mm .
請求項2の発明は、請求項1において、前記非多孔質体の100質量%中には、前記ポリオレフィン系樹脂に非相溶性樹脂を1〜20質量%含むことを特徴とする。
請求項3の発明は、請求項1又は2において、前記無機粉末が炭酸カルシウムであることを特徴とする。
The invention of claim 2 is characterized in that, in 100% by mass of the non-porous body, 1 to 20% by mass of an incompatible resin is contained in the polyolefin resin.
The invention of
本発明の微生物担体は、メルトマスフローレイト(MFR:JIS K7210:1999)が0.01(g/10min)以上5未満(g/10min)であるポリオレフィン系樹脂を用いることで、外周面に相対的に外径の大きい大径部と相対的に外径の小さい小径部とが交互に存在する波形状の凹凸を有するため、小径部が凹部となって該凹部に微生物が効率よく付着保持される。また、本発明の微生物担体は、非多孔質体からなるため、多孔質体の場合のように気孔に気泡が溜まって浮き上がり易くなることが無いため、水処理能力に優れ、かつ比重が1より大であるために水沈降性が高く、水に投入直後から微生物付着開始までの時間を短縮することができる。さらに、本発明の微生物担体は、微生物担体を脆くする木粉等からなるセルロース系粉末を含まなくてもよいため、水中で長時間使用しても、微生物担体の形状が崩れてセルロース系粉末が水中に流出する虞がなく、水を汚染することがない。 The microbial carrier of the present invention uses a polyolefin resin having a melt mass flow rate (MFR: JIS K7210: 1999) of 0.01 (g / 10 min) or more and less than 5 (g / 10 min), so that the Since there are wavy irregularities in which a large-diameter portion having a large outer diameter and a small-diameter portion having a relatively small outer diameter are alternately present, the small-diameter portion becomes a concave portion, and microorganisms are efficiently attached and held in the concave portion. . In addition, since the microbial carrier of the present invention is composed of a non-porous body, bubbles do not accumulate in the pores and do not easily float as in the case of the porous body, so that the water treatment capacity is excellent and the specific gravity is more than 1. Since it is large, the water sedimentation property is high, and it is possible to shorten the time from immediately after the addition to water to the start of microorganism adhesion. Furthermore, since the microbial carrier of the present invention does not need to contain a cellulose-based powder made of wood powder or the like that makes the microbial carrier brittle, the shape of the microbial carrier collapses even when used in water for a long time, and the cellulose-based powder becomes There is no risk of spilling into the water and the water will not be contaminated.
さらに本発明の微生物担体は、非多孔質体の100質量%中における前記ポリオレフィン系樹脂に非相溶性樹脂を1〜20質量%含ませることによって、無機粉末の含有量を増加させても波形状の凹凸を形成させることができ、無機粉末の含有量増加によって微生物担体の比重を一層大にして水沈降性を高めることができる。 Furthermore, the microorganism carrier of the present invention has a corrugated shape even when the content of the inorganic powder is increased by including 1 to 20% by mass of an incompatible resin in the polyolefin resin in 100% by mass of the non-porous body. As a result, the specific gravity of the microorganism carrier can be further increased by increasing the content of the inorganic powder, thereby improving the water sedimentation property.
以下、本発明の一実施形態に係る微生物担体について説明する。図1及び図2に示す微生物担体10は、嫌気性処理に使用されるものであり、比重(JIS K 7112:1999 B法準拠)が1より大の非多孔質体からなり、外周面に相対的に外径の大きい大径部13と相対的に外径の小さい小径部15を、非多孔質体の長さ方向に交互に有する波形状の凹凸を有するペレットからなる。前記微生物担体10の長さL(軸方向寸法)は1〜10mm、大径部13の平均外径Dは2.5〜5.0mm、小径部15の平均外径dは2.0〜4.5mm、大径部の平均外径と小径部の平均外径の比(D/d)は1.02〜1.50、隣り合う大径部13の間隔Pは0.8〜2.5mmが好ましい。
Hereinafter, a microbial carrier according to an embodiment of the present invention will be described. The
前記D/dが1.50より大の場合には表面の凹凸差が大きくなり、前記微生物担体10を水中に投入した際に、前記小径部15に気泡が溜まりやすくなって水沈降性が低下するようになる。一方、D/dが1.02より小の場合には表面の凹凸差が小さくなって、微生物の付着面積が低下すると同時に、前記小径部15に微生物が保持されにくくなる。
前記大径部13の間隔Pが2.5mmよりも大の場合には、微生物の付着面積が低下すると同時に、前記小径部15で構成される表面の凹部における開口程度が大になり、微生物が保持されにくくなる。一方、大径部間の間隔Pが0.8mmより小の場合には、前記小径部15で構成される表面の凹部が深くなりすぎて、前記微生物担体10を水中に投入した際に小径部15に空気が閉じ込められやすくなり、水沈降性が低下するようになる。また、汚水浄化槽における水圧および微生物担体の充填量によって、大径部13の間隔Pを適正にすることで、処理量や負荷量を調整することが好ましい。
なお、前記微生物担体10の形状は、全て一定でもよいが、長さ、外径、D/d、大径部13の間隔および波形状そのものが所定範囲でランダムに変化していてもよい。
When the D / d is greater than 1.50, the unevenness of the surface becomes large, and when the
When the interval P between the large-diameter portions 13 is larger than 2.5 mm, the adhesion area of the microorganisms decreases, and at the same time, the degree of opening in the concave portion of the surface constituted by the small-
The shape of the
前記微生物担体10を構成する非多孔質体は、ポリオレフィン系樹脂と無機粉末、さらには適宜含まれる非相溶性樹脂とからなる樹脂原料を、押出機から気相中に押し出してストランドを形成させることによって外周面に前記大径部13と小径部15を形成し、水相中で冷却後に所定長でカットしたものからなる。
The non-porous body constituting the
前記ポリオレフィン系樹脂としては、ポリエチレン(PE)樹脂、ポリプロピレン(PP)樹脂、エチレン−酢酸ビニル共重合体(EVA)樹脂、ポリスチレン(PS)樹脂等を挙げることができ、それらが単独で又は二種類以上組み合わせて使用される。特にポリエチレン樹脂は、本発明において好適なポリオレフィン系樹脂の一つである。ポリオレフィン系樹脂の量は、非多孔質体100質量%中、30〜90質量%が好ましく、特に30〜70質量%が好ましい。30質量%未満の場合には波形状の凹凸が形成されにくくなり、また非多孔質体の結合力が弱くなるため、成形時にはストランドが切断しやすく、かつ水中では微生物担体の形状が保持しにくい。一方90質量%を超える場合には非多孔質体の比重が1未満になって微生物担体10の水沈降性が低下(悪化)する。
Examples of the polyolefin resin include polyethylene (PE) resin, polypropylene (PP) resin, ethylene-vinyl acetate copolymer (EVA) resin, polystyrene (PS) resin, and the like. Used in combination. In particular, polyethylene resin is one of the preferred polyolefin resins in the present invention. The amount of the polyolefin-based resin is preferably 30 to 90% by mass, particularly preferably 30 to 70% by mass in 100% by mass of the non-porous body. If it is less than 30% by mass, it becomes difficult to form corrugated irregularities, and the binding force of the non-porous body is weakened. Therefore, the strand is easily cut during molding, and the shape of the microbial carrier is difficult to maintain in water. . On the other hand, when it exceeds 90% by mass, the specific gravity of the non-porous body is less than 1, and the water sedimentation property of the
前記無機粉末としては、炭酸カルシウム、硫酸バリウム、ゼオライト、タルク、酸化チタン、チタン酸カリウム、水酸化アルミニウム等を挙げることができ、それらの一種あるいは複数種類を組み合わせて使用することができる。特に炭酸カルシウムは好適である。無機粉末は、前記微生物担体10を構成する非多孔質体の比重を増大させる作用を有する。無機粉末の量は、非多孔質体100質量%中、10〜70質量%が好ましく、特に30〜50質量%が好ましい。10質量%未満の場合、非多孔質体の比重が1未満になって微生物担体10の水沈降性が低下(悪化)し、一方、70質量%を超える場合には、波形状の凹凸が形成されにくくなり、また結合力が弱くなって水中で微生物担体10が分離し易くなる。
Examples of the inorganic powder include calcium carbonate, barium sulfate, zeolite, talc, titanium oxide, potassium titanate, aluminum hydroxide, and the like, and one or more of them can be used in combination. Calcium carbonate is particularly preferred. The inorganic powder has an action of increasing the specific gravity of the non-porous body constituting the
前記非相溶性樹脂は、前記ポリオレフィン系樹脂とは異なる樹脂であって、前記ポリオレフィン系樹脂よりも溶解度パラメータδ(SP値)が1〜5(MJ/m3)1/2大きいものが好ましい。SP値の差が1(MJ/m3)1/2未満では、ポリエチレン(PE)樹脂およびポリプロピレン(PP)樹脂中において相溶化しやすく、波形状の凹凸を発生させる作用を生じにくく、逆に、SP値の差が5(MJ/m3)1/2より大きい場合、押し出し成形時にストランドが切断されやすく、微生物担体として長期使用時に分離しやすくなる。 The incompatible resin is a resin different from the polyolefin resin and preferably has a solubility parameter δ (SP value) of 1 to 5 (MJ / m 3 ) 1/2 larger than that of the polyolefin resin. If the difference in SP value is less than 1 (MJ / m 3 ) 1/2, it is easy to be compatible in polyethylene (PE) resin and polypropylene (PP) resin, and it is difficult to produce the effect of generating corrugated irregularities. When the difference in SP value is larger than 5 (MJ / m 3 ) 1/2 , the strands are easily cut during extrusion molding and are easily separated when used as a microbial carrier for a long time.
前記非相溶性樹脂としては、アクリル樹脂(ポリメタクリル酸メチル:PMMA)、ポリカーボネート樹脂、ABS樹脂、ポリ塩化ビニル樹脂、ポリエチレンテレフタレート樹脂、ポリウレタン樹脂等を挙げることができ、それらの一種類あるいは複数種類を組み合わせて使用することができる。特にアクリル樹脂、ポリカーボネート樹脂およびABS樹脂は、ポリエチレン(PE)樹脂およびポリプロピレン(PP)樹脂よりもSP値が大きく、その差は1〜5(MJ/m3)1/2であるため、ポリエチレン(PE)樹脂やポリプロピレン(PP)樹脂と混合されると、押し出し成形時にダイ内壁面で臨界せん断応力を超え、表面に波形状の凹凸を発生させやすく、好ましいものである。前記非相溶性樹脂は、前記非多孔質体に適宜含まれる添加剤であり、非多孔質体に含まれることによって、大径部の平均外径と小径部の平均外径の比(D/d)を大きくする作用があるため、前記無機粉末の含有量を増加させ、波形状の凹凸が形成されにくい場合でも波形状の凹凸を形成させることができ、それにより微生物担体10の水沈降性を向上させることができる。前記アクリル樹脂は、前記非多孔質体に含有させる場合、前記非多孔質体100質量%中1〜20質量%が好ましい。1質量%未満の場合、アクリル樹脂による効果が得られず、一方、20質量%を超える場合には、ポリオレフィン系樹脂の含有量が少なくなって成形しにくくなり、D/dが小さくなる傾向にある。 Examples of the incompatible resin include acrylic resin (polymethyl methacrylate: PMMA), polycarbonate resin, ABS resin, polyvinyl chloride resin, polyethylene terephthalate resin, polyurethane resin, and the like. Can be used in combination. In particular, acrylic resin, polycarbonate resin, and ABS resin have a larger SP value than polyethylene (PE) resin and polypropylene (PP) resin, and the difference is 1 to 5 (MJ / m 3 ) 1/2. When it is mixed with PE) resin or polypropylene (PP) resin, it is preferable because it exceeds the critical shear stress on the inner wall surface of the die at the time of extrusion molding and tends to generate corrugated irregularities on the surface. The incompatible resin is an additive appropriately contained in the non-porous body, and by being contained in the non-porous body, the ratio of the average outer diameter of the large diameter portion to the average outer diameter of the small diameter portion (D / Since d) is increased, the content of the inorganic powder is increased, and even when the corrugated irregularities are difficult to be formed, the corrugated irregularities can be formed. Can be improved. When the acrylic resin is contained in the non-porous body, it is preferably 1 to 20% by mass in 100% by mass of the non-porous body. When the amount is less than 1% by mass, the effect of the acrylic resin cannot be obtained. On the other hand, when the amount exceeds 20% by mass, the content of the polyolefin-based resin is reduced and molding becomes difficult, and the D / d tends to decrease. is there.
なお、溶解度パラメータδ(SP値)は、フェダーズ(Fedors)の方法により決定される25℃におけるポリマーの繰り返し単位の値を指す。当該方法は、R.F.Fedors,Polym.Eng.Sci.,14(2),147(1974)に記載されている。即ち、求める化合物の構造式において、原子および原子団の蒸発エネルギーとモル体積のデータより次式により決定される。
δ=(ΣΔei/ΣΔvi)1/2
ただし、式中、ΔeiおよびΔviは、それぞれ原子または原子団の蒸発エネルギーおよびモル体積を表す。求める化合物の構造式はIR、NMR、マススペクトルなどの通常の構造分析手法を用いて決定する。
The solubility parameter δ (SP value) refers to the value of the repeating unit of the polymer at 25 ° C. determined by the method of Fedors. The method is described in RFFedors, Polym. Eng. Sci., 14 (2), 147 (1974). That is, in the structural formula of the desired compound, it is determined by the following formula from the evaporation energy and molar volume data of atoms and atomic groups.
δ = (ΣΔei / ΣΔvi) 1/2
However, in formula, (DELTA) ei and (DELTA) vi represent the evaporation energy and molar volume of an atom or an atomic group, respectively. The structural formula of the compound to be determined is determined using a general structural analysis technique such as IR, NMR, and mass spectrum.
図3は前記微生物担体10の製造装置の概略図である。前記製造装置30は、押出機(単軸又は多軸押出機)31、水中冷却槽33、ストランドカッター(引き取り装置及び切断装置)35からなる。前記製造装置30を用いる微生物担体10の製造は、次のようにして行われる。まず、前記ポリオレフィン系樹脂、無機粉末、及び適宜添加する非相溶性樹脂を前記の量で押出機31に投入し、前記押出機31内で溶融混練して押出機31から気相中に非多孔質状態で表面に波形状の凹凸を有するストランド状に押し出し、水中冷却槽33中を通して冷却硬化させ、前記ストランドをストランドカッター35の引き取り装置で引き取って、切断装置で切断し、ペレット化する。なお、前記非多孔質体を形成する混合材料を、バレル温度、ダイの形状、吐出量を調整して、ダイ内において前記混合材料のもつ臨界せん断応力以上とすることで、ストランド表面に波形状の凹凸を発生させる。その際、前記引き取り装置35によるストランドの引き取り速度は、押し出し速度に対して相対的に変化させることで波形状の凸部である大径部間の距離を調整することができる。これにより、汚水浄化槽における水圧および微生物担体の充填量によって、大径部13の間隔Pを適正にすることができ、処理量や負荷量を調整することができる。前記押し出し速度の好ましい例として4.0〜8.0m/分を挙げる。この範囲よりも遅いと、臨界せん断応力を得られず、逆に早すぎると、ダイのせん断発熱が高くなって樹脂粘度が低下するため、表面に波形状の凹凸が得られない。前記引き取り速度の例として5.5〜16.0m/分を挙げる。前記大径部13と小径部15を交互に形成したストランドを、前記ストランドカッター35の切断装置で所定長のペレットに切断して前記微生物担体10を得る。
FIG. 3 is a schematic view of an apparatus for producing the
以下の原料から、表1、表2に示す配合とし、図3に示した製造装置30を用いて実施例1〜15、比較例1〜3の微生物担体を製造した。
・ポリオレフィン系樹脂1:ポリエチレン樹脂、品名;ニポロンハード5700、MFR1.0(g/10min)、東ソー社製
・ポリオレフィン系樹脂2:ポリエチレン樹脂、品名;ニポロンハード2500、MFR8.0(g/10min)、東ソー社製
・無機粉末:炭酸カルシウム、品名;BF300、備北粉化工業社製
・アクリル樹脂:品名;アクリペットVH−001、三菱レイヨン社製
・ポリカーボネート:品名;パンライトL1225、帝人化成社製
・ABS樹脂:品名;PA767R、チーメイ社製
・親水化剤:木粉
・発泡剤:重曹(炭酸水素ナトリウム)、東ソー社製
押出機は、品名;二軸押出機KTX30、神戸製鋼社製であり、押出機の条件は、ダイ3mmφ×4つ、バレルおよびダイ温度180℃、吐出量40kg/時、押し出し速度5.5m/分、スクリュー回転数400rpmである。また、微生物担体の長さ(ストランドの切断長さ)は3mmであり、引き取り速度は各々表1及び表2に示すとおりである。
From the following raw materials, the microbial carriers of Examples 1 to 15 and Comparative Examples 1 to 3 were manufactured using the
Polyolefin resin 1: Polyethylene resin, product name: Nipolon Hard 5700, MFR 1.0 (g / 10 min), manufactured by Tosoh Corporation Polyolefin resin 2: Polyethylene resin, product name: Nipolon hard 2500, MFR 8.0 (g / 10 min), Tosoh -Inorganic powder: Calcium carbonate, product name: BF300, manufactured by Bihoku Powder Chemical Co., Ltd.-Acrylic resin: Product name: Acripet VH-001, manufactured by Mitsubishi Rayon Co., Ltd.-Polycarbonate: Product name: Panlite L1225, manufactured by Teijin Chemicals Ltd.-ABS Resin: Product name: PA767R, manufactured by Chimei Corporation ・ Hydrophilic agent: Wood flour ・ Blowing agent: Baking soda (sodium hydrogen carbonate), manufactured by Tosoh Corporation Extruder is a product name: twin screw extruder KTX30, manufactured by Kobe Steel Co., Ltd., extruded The conditions of the machine are: die 3mmφ × 4, barrel and die temperature 180 ° C, discharge rate 40 g / time, extrusion speed 5.5 m / min, a screw speed of 400 rpm. Further, the length of the microorganism carrier (strand cut length) is 3 mm, and the take-up speed is as shown in Table 1 and Table 2, respectively.
実施例1〜15、比較例1〜3の微生物担体に対して、見掛け密度(g/ml)、比重、大径部の平均外径D(mm)、小径部の平均外径d(mm)、径比D/d、大径部間距離(mm)、水沈降性(%)について測定した。見掛け密度の測定はJIS K 7365:1999、比重の測定はJIS K 7112:1999 B法に従って行った。大径部の平均外径の測定および小径部の平均外径の測定はノギスにより1/100mmの単位でn=5測定した平均値である。水沈降性は50個のペレット(微生物担体)を表面が水に濡れるように水槽表面で水に付着した後、20cmの水深の水槽に2分間放置した場合における該水槽底部へ沈殿したペレット数の百分率である。沈降速度は、ペレットを表面が水に濡れるように水槽表面で水に付着した後、水深20cm水槽において、水槽上部から底部への落下時間をストップウォッチにて測定し、5個の平均を算出した。実施例及び比較例の測定結果を表1、表2の下部に示す。 For the microorganism carriers of Examples 1 to 15 and Comparative Examples 1 to 3, the apparent density (g / ml), specific gravity, average outer diameter D (mm) of the large diameter portion, and average outer diameter d (mm) of the small diameter portion , Diameter ratio D / d, distance between large diameter portions (mm), water sedimentation (%). The apparent density was measured according to JIS K 7365: 1999, and the specific gravity was measured according to JIS K 7112: 1999 B method. The measurement of the average outer diameter of the large diameter portion and the average outer diameter of the small diameter portion are average values obtained by measuring n = 5 in units of 1/100 mm with a caliper. Water sedimentation is the number of pellets that settled to the bottom of the water tank when 50 pellets (microbe carrier) adhere to water on the surface of the water tank so that the surface gets wet and then left in a water tank at a depth of 20 cm for 2 minutes. Percentage. The sedimentation speed was calculated by calculating the average of 5 pieces by measuring the falling time from the top of the aquarium to the bottom with a stopwatch in a 20 cm water tank after the pellets adhered to the water so that the surface was wet with water. . The measurement results of Examples and Comparative Examples are shown in the lower part of Tables 1 and 2.
なお、比較例1は図4の(4−1)に示す比較例1の外周面に対する電子顕微鏡写真のように、外周面に微細な凹凸面が形成されるものの、小径部と大径部が測定可能な波形状ではなく測定できなかった。比較例2は外周面に波形状の凹凸が存在した。比較例3については表面に波形状ができなかった。 In addition, although the comparative example 1 has a fine uneven | corrugated surface formed in an outer peripheral surface like the electron micrograph with respect to the outer peripheral surface of the comparative example 1 shown to (4-1) of FIG. 4, a small diameter part and a large diameter part are It was not measurable wave shape and could not be measured. In Comparative Example 2, corrugated irregularities existed on the outer peripheral surface. In Comparative Example 3, the surface was not corrugated.
実施例1〜15については、表1の測定結果に示すとおり、比重が1より大きく、水沈降性が100%と良好であった。また、非多孔質物質からなって、大径部の平均外径と小径部の平均外径の比(D/d)を1.03〜1.28、大径部間距離を0.86〜2.14と調整することができた。なお、図4の(4−2)は、実施例2の外周面に対する電子顕微鏡写真であり、実施例2の外周面に大径部と小径部が交互に明確に形成されている。これにより、実施例1〜15では、担体表面にのみ微生物を適正量付着させることができるため水処理能力に優れ、かつ水中で長時間使用しても水中汚染を生じることもなく、その上、微生物の発生するガスによる浮力も発生することがない嫌気性処理に好適な微生物担体を得ることができた。 About Examples 1-15, as shown in the measurement result of Table 1, specific gravity was larger than 1, and the water sedimentation property was as favorable as 100%. Moreover, it consists of a non-porous substance, ratio (D / d) of the average outer diameter of a large diameter part and the average outer diameter of a small diameter part is 1.03-1.28, and the distance between large diameter parts is 0.86- It was possible to adjust to 2.14. In addition, (4-2) of FIG. 4 is an electron micrograph of the outer peripheral surface of Example 2, and large diameter portions and small diameter portions are clearly and alternately formed on the outer peripheral surface of Example 2. Thereby, in Examples 1-15, since it is possible to attach an appropriate amount of microorganisms only to the surface of the carrier, it is excellent in water treatment capacity, and does not cause underwater contamination even when used in water for a long time. A microbial carrier suitable for anaerobic treatment that does not generate buoyancy due to gas generated by microorganisms could be obtained.
一方、発泡剤および親水化剤を含んだ比較例1は、表2の測定結果に示すとおり、水沈降性が0%であり、さらに外周面に微細な凹凸面が形成されるものの、表面の凹凸を擦ると削れてしまい、嫌気性処理に不適であった。また、無機粉末の添加量が本発明構成より少ない比較例2は、表2の測定結果に示すとおり、水沈降性が0%であり、嫌気性処理に不適であった。また、MFRが5(g/10min)以上のポリオレフィン系樹脂を用いた比較例3は、水沈降性は良好であったものの、表面に波形状ができず微生物を適正量付着させることができなかった。 On the other hand, Comparative Example 1 containing a foaming agent and a hydrophilizing agent has a water sedimentation property of 0% as shown in the measurement results of Table 2, and a fine irregular surface is formed on the outer peripheral surface. When the unevenness was rubbed, it was scraped off, which was not suitable for anaerobic treatment. Moreover, as shown in the measurement results of Table 2, Comparative Example 2 in which the amount of the inorganic powder added was smaller than that of the present invention had a water sedimentation property of 0% and was unsuitable for anaerobic treatment. Further, Comparative Example 3 using a polyolefin resin having an MFR of 5 (g / 10 min) or more had good water sedimentation property, but could not be corrugated on the surface and could not attach an appropriate amount of microorganisms. It was.
10 微生物担体
13 大径部
15 小径部
10 Microorganism carrier 13
Claims (3)
前記微生物担体は非多孔質体からなり、
前記非多孔質体は、該非多孔質体の100質量%中にメルトマスフローレイト(JIS K7210:1999)が0.01(g/10min)以上5(g/10min)未満であるポリオレフィン系樹脂30〜90質量%と無機粉末10〜70質量%を含み、比重が1より大で、外周面に相対的に外径の大きい大径部と相対的に外径の小さい小径部とが前記非多孔質体の長さ方向に交互に存在する波形状の凹凸を有し、
前記非多孔質体の長さが、1〜10mmであり、
前記大径部の平均外径が、2.5〜5.0mmであり、
前記小径部の平均外径が、2.0〜4.5mmであり、
前記大径部の平均外径と前記小径部の平均外径の比(大径部の平均外径/小径部の平均外径)が、1.02〜1.50であり、
隣り合う前記大径部の間隔が0.8〜2.5mmであることを特徴とする微生物担体。 In a microbial carrier for holding microorganisms on the surface,
The microbial carrier comprises a non-porous body,
The non-porous body is a polyolefin resin 30 to 100 having a melt mass flow rate (JIS K7210: 1999) of 0.01 (g / 10 min) or more and less than 5 (g / 10 min) in 100% by mass of the non-porous body. comprises 90 wt% and the inorganic powder 10 to 70 wt%, specific gravity at greater than 1, it said and a small diameter portion having a relatively outer diameter greater large diameter portion of the relatively outer diameter to the outer peripheral surface nonporous have a wave-like irregularities present alternately in the longitudinal direction of the body,
The non-porous body has a length of 1 to 10 mm,
An average outer diameter of the large diameter portion is 2.5 to 5.0 mm,
The average outer diameter of the small diameter portion is 2.0 to 4.5 mm,
The ratio of the average outer diameter of the large diameter portion and the average outer diameter of the small diameter portion (average outer diameter of the large diameter portion / average outer diameter of the small diameter portion) is 1.02-1.50,
A microorganism carrier characterized in that the interval between the adjacent large diameter portions is 0.8 to 2.5 mm .
The microbial carrier according to claim 1 or 2, wherein the inorganic powder is calcium carbonate.
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