JP7398807B2 - Microbial adsorbent and microbial sterilization method using the same - Google Patents
Microbial adsorbent and microbial sterilization method using the same Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims description 65
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- 238000000034 method Methods 0.000 title claims description 9
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Sludge (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
本発明は、糞尿等に含まれる大腸菌等の細菌、鳥インフルエンザウイルス等のウイルス等の微生物を吸着する微生物吸着材およびこれを用いた微生物殺菌方法に関する。 The present invention relates to a microorganism adsorbent that adsorbs microorganisms such as bacteria such as Escherichia coli and viruses such as avian influenza virus contained in excrement and the like, and a method of sterilizing microorganisms using the same.
人や家畜にとって有害な細菌やウイルスに対しては種々の対策がなされている。例えば、家畜の糞尿の処理方法は、形状や畜種によって異なっているが、「野積み」、「素掘り」での処理は、水質汚濁、悪臭の発生源となっており改善が求められている。また、畜産農家から発生した処理水を河川や湖沼等の公共用水域に排出する場合、「水質汚濁防止法」に基づき排水基準(生活環境項目および健康項目)が適用される。このように、処理水の排出には、排水基準が設けられているものの、処理水に含まれる大腸菌群数は、限りなくゼロにすることが望ましいのは言うまでもない。 Various measures have been taken against bacteria and viruses that are harmful to humans and livestock. For example, methods for disposing of livestock manure vary depending on the shape and species of livestock, but methods such as "piling up in the open" or "digging" are sources of water pollution and foul odors, and improvements are needed. . Furthermore, when treated water generated by livestock farms is discharged into public water bodies such as rivers and lakes, wastewater standards (living environment items and health items) are applied based on the Water Pollution Control Act. Although wastewater standards are set for the discharge of treated water, it goes without saying that it is desirable to reduce the number of coliform bacteria contained in treated water to zero.
ここで、処理水に含まれる大腸菌群の除去方法として、塩素またはオゾン注入、紫外線照射等が一般的であるが、塩素注入は、安価であるものの鋼製配管等の設備を腐食させるという問題がある。また、オゾン注入や紫外線照射は、処理コストが高くなるため、特に小規模の畜産農家では設備導入が難しいという問題がある。 Common methods for removing coliform bacteria contained in treated water include chlorine or ozone injection, ultraviolet irradiation, etc. Although chlorine injection is inexpensive, it has the problem of corroding equipment such as steel piping. be. Furthermore, ozone injection and ultraviolet irradiation have the problem of high processing costs, making it difficult for small-scale livestock farms in particular to introduce equipment.
また、鳥インフルエンザウイルスは、変異によって高病原性鳥インフルエンザウイルスに変化することがある。野鳥の腸管内に高病原性鳥インフルエンザウイルスが保有されると、養鶏農場周囲にウイルスを含む糞便を落下させ、それらが鶏の感染源となっていると考えられている。ここで、高病原性鳥インフルエンザウイルスの鶏舎内への侵入を防ぐためには、鶏舎周囲への石灰等の薬剤散布が重要となるが、化学薬品の大量使用による環境負荷とコスト面が課題となっていた。 Furthermore, avian influenza viruses may change into highly pathogenic avian influenza viruses due to mutations. It is believed that when highly pathogenic avian influenza viruses are carried in the intestinal tracts of wild birds, they drop virus-containing feces around poultry farms, which becomes a source of infection for chickens. In order to prevent the highly pathogenic avian influenza virus from entering the poultry house, it is important to spray chemicals such as lime around the poultry house, but the environmental burden and cost of using large amounts of chemicals are issues. was.
発明者らは、特定の火山灰土壌、特に特定の鬼界アカホヤ火山灰土壌が腸管出血性大腸菌や鳥インフルエンザウイルスの吸着性能に優れるのみならず、驚くことに殺菌効果もあることを見出した。 The inventors have discovered that a specific volcanic ash soil, particularly a specific Kikai Akahoya volcanic ash soil, not only has excellent adsorption performance for enterohemorrhagic E. coli and avian influenza virus, but also surprisingly has a bactericidal effect.
本発明は、このような問題点に着目してなされたもので、安価にかつ環境への負担の少ない細菌やウイルス等の微生物を吸着・殺菌できる微生物吸着材およびこれを用いた微生物殺菌方法を提供することを目的とする。 The present invention has been made in view of these problems, and provides a microbial adsorbent that can adsorb and sterilize microorganisms such as bacteria and viruses at low cost and with less burden on the environment, and a microbial sterilization method using the same. The purpose is to provide.
前記課題を解決するために、本発明の微生物吸着材は、
Al2O3が30wt%以上である火山灰土壌を用いたことを特徴としている。
この特徴によれば、細菌、ウイルス等の微生物を含む水分を吸着しやすく、吸着・殺菌能力が高い。In order to solve the above problems, the microbial adsorbent of the present invention has the following features:
It is characterized by using volcanic ash soil containing 30 wt% or more of Al 2 O 3 .
According to this feature, it easily adsorbs moisture containing microorganisms such as bacteria and viruses, and has high adsorption and sterilization ability.
前記火山灰土壌は、Fe2O3が3~8wt%である鬼界アカホヤ火山灰土壌であることを特徴としている。
この特徴によれば、Al2O3の割合がFe2O3に比べ3倍以上と多く、アルミニウムイオンとリン酸イオンで錯体を形成しやすいため、リン酸を含む微生物等の吸着・殺菌能力に優れる。The volcanic ash soil is characterized by being Kikai Akahoya volcanic ash soil containing 3 to 8 wt% of Fe 2 O 3 .
According to this feature, the proportion of Al 2 O 3 is more than 3 times that of Fe 2 O 3 , and it is easy to form a complex with aluminum ions and phosphate ions, which improves the ability to adsorb and sterilize microorganisms containing phosphoric acid. Excellent in
前記火山灰土壌は、SiO2が39~65wt%、Al2O3が31~45wt%、Fe2O3が3~8wt%、その他が0~22wt%からなることを特徴としている。
この特徴によれば、天然の鬼界アカホヤ火山灰土壌への加工処理が少ない。The volcanic ash soil is characterized by containing 39 to 65 wt% of SiO 2 , 31 to 45 wt% of Al 2 O 3 , 3 to 8 wt% of Fe 2 O 3 , and 0 to 22 wt% of other components.
According to this characteristic, there is little processing required for the natural Kikai Akahoya volcanic ash soil.
前記火山灰土壌は、焼成されていることを特徴としている。
この特徴によれば、天然の鬼界アカホヤ火山灰土壌中に含まれている雑菌を消滅させることができる。The volcanic ash soil is characterized by being calcined.
According to this feature, it is possible to eliminate various bacteria contained in the natural Kikai Akahoya volcanic ash soil.
前記焼成は、1000℃以下で行われることを特徴としている。
この特徴によれば、火山灰土壌が有する細孔の径が小さいものが存在しやすく、微生物を吸着しやすい。The firing is characterized in that it is performed at a temperature of 1000°C or lower.
According to this feature, volcanic ash soil tends to have small pores, which makes it easy to adsorb microorganisms.
前記火山灰土壌は、少なくとも径100nm以下の細孔を有することを特徴としている。
この特徴によれば、細孔の径が小さいものが存在しやすく、微生物を吸着しやすい。The volcanic ash soil is characterized by having pores with a diameter of at least 100 nm or less.
According to this feature, pores with small diameters tend to exist, and microorganisms are easily adsorbed.
前記火山灰土壌は、比表面積が3.9m2g-1以上であることを特徴としている。
この特徴によれば、表面積が広く、微生物を吸着しやすい。The volcanic ash soil is characterized by having a specific surface area of 3.9 m 2 g -1 or more.
According to this feature, the surface area is large and microorganisms can be easily adsorbed.
前記火山灰土壌は、粒径1mm以下の粉末であることを特徴としている。
この特徴によれば、粉末状であるので散布して使用することが簡便である。The volcanic ash soil is characterized in that it is a powder with a particle size of 1 mm or less.
According to this feature, since it is in powder form, it is easy to use it by scattering it.
前記火山灰土壌は、土粒子密度2.6~2.7g/cm3の粉末であることを特徴としている。
この特徴によれば、土粒子密度が低いため、攪拌やばっ気を行うことで水に浮かせた状態で使用することができる。The volcanic ash soil is characterized in that it is a powder with a soil particle density of 2.6 to 2.7 g/cm 3 .
According to this feature, since the soil particle density is low, it can be used while floating on water by stirring or aerating.
前記課題を解決するために、本発明の微生物吸着材を用いた微生物殺菌方法は、前記微生物吸着材を用いたことを特徴としている。
この特徴によれば、細菌やウイルス等の微生物を安価にかつ環境への負担の少なく殺菌することができる。In order to solve the above problems, a microorganism sterilization method using a microorganism adsorbent according to the present invention is characterized in that the microorganism adsorbent is used.
According to this feature, microorganisms such as bacteria and viruses can be sterilized at low cost and with less burden on the environment.
発明者らは、家畜の糞尿等に含まれる腸管出血性大腸菌(以下、単に「大腸菌」と表記することもある。)等の細菌、鳥インフルエンザウイルス等のウイルス等の微生物を吸着ないし殺菌する素材として、火山灰土壌、特に天然の鬼界アカホヤ火山灰土壌(以下、単に「アカホヤ」と表記する。)が優れるとの知見を得た。研究の結果から、成分および構造に着目することが有意であったことから、先ずこの事項について説明する。 The inventors have developed a material that adsorbs or sterilizes microorganisms such as enterohemorrhagic Escherichia coli (hereinafter sometimes simply referred to as "Escherichia coli") and other bacteria and viruses such as avian influenza virus, which are contained in livestock manure, etc. As a result, we have found that volcanic ash soil, especially natural Kikai Akahoya volcanic ash soil (hereinafter simply referred to as "Akahoya"), is excellent. Based on the research results, it was significant to focus on the components and structure, so this point will be explained first.
微生物吸着材による微生物の吸着ないし殺菌のメカニズムについて説明する。微生物吸着材は、径100nm以下の無数の細孔を有し、その比表面積が大きいため、ファンデルワールス力や水素結合による微生物に対する物理的な吸着性に優れているとともに、吸水性にも優れている。さらに、微生物吸着材は、Al2O3(酸化アルミニウム)およびFe2O3(酸化鉄)の組成比が高く、親水性を示すため、吸水後では、イオン化したAl3+(アルミニウムイオン)およびFe3+(鉄イオン)が微生物の細胞膜の表面(リン脂質の親水基)を構成するPO4 3-(リン酸イオン)と高い化学結合性(化学反応性)を示し、不溶性のAlPO4(リン酸アルミニウム)およびFePO4(リン酸鉄)が生成される。イオン化したAl3+およびFe3+とPO4 3-との化学結合の化学式を下記の化1に示す。The mechanism of adsorption or sterilization of microorganisms by the microorganism adsorbent will be explained. Microbial adsorbents have countless pores with a diameter of 100 nm or less and have a large specific surface area, so they have excellent physical adsorption to microorganisms due to van der Waals forces and hydrogen bonds, as well as excellent water absorption. ing. Furthermore, the microbial adsorbent has a high composition ratio of Al 2 O 3 (aluminum oxide) and Fe 2 O 3 (iron oxide) and exhibits hydrophilicity, so after water absorption, it absorbs ionized Al 3+ (aluminum ions) and Fe 3+ (iron ion) exhibits high chemical bonding (chemical reactivity) with PO 4 3- (phosphate ion) that constitutes the surface of microbial cell membranes (hydrophilic groups of phospholipids), and insoluble AlPO 4 (phosphate aluminum) and FePO 4 (iron phosphate) are produced. The chemical formula of the chemical bond between ionized Al 3+ and Fe 3+ and PO 4 3- is shown in Chemical Formula 1 below.
尚、微生物の細胞膜は、リン脂質の自己組織化により脂質二重層を構成しているが、細胞膜の表面(リン脂質の親水基)を構成するPO4 3-が微生物吸着材のAl3+およびFe3+と化学結合してAlPO4およびFePO4を生成することにより、リン脂質が分解する。特に、大腸菌については、このリン脂質の分解を原因として細胞膜の分解が起こり死滅するものと考えられる。尚、微生物吸着材に吸着されず処理水中を浮遊している大腸菌についても、処理水中に溶け出したAl3+およびFe3+と化学結合することにより同様に死滅する。Note that the cell membrane of microorganisms constitutes a lipid bilayer due to the self-assembly of phospholipids, and the PO 4 3- that constitutes the surface of the cell membrane (hydrophilic groups of phospholipids) is combined with Al 3+ and Fe of the microbial adsorbent. Phospholipids are degraded by chemically bonding with 3+ to produce AlPO4 and FePO4 . In particular, E. coli is thought to die due to the decomposition of its cell membrane due to the decomposition of this phospholipid. Note that Escherichia coli floating in the treated water without being adsorbed by the microbial adsorbent is also killed by chemical bonding with Al 3+ and Fe 3+ dissolved in the treated water.
このように、微生物吸着材は、径100nm以下の無数の細孔により微生物を物理的に吸着するとともに、イオン化したAl3+およびFe3+が微生物の細胞膜を構成するPO4 3-と高い化学結合性を示してAlPO4およびFePO4を生成することにより、微生物を効率よく吸着ないし殺菌することができる。In this way, microbial adsorbents physically adsorb microorganisms through countless pores with a diameter of 100 nm or less, and ionized Al 3+ and Fe 3+ have a high chemical bond with PO 4 3- , which constitutes the cell membrane of microorganisms. By producing AlPO 4 and FePO 4 with the above expression, microorganisms can be efficiently adsorbed or sterilized.
本発明に係る微生物吸着材を実施するための形態を実施例に基づいて以下に説明する。尚、本実施例において成分組成比等の各試験結果はサンプル数3以上の平均値である。 Embodiments for carrying out the microbial adsorbent according to the present invention will be described below based on Examples. In this example, each test result such as the component composition ratio is an average value of three or more samples.
微生物吸着材は、宮崎県東諸県郡地区産出のアカホヤを粉砕してふるいにかけた後、次の条件で焼成することにより土壌由来の細菌を死滅させるとともに、構成化合物を安定させ、一定の形状と強度を確保する。
温度 800℃
保持時間 60分(昇温100℃/1時間)
焼成装置(ADVANTEC社製電気マッフル炉FUW220PA)The microbial adsorbent is made by crushing and sifting Acahoya grown in the Higashimorokken District, Miyazaki Prefecture, and then firing it under the following conditions to kill soil-borne bacteria, stabilize the constituent compounds, and maintain a certain shape and strength. ensure that
Temperature 800℃
Holding time 60 minutes (temperature increase 100℃/1 hour)
Firing equipment (ADVANTEC electric muffle furnace FUW220PA)
焼成前のアカホヤの成分組成比は以下のとおりであった。尚、成分組成比は、島津製作所社製エネルギー分散型蛍光X線分析装置EDX-720を用いてJIS K0119:2008により分析した。
51.0wt% SiO2
39.7wt% Al2O3
4.71wt% Fe2O3
1.49wt% K2O
1.40wt% CaO
0.51wt% MgO
0.53wt% TiO2
0.66wt% その他The component composition ratios of Acahoya before firing were as follows. The component composition ratio was analyzed in accordance with JIS K0119:2008 using an energy dispersive X-ray fluorescence spectrometer EDX-720 manufactured by Shimadzu Corporation.
51.0wt% SiO2
39.7wt % Al2O3
4.71wt % Fe2O3
1.49wt% K2O
1.40wt% CaO
0.51wt% MgO
0.53wt% TiO2
0.66wt% Others
焼成後のアカホヤの成分組成比は以下の表1のとおりであった。 The component composition ratio of Acacacia after firing was as shown in Table 1 below.
焼成後のアカホヤは、Al2O3の成分組成比が38.3wt%、Fe2O3の成分組成比が3.96wt%であり、SiO2に対してAl2O3およびFe2O3の比率が高い。Akahoya after firing has a component composition ratio of Al 2 O 3 of 38.3 wt % and a component composition ratio of Fe 2 O 3 of 3.96 wt %, and has a composition ratio of Al 2 O 3 and Fe 2 O 3 with respect to SiO 2. The ratio of
ここで、焼成温度によって細孔径分布、比表面積が変化しているので以下説明する。尚、細孔径分布は、Micromeritics社製AutoPoreV9620を用いて水銀圧入法(JIS R1655)により分析した。 Here, the pore size distribution and specific surface area change depending on the firing temperature, which will be explained below. Note that the pore size distribution was analyzed by mercury intrusion method (JIS R1655) using AutoPore V9620 manufactured by Micromeritics.
図1のグラフに示されるように、アカホヤの細孔は、径0.01~10μm(100~10000nm)に分布しており、焼成温度800~1000℃では、径100nm以下の細孔は1体積%以上であり細孔の分布があるが、焼成温度1100℃、1150℃では、径100nm以下の細孔は1体積%未満であり細孔の分布がなくなっている。すなわち、焼成温度が高くなるにつれて細孔が閉塞し、細孔径分布が変化することが確認された。 As shown in the graph of Fig. 1, the pores of Acacacia are distributed with a diameter of 0.01 to 10 μm (100 to 10,000 nm), and at a firing temperature of 800 to 1,000°C, the pores with a diameter of 100 nm or less are 1 volume. % or more, and there is a pore distribution, but at firing temperatures of 1100°C and 1150°C, pores with a diameter of 100 nm or less are less than 1% by volume, and there is no pore distribution. That is, it was confirmed that as the firing temperature increases, the pores become clogged and the pore size distribution changes.
また、比表面積は、Micromeritics社製FlowSorb3 2310を用いてBET法(JIS Z8830)により求めた。 Further, the specific surface area was determined by the BET method (JIS Z8830) using FlowSorb3 2310 manufactured by Micromeritics.
表2に示されるように、アカホヤの比表面積は、焼成無しで68.7m2g-1であったものが、焼成温度800℃で36.0m2g-1、焼成温度900℃で9.54m2g-1、焼成温度1000℃で3.9m2g-1、焼成温度1100℃で1.35m2g-1、焼成温度1150℃で0.79m2g-1と低下している。すなわち、焼成温度が高くなるにつれて細孔の閉塞に伴い比表面積が低下する。As shown in Table 2, the specific surface area of Acahoya was 68.7 m 2 g -1 without firing, 36.0 m 2 g -1 at a firing temperature of 800°C, and 9.0 m 2 g -1 at a firing temperature of 900°C. 54 m 2 g -1 , 3.9 m 2 g -1 at a firing temperature of 1000°C, 1.35 m 2 g -1 at a firing temperature of 1100°C, and 0.79 m 2 g -1 at a firing temperature of 1150°C. That is, as the firing temperature increases, the specific surface area decreases due to pore blockage.
また、図2の写真に示されるように、焼成温度800℃で焼成したアカホヤに大腸菌の浮遊液をろ過した後の通過液を培養すると、生菌が検出されなかった(図2の中段参照)。また、大腸菌の浮遊液をろ過した後のアカホヤに再びバッファ液を通して洗浄した洗浄液を培養しても、同様の結果が得られた(図2の下段参照)。すなわち、アカホヤの焼成は、径100nm以下の細孔の分布があり、その比表面積が3.9m2g-1以上(好ましくは36.0~69.0m2g-1)となる焼成温度1000℃以下(好ましくは800℃以下)で行われることにより、アカホヤの細孔による微生物の物理的な吸着能力を維持することができる。また、焼成温度が100℃未満では、土壌由来の細菌が十分に死滅しない可能性があることから、焼成温度は、好ましくは100~1000℃、さらに好ましくは180~800℃であることが判明した。さらに、火山灰土壌中の有機物は無い方が好ましく、この場合、焼成温度は800℃以上であることが望ましい。Furthermore, as shown in the photograph in Figure 2, when the suspension of E. coli was cultured in Akahoya fired at a firing temperature of 800°C, no viable bacteria were detected (see the middle row of Figure 2). . Furthermore, similar results were obtained when the E. coli suspension was filtered and the washed solution was cultured by passing the buffer solution through the Aca ascidia again (see the lower part of FIG. 2). That is, the firing of Acacacia is carried out at a firing temperature of 1000 which results in a distribution of pores with a diameter of 100 nm or less and a specific surface area of 3.9 m 2 g -1 or more (preferably 36.0 to 69.0 m 2 g -1 ). By carrying out the heating at a temperature of 800° C. or lower (preferably 800° C. or lower), the physical adsorption ability of microorganisms by the pores of the Acacia can be maintained. In addition, if the firing temperature is less than 100°C, soil-derived bacteria may not be sufficiently killed, so it was found that the firing temperature is preferably 100 to 1000°C, and more preferably 180 to 800°C. . Furthermore, it is preferable that there be no organic matter in the volcanic ash soil, and in this case, the firing temperature is desirably 800° C. or higher.
次に、上述したアカホヤと同様の加工処理を行った栃木県鹿沼地区産出の赤玉土について説明する。 Next, Akadama soil produced in the Kanuma area of Tochigi Prefecture, which has been processed in the same manner as the Akahoya described above, will be explained.
焼成前の赤玉土の成分組成比は以下のとおりであった。
46.5wt% SiO2
34.9wt% Al2O3
13.2wt% Fe2O3
1.37wt% K2O
0.58wt% CaO
1.31wt% MgO
1.35wt% TiO2
0.79wt% その他The component composition ratio of Akadama clay before firing was as follows.
46.5wt% SiO2
34.9wt % Al2O3
13.2wt % Fe2O3
1.37wt% K2O
0.58wt% CaO
1.31wt% MgO
1.35wt% TiO2
0.79wt% Others
焼成後の赤玉土の成分組成比は以下の表3のとおりであった。 The component composition ratio of Akadama clay after firing was as shown in Table 3 below.
焼成後の赤玉土は、Al2O3の成分組成比が33.0wt%、Fe2O3の成分組成比が12.5wt%であり、SiO2に対してAl2O3およびFe2O3の比率が高い。また、アカホヤと比べてAl2O3の成分組成比が低く、Fe2O3の成分組成比が高い。Akadama soil after firing has a component composition ratio of Al 2 O 3 of 33.0 wt %, a component composition ratio of Fe 2 O 3 of 12.5 wt %, and a ratio of Al 2 O 3 and Fe 2 O to SiO 2. The ratio of 3 is high. Furthermore, compared to Acacacia, the component composition ratio of Al 2 O 3 is lower and the component composition ratio of Fe 2 O 3 is higher.
次に、上述したアカホヤおよび赤玉土と同様の加工処理を行った宮崎県新富地区産出の粘土について説明する。 Next, clay produced in the Shintomi area of Miyazaki Prefecture that has been processed in the same manner as the Akahoya and Akadama clay described above will be described.
焼成前の成分組成比は以下のとおりであった。
65.2wt% SiO2
23.0wt% Al2O3
5.18wt% Fe2O3
3.71wt% K2O
0.24wt% CaO
1.65wt% MgO
0.81wt% TiO2
0.21wt% その他The component composition ratio before firing was as follows.
65.2wt% SiO2
23.0wt % Al2O3
5.18wt % Fe2O3
3.71wt% K2O
0.24wt% CaO
1.65wt% MgO
0.81wt% TiO2
0.21wt% Others
焼成後の粘土の成分組成比は以下の表4のとおりであった。 The composition ratio of the clay after firing was as shown in Table 4 below.
焼成後の粘土は、Al2O3の成分組成比が22.7wt%、Fe2O3の成分組成比が4.76wt%であり、SiO2に対してAl2O3およびFe2O3の比率が低い。また、アカホヤと比べてAl2O3の成分組成比が低く、Fe2O3の成分組成比が略同じである。The clay after firing has a component composition ratio of Al 2 O 3 of 22.7 wt %, a component composition ratio of Fe 2 O 3 of 4.76 wt %, and a ratio of Al 2 O 3 and Fe 2 O 3 to SiO 2 . The ratio of Moreover, the component composition ratio of Al 2 O 3 is lower than that of Acacacia, and the component composition ratio of Fe 2 O 3 is approximately the same.
尚、上述したアカホヤ、赤玉土および粘土と同様の加工処理を行った宮崎県都城地区産出のシラスについて、焼成後のシラスは、一般的な成分の特徴として、SiO2に対してAl2O3およびFe2O3の比率が低い。また、アカホヤと比べてAl2O3およびFe2O3の成分組成比が低い。Regarding whitebait produced in the Miyakonojo area of Miyazaki Prefecture, which has been processed in the same way as the Akahoya, Akadama soil, and clay mentioned above, the whitebait after firing has a general composition characteristic that is Al 2 O 3 compared to SiO 2 . and a low proportion of Fe 2 O 3 . Moreover, the component composition ratio of Al 2 O 3 and Fe 2 O 3 is lower than that of Acacia.
同じく、栃木県鹿沼地区産出の鹿沼土について、焼成後の鹿沼土は、一般的な成分の特徴として、SiO2に対してAl2O3およびFe2O3の比率が低い。また、アカホヤと比べてAl2O3およびFe2O3の比率が低い。Similarly, regarding Kanuma soil produced in the Kanuma area of Tochigi Prefecture, the Kanuma soil after firing has a low ratio of Al 2 O 3 and Fe 2 O 3 to SiO 2 as a general component characteristic. Moreover, the ratios of Al 2 O 3 and Fe 2 O 3 are lower than that of Acacia.
すなわち、アカホヤは、赤玉土、粘土、シラスおよび鹿沼土と比べて、安定度定数の高いAl3+を生じるAl2O3の成分組成比が高く、かつ赤玉土と比べてFe2O3の成分組成比が低いため、例えばAl3+(アルミニウムイオン)と糞尿中のPO4 3-(リン酸イオン)で錯体を形成しやすく、当該錯体と微生物の細胞膜を構成するPO4 3-との逐次反応が起こり、微生物をより効率よく吸着することができる。That is, Akahoya has a higher component composition ratio of Al 2 O 3 that produces Al 3+ with a high stability constant than Akadama soil, clay, Shirasu, and Kanuma soil, and has a higher component composition ratio of Fe 2 O 3 than Akadama soil. Because the composition ratio is low, it is easy to form a complex with, for example, Al 3+ (aluminum ion) and PO 4 3- (phosphate ion) in excrement, and the sequential reaction between this complex and PO 4 3- that constitutes the cell membrane of microorganisms occurs. occurs, and microorganisms can be adsorbed more efficiently.
このように、微生物吸着材は、九州南部において地下の比較的浅い場所に無尽蔵に存在する自然素材であるアカホヤから構成されることにより、細菌やウイルス等の微生物に対する高い吸着能力を有しながら、安価にかつ環境への負担の少なくすることができる。尚、微生物吸着材として用いるアカホヤは、九州南部において産出されたものであれば、宮崎県東諸県郡地区産出のものに限らない。 In this way, the microbial adsorbent is composed of Aka ascidia, a natural material that exists in inexhaustible quantities in relatively shallow underground areas in southern Kyushu, and has a high ability to adsorb microorganisms such as bacteria and viruses. It can be done inexpensively and with less burden on the environment. Incidentally, the Acahoya used as the microbial adsorbent is not limited to those produced in the Higashimorokken District, Miyazaki Prefecture, as long as it is produced in southern Kyushu.
尚、以下の各実施例におけるアカホヤ等の火山灰土壌は、上述した成分のものを用いている。 Incidentally, the volcanic ash soil of Acahoya or the like in each of the following Examples uses the one having the above-mentioned components.
実施例1に係る微生物吸着材について説明する。実施例1の微生物吸着材は、粉砕し次の条件で乾熱滅菌した後、粒径0.5mm以下に調整したアカホヤ10gを径15mmの円筒形状のカラム内に充填することにより構成されている。
温度 180℃
時間 40分
乾熱滅菌器(ADVANTEC社製STA620DA)The microbial adsorbent according to Example 1 will be explained. The microbial adsorbent of Example 1 was constructed by filling a cylindrical column with a diameter of 15 mm with 10 g of Acacia japonica, which was pulverized and sterilized with dry heat under the following conditions, and then adjusted to a particle size of 0.5 mm or less. .
Temperature 180℃
Time: 40 minutes Dry heat sterilizer (ADVANTEC STA620DA)
微生物吸着材に大腸菌(105cfu/ml)10mlを通過させた後、カラム内のアカホヤ10mgを4℃で保存し、吸着した大腸菌の生存性を培養法により確認すると、図3の写真に示されるように、アカホヤに吸着された大腸菌は時間の経過と共に死滅していき、6日以降は生菌が検出されなかった(図3の左シャーレ参照)。尚、対照実験として、同一のカラムに宮崎県都城地区産出のシラス10gを充填して同様の実験を行った場合には、17日後まで生菌が検出された(図3の右シャーレ参照)。すなわち、アカホヤを素材とする微生物吸着材は、大腸菌の吸着・殺菌能力を有する。After passing 10 ml of Escherichia coli (10 5 cfu/ml) through the microbial adsorbent, 10 mg of Acacacia in the column was stored at 4°C, and the viability of the adsorbed Escherichia coli was confirmed by a culture method, as shown in the photograph in Figure 3. As shown, the E. coli that was adsorbed to the Acacia died over time, and no viable bacteria were detected after 6 days (see the left Petri dish in Figure 3). As a control experiment, when the same column was filled with 10 g of whitebait produced in the Miyakonojo area of Miyazaki Prefecture and a similar experiment was conducted, viable bacteria were detected until 17 days later (see the petri dish on the right in Figure 3). In other words, the microbial adsorbent made from Acacia as a material has the ability to adsorb and sterilize Escherichia coli.
尚、本実施例では、180℃で40分乾熱滅菌したアカホヤを使用する例について説明したが、焼成温度800℃で焼成されたアカホヤについても、同様の結果が得られた。 In this example, an example was explained in which Acacia sterilized by dry heat at 180°C for 40 minutes, but similar results were obtained with Acacacia sintered at a firing temperature of 800°C.
実施例2に係る微生物吸着材について説明する。実施例2の微生物吸着材は、粉砕し乾熱滅菌したアカホヤ0.2gを0.6mlのカラム(マイクロチューブ)に入れることにより構成されている。 The microbial adsorbent according to Example 2 will be explained. The microbial adsorbent of Example 2 was constructed by placing 0.2 g of crushed and dry-heat sterilized Acaca japonica into a 0.6 ml column (microtube).
微生物吸着材に鳥インフルエンザウイルス(H3N2亜型)0.4ml(HA価16倍、図4の上から2段目参照)を接種し、アカホヤを通過した後の通過液を2~256倍に希釈して血球凝集価(HA価)を測定すると、図4の写真に示されるように、鳥インフルエンザウイルスがアカホヤに吸着され、血球と凝集しなかった(HA価陰性、図4の下から2段目参照)。尚、対照実験として、0.6mlのカラムに宮崎県都城地区産出のシラス0.2gを入れて同様の実験を行った場合には、鳥インフルエンザウイルスがシラスにほとんど吸着されず血球と凝集した(HA価8倍,図4の最下段参照)。すなわち、アカホヤを素材とする微生物吸着材は、鳥インフルエンザウイルスの吸着能力を有する。 Inoculate 0.4 ml of avian influenza virus (H3N2 subtype) (HA value 16 times, see second row from the top of Figure 4) onto the microbial adsorbent, and dilute the liquid that has passed through the Aka ascidian 2 to 256 times. When the hemagglutination titer (HA titer) was measured, as shown in the photograph in Figure 4, the avian influenza virus was adsorbed to the red ascidian and did not agglutinate with blood cells (HA titer negative, two rows from the bottom of Figure 4). (see item). As a control experiment, when a similar experiment was carried out using 0.2 g of whitebait produced in the Miyakonojo area of Miyazaki Prefecture in a 0.6ml column, the avian influenza virus was hardly adsorbed to the whitebait and aggregated with blood cells ( HA value 8 times, see bottom row of Figure 4). In other words, the microbial adsorbent made from Acacia japonica has the ability to adsorb avian influenza virus.
実施例3に係る微生物吸着材について説明する。実施例3の微生物吸着材は、天然または焼成されたアカホヤであり、大型の容器に家畜の糞尿等の処理対象と一緒に投入した後、攪拌ことにより、処理対象物に含まれる大腸菌等の微生物との接触を促進しながら吸着ないし殺菌する。尚、これらの処理において発生する汚泥(使用後の微生物吸着材)は、大地還元が可能であることから処理コストが安く、汚泥の処理設備も不要となる。 The microbial adsorbent according to Example 3 will be explained. The microorganism adsorbent of Example 3 is natural or calcined Acacacia, which is put into a large container together with the object to be treated such as livestock manure, and then stirred to remove microorganisms such as Escherichia coli contained in the object to be treated. adsorbs or sterilizes while promoting contact with Note that the sludge (microbial adsorbent after use) generated in these treatments can be returned to the earth, so the treatment cost is low and sludge treatment equipment is not required.
実施例4に係る微生物吸着材について説明する。実施例4の微生物吸着材は、粒径0.5mm以下の粉末状に加工処理された天然または焼成されたアカホヤであり、散布しやすくなっている。粉末状の微生物吸着材は、例えば畜舎周囲に散布されることにより、畜舎周囲に存在する微生物を吸着ないし殺菌し、微生物の畜舎内への侵入を防ぐことができる。また、微生物吸着材として自然素材であるアカホヤを使用することにより、大量散布してもコストが安く、環境負荷も少ない。 The microbial adsorbent according to Example 4 will be explained. The microbial adsorbent of Example 4 is a natural or calcined Acaca sacrifice that has been processed into a powder with a particle size of 0.5 mm or less, making it easy to disperse. The powdered microbial adsorbent can adsorb or sterilize microorganisms present around the livestock barn, for example, by being sprayed around the livestock barn, thereby preventing microorganisms from entering the livestock barn. In addition, by using the natural material Acacia as a microbial adsorbent, the cost is low even when spraying in large quantities, and the environmental impact is low.
これらのことから、粒径は1mm以下、好ましくは0.5mm以下、さらに好ましくは0.1mm以下である。 For these reasons, the particle size is 1 mm or less, preferably 0.5 mm or less, and more preferably 0.1 mm or less.
さらに、微生物吸着材の素材としてのアカホヤを攪拌またはばっ気させることにより、水中に浮遊させた状態で使用できるようにしてもよい。また、例えば畜舎の出入口等に設置したトレー等に水を張り、水面に微生物吸着材を散布し、水面に浮かせた状態とすることにより、微生物吸着材を靴や家畜の脚等に確実に付着させ、靴や家畜の脚等に存在する微生物を確実に吸着ないし殺菌し、微生物の畜舎内への侵入を防ぐことができる。 Furthermore, the microorganism adsorbent material may be agitated or aerated so that it can be used in a suspended state in water. In addition, for example, by filling a tray installed at the entrance of a livestock barn with water, spraying the microbial adsorbent on the water surface, and leaving it floating on the water surface, the microbial adsorbent can be firmly attached to shoes, livestock legs, etc. It is possible to reliably adsorb or sterilize microorganisms present on shoes, livestock legs, etc., and prevent microorganisms from entering the livestock barn.
これらのことから、土粒子密度は2.6~2.7g/cm3が好ましく、さらにできる限り密度が低いことが好ましい。尚、土粒子密度は、JIS A1202:2009により求めた。For these reasons, the soil particle density is preferably 2.6 to 2.7 g/cm 3 , and it is further preferable that the density is as low as possible. Note that the soil particle density was determined according to JIS A1202:2009.
実施例5では大腸菌の生存試験について説明する。実施例5の微生物吸着材は、粉砕し次の条件で乾熱滅菌した後、粒径0.5mm以下に調整したアカホヤ、赤玉土、鹿沼土、シラス各10gを径15mmの円筒形状のカラム内にそれぞれ充填することにより構成されている。
温度 180℃
時間 40分
乾熱滅菌器(ADVANTEC社製STA620DA)Example 5 describes a survival test for E. coli. The microbial adsorbent of Example 5 was pulverized and dry heat sterilized under the following conditions, and then 10 g each of Akahoya, Akadama soil, Kanuma soil, and Shirasu adjusted to a particle size of 0.5 mm or less was placed in a cylindrical column with a diameter of 15 mm. It is constructed by filling each.
Temperature 180℃
Time: 40 minutes Dry heat sterilizer (ADVANTEC STA620DA)
微生物吸着材に定量の大腸菌を通過させた後、カラム内のアカホヤ、赤玉土、鹿沼土、シラス各10mgをそれぞれ4℃で保存し、吸着した大腸菌の生存性を培養法により確認すると、図5のグラフに示されるように、アカホヤ、赤玉土、鹿沼土、シラスに吸着された大腸菌は時間の経過と共にその菌数が減少していくことが確認された。このように、アカホヤ、赤玉土、鹿沼土、シラスを素材とする微生物吸着材は、大腸菌の吸着・殺菌能力を有する。 After passing a fixed amount of E. coli through the microbial adsorbent, 10 mg each of Akahoya, Akadama soil, Kanuma soil, and Shirasu in the column were stored at 4°C, and the viability of the adsorbed E. coli was confirmed by a culture method. As shown in the graph, it was confirmed that the number of E. coli bacteria adsorbed to Akahoya, Akadama soil, Kanuma soil, and Shirasu decreased over time. In this way, microbial adsorbents made from Acacia, Akadama soil, Kanuma soil, and whitebait have the ability to adsorb and sterilize Escherichia coli.
ここで、菌数が100分の1まで減少、すなわち99%の菌が死滅することで、有意な殺菌効果と言えるので、この値を評価基準とした。菌数が100分の1未満となる日数、すなわち大腸菌が死滅する日数は、アカホヤ、赤玉土に吸着された大腸菌は3日後、鹿沼土に吸着された大腸菌は9日後、シラスに吸着された大腸菌は17日後であり、それぞれ殺菌効果が確認された。このように、アカホヤ、赤玉土を素材とする微生物吸着材は、短期間で殺菌効果が得られることが確認された。尚、アカホヤ、赤玉土、鹿沼土に吸着された大腸菌は、その菌数が17日後には約1log cfu/gまで減少しており、長期間かけて略全ての菌が殺菌されることが確認された。 Here, since it can be said that a significant bactericidal effect is achieved when the number of bacteria is reduced to 1/100, that is, 99% of bacteria are killed, this value was used as the evaluation standard. The number of days for the number of bacteria to decrease to less than 1/100th, that is, the number of days for E. coli to die, is 3 days for E. coli adsorbed to Akahoya and Akadama soil, 9 days for E. coli adsorbed to Kanuma soil, and 9 days for E. coli adsorbed to Shirasu. After 17 days, the bactericidal effects of each were confirmed. In this way, it was confirmed that the microbial adsorbent made from Akahoya and Akadama soil can provide a bactericidal effect in a short period of time. Furthermore, the number of E. coli bacteria adsorbed to Akahoya, Akadama soil, and Kanuma soil decreased to approximately 1 log cfu/g after 17 days, confirming that almost all bacteria were sterilized over a long period of time. It was done.
実施例6では腸管出血性大腸菌O-157の生存試験について説明する。尚、微生物吸着材は実施例5と同様に製作したものを用いた。 Example 6 describes a survival test for enterohemorrhagic E. coli O-157. Note that the microbial adsorbent manufactured in the same manner as in Example 5 was used.
微生物吸着材に定量の腸管出血性大腸菌O-157(以下、単に「O-157」と表記する。)を通過させた後、カラム内のアカホヤ、赤玉土、鹿沼土、シラス各10mgをそれぞれ4℃で保存し、吸着したO-157の生存性を培養法により確認すると、図6のグラフに示されるように、アカホヤ、赤玉土、鹿沼土に吸着されたO-157は時間の経過と共にその菌数が減少していくことが確認された。このように、アカホヤ、赤玉土、鹿沼土を素材とする微生物吸着材は、O-157の吸着・殺菌能力を有する。 After passing a fixed amount of enterohemorrhagic Escherichia coli O-157 (hereinafter simply referred to as "O-157") through the microbial adsorbent, 10 mg each of Akahoya, Akadama soil, Kanuma soil, and Shirasu in the column were added to 4 When the viability of the adsorbed O-157 was confirmed by a culture method after storage at ℃, as shown in the graph in Figure 6, the O-157 adsorbed to Akahoya, Akadama soil, and Kanuma soil deteriorated over time. It was confirmed that the number of bacteria was decreasing. In this way, microbial adsorbents made of Akahoya, Akadama soil, and Kanuma soil have the ability to adsorb and sterilize O-157.
ここで、菌数が100分の1まで減少、すなわち99%の菌が死滅することで、有意な殺菌効果と言えるので、この値を評価基準とした。菌数が100分の1未満となる日数、すなわちO-157が死滅する日数は、アカホヤ、赤玉土に吸着されたO-157は7日後、鹿沼土に吸着されたO-157は14日以上後であり、それぞれ殺菌効果が確認された。このように、アカホヤ、赤玉土を素材とする微生物吸着材は、短期間で殺菌効果が得られることが確認された。尚、アカホヤ、赤玉土に吸着されたO-157は、その菌数が1ヶ月後には約1log cfu/gまで減少しており、長期間かけて略全ての菌が殺菌されることが確認された。 Here, since it can be said that a significant bactericidal effect is achieved when the number of bacteria is reduced to 1/100, that is, 99% of bacteria are killed, this value was used as the evaluation standard. The number of days for the number of bacteria to decrease to less than 1/100th, that is, the number of days for O-157 to die, is 7 days for O-157 adsorbed on Akahoya and Akadama soil, and 14 days or more for O-157 adsorbed on Kanuma soil. After that, the bactericidal effect of each was confirmed. In this way, it was confirmed that the microbial adsorbent made from Akahoya and Akadama soil can provide a bactericidal effect in a short period of time. Furthermore, the number of O-157 bacteria adsorbed on Akahoya and Akadama clay decreased to approximately 1 log cfu/g after one month, confirming that almost all bacteria were sterilized over a long period of time. Ta.
これら実施例5,6から、表5に示されるように、アカホヤ、赤玉土を素材とする微生物吸着材は、鹿沼土、シラスを素材とする微生物吸着材と比べて大腸菌およびO-157に対する有意な殺菌能力を有する。尚、表5中の「○」は有意な殺菌能力があることを示し、「△」は長い期間を要するものの殺菌能力があること示し、「×」は殺菌能力が不十分であったものを示している。 From these Examples 5 and 6, as shown in Table 5, the microbial adsorbent made from Akahoya and Akadama soil has a significant effect on E. coli and O-157 compared to the microbial adsorbent made from Kanuma soil and whitebait. It has excellent sterilizing ability. In addition, "○" in Table 5 indicates that there is a significant bactericidal ability, "△" indicates that the bactericidal ability is present although it takes a long period of time, and "x" indicates that the bactericidal ability was insufficient. It shows.
また、図5を参照し大腸菌に対する短期間(3日間以内)での殺菌能力、すなわち0日から3日後までの菌数の減少率は、アカホヤが赤玉土よりも優位である。同様に、図6を参照しO-157に対する短期間(7日間以内)での殺菌能力、すなわち0日から7日後までの菌数の減少率は、赤玉土がアカホヤよりも優位である。
Furthermore, referring to FIG. 5, Akahoya is superior to Akadama soil in terms of short-term (within 3 days) bactericidal ability against E. coli, that is, the rate of decrease in the number of bacteria from
以上、本発明の実施例を図面により説明してきたが、具体的な構成はこれら実施例に限られるものではなく、本発明の要旨を逸脱しない範囲における変更や追加があっても本発明に含まれる。 Although the embodiments of the present invention have been described above with reference to the drawings, the specific configuration is not limited to these embodiments, and any changes or additions that do not depart from the gist of the present invention are included in the present invention. It will be done.
例えば、前記実施例1~4では、微生物吸着材に天然または焼成等の加工処理が行われたアカホヤが用いられる例について説明したが、これに限らず、Al2O3を30wt%以上含有している火山灰土壌であれば、例えば天然の赤玉土、あるいは焼成された赤玉土であってもよく、鹿沼土や粘土やシラス等の火山灰土壌にAl2O3を30wt%以上含有させるように加工処理したものであってもよい。For example, in Examples 1 to 4, examples were explained in which the microbial adsorbent was natural or processed such as calcination , but the invention is not limited to this. For example, natural Akadama soil or fired Akadama soil may be used as long as it is a volcanic ash soil, such as Kanuma soil, clay, whitebait, etc., which is processed to contain 30 wt% or more of Al 2 O 3 . It may be a processed one.
また、微生物吸着材は、大腸菌以外の細菌(例えば、黄色ブドウ球菌、サルモネラ属菌、カンピロバクター、枯草菌芽胞、炭疽菌芽胞等)、鳥インフルエンザウイルス以外のウイルス等の微生物に対しても吸着効果を奏する。 In addition, the microbial adsorbent has an adsorption effect on microorganisms other than E. coli (e.g., Staphylococcus aureus, Salmonella spp., Campylobacter, Bacillus subtilis spores, Bacillus anthrax spores, etc.) and viruses other than avian influenza virus. play.
また、微生物吸着材は、焼成に限らず、例えば紫外線等により殺菌処理されてもよい。 Further, the microbial adsorbent is not limited to firing, and may be sterilized by, for example, ultraviolet rays.
1.家畜飼育環境の浄化システムの吸着材としての利用。
2.空気の浄化システム、例えば大気中の微生物を吸着する吸着材としての利用。
3.水の浄化システム、例えば閉鎖性水域(湖沼)における富栄養塩(リン)除去および大腸菌または大腸菌群等の微生物の吸着材としての利用。
4.バイオテロ対策システムにおける炭疽菌芽胞等の細菌やウイルスの吸着材としての利用。
5.病原体吸着物質含有飼料としての利用。1. Use as an adsorbent in purification systems for livestock breeding environments.
2. Use in air purification systems, for example as an adsorbent to adsorb microorganisms in the air.
3. Water purification systems, such as removal of nutrient salts (phosphorus) in closed water bodies (lakes) and use as an adsorbent for microorganisms such as Escherichia coli or coliform bacteria.
4. Use as an adsorbent for bacteria and viruses such as anthrax spores in bioterrorism countermeasure systems.
5. Use as feed containing pathogen-adsorbing substances.
Claims (8)
前記火山灰土壌は、Fe2O3が3~8wt%である鬼界アカホヤ火山灰土壌であることを特徴とする微生物吸着材。 Using volcanic ash soil containing 30 wt% or more of Al 2 O 3 ,
A microbial adsorbent characterized in that the volcanic ash soil is Kikai Akahoya volcanic ash soil containing 3 to 8 wt% of Fe 2 O 3 .
前記火山灰土壌は、SiO2が39~65wt%、Al2O3が31~45wt%、Fe2O3が3~8wt%、その他が0~22wt%からなることを特徴とする微生物吸着材。 Using volcanic ash soil containing 30 wt% or more of Al 2 O 3 ,
A microbial adsorbent characterized in that the volcanic ash soil contains 39 to 65 wt% of SiO 2 , 31 to 45 wt% of Al 2 O 3 , 3 to 8 wt % of Fe 2 O 3 , and 0 to 22 wt % of others.
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