JP6806361B2 - Method for manufacturing radiation-attenuating carbide composite material - Google Patents
Method for manufacturing radiation-attenuating carbide composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 65
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 65
- 235000005822 corn Nutrition 0.000 claims description 65
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 241000209149 Zea Species 0.000 claims 2
- 238000013016 damping Methods 0.000 claims 1
- 240000008042 Zea mays Species 0.000 description 63
- 239000002689 soil Substances 0.000 description 32
- 150000002500 ions Chemical class 0.000 description 24
- 238000001179 sorption measurement Methods 0.000 description 21
- 229910052792 caesium Inorganic materials 0.000 description 19
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 18
- 150000001247 metal acetylides Chemical class 0.000 description 18
- 230000005855 radiation Effects 0.000 description 16
- 230000002285 radioactive effect Effects 0.000 description 13
- 229910052793 cadmium Inorganic materials 0.000 description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 12
- 241000209094 Oryza Species 0.000 description 11
- 235000007164 Oryza sativa Nutrition 0.000 description 11
- 235000009566 rice Nutrition 0.000 description 11
- 239000003610 charcoal Substances 0.000 description 10
- 239000003516 soil conditioner Substances 0.000 description 9
- 239000004927 clay Substances 0.000 description 7
- -1 iron ions Chemical class 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 240000005109 Cryptomeria japonica Species 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229910052732 germanium Inorganic materials 0.000 description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 240000005020 Acaciella glauca Species 0.000 description 4
- 235000018782 Dacrydium cupressinum Nutrition 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 235000013697 Pinus resinosa Nutrition 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000035558 fertility Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 241001544353 Barringtonia racemosa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
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- 229910001417 caesium ion Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Description
本発明は、炭化物を用いた炭化物複合材料に関する。 The present invention relates to carbide composite materials using carbides.
炭化物を農業において土壌改良剤として活用する事例は非常に多い。したがって、コーンコブ（トウモロコシの芯）を焼成して炭化したコーンコブ炭化物も土壌改良剤としては例外ではない。また原材料であるコーンコブは産業廃棄物であり、かつ、安価に入手可能であることから、通常の土壌改良剤よりも使用される可能性は高い。また、コーンコブ炭化物は、コーンコブ特有の微細空間の多い多孔質構造を有し、さらに鉄イオンを多く含むものについては炭化物の結晶性が向上するため吸着剤としての効果がより高いことが分かっている。その結果、農業用地での土壌浄化に関する、様々な研究開発が進められている（例えば、特許文献１参照）。具体的な浄化の対象物としては、土壌環境中の有害金属（クロム、カドミウム、ヒ素、鉛イオン等）、残留農薬、過剰肥料等などあるが、これらが農作物に吸収されることでおきる食物汚染を防ぐ方法として炭化物の活用は有効的である。すなわち、多くの陽イオンの吸着が可能であることから、セシウムイオンもその例外ではない。そのことは、放射性セシウムに汚染された農業用地での土壌環境の浄化にも効果的に働くことを意味している。しかしながら、農業土壌でコーンコブ炭化物が土中にある放射性セシウムに対して吸着性能が高かったとしても、放射線（放射性セシウムの場合はγ線）を防ぐことはできず、農地から放射性セシウムを吸着した炭化物を取り除かない限りは、放射線は危険なままである。しかし、コーンコブ炭化物を用いる用途によっては、コーンコブ炭化物を単独で用いるよりも、他の材料と複合化した方が、目的に応じた特性をより高めることができ、用途も広げることができる。すなわち、炭化物に吸着した放射性セシウムからの放射線を阻止する機能を持った炭化物に複合化することで、それらの問題点は解決できる。 There are many cases where carbides are used as soil conditioners in agriculture. Therefore, carbonized corn hump obtained by calcining corn hump (corn core) is no exception as a soil conditioner. In addition, since the raw material, corn cob, is an industrial waste and can be obtained at a low price, it is more likely to be used than a normal soil conditioner. Further, it is known that the carbide of corn hump has a porous structure with many fine spaces peculiar to corn hump, and that the carbide containing a large amount of iron ions is more effective as an adsorbent because the crystallinity of the carbide is improved. .. As a result, various researches and developments on soil purification on agricultural land are underway (see, for example, Patent Document 1). Specific objects to be purified include harmful metals (chromium, cadmium, arsenic, lead ions, etc.) in the soil environment, residual pesticides, excess fertilizers, etc., but food contamination caused by absorption of these by agricultural crops. Utilization of carbides is effective as a method of preventing. That is, cesium ions are no exception because many cations can be adsorbed. This means that it also works effectively to purify the soil environment on agricultural land contaminated with radioactive cesium. However, even if corn cob charcoal has high adsorption performance for radioactive cesium in the soil in agricultural soil, it cannot prevent radiation (γ-rays in the case of radioactive cesium), and charcoal that adsorbs radioactive cesium from farmland. Radiation remains dangerous unless it is removed. However, depending on the use of the corn cob carbide, it is possible to further enhance the properties according to the purpose and expand the use by combining the corn cob carbide with another material rather than using the corn cob carbide alone. That is, those problems can be solved by combining the carbide with a carbide having a function of blocking radiation from radioactive cesium adsorbed on the carbide.
本発明は、このような問題に基づきなされたものであり、炭化物が土中にある放射性セシウムを吸着し、さらに放射線（放射性セシウムの場合はγ線）を防ぐことができる炭化物複合材料を提供することを目的とする。 The present invention has been made based on such a problem, and provides a carbide composite material capable of adsorbing radioactive cesium in the soil by carbides and further preventing radiation (γ-rays in the case of radioactive cesium). The purpose is.
本発明の炭化物複合材料は、粒子状の炭化物に、鉄を成分として含む粒子状の被覆物が付着されたものである。 The carbide composite material of the present invention is obtained by attaching a particulate coating containing iron as a component to a particulate carbide.
本発明によれば、粒子状の炭化物に、鉄を成分として含む粒子状被覆物を表面に付着することで、土壌中の放射性セシウムを吸着しつつ、空間の放射線量を低減させることができる。更に土壌改良材として用いることにより、植物の生長を促進し、収穫量を増量させることができると共に、食味も向上させることができ、かつ、病気の発生を抑制することができる。また、土壌の地力を向上させることができ、肥料や農薬の投入量を低減することができる。更に、土壌中のカドミウムやセシウム等の重金属が植物に移行することを抑制することができる。加えて、空間の放射線量を低減させることもできる。更にまた、重さが重くなるので、地面に定着させることができ、土壌改良材としての効果を高めることができる。 According to the present invention, by adhering a particulate coating containing iron as a component to a particulate carbide, it is possible to reduce the amount of radiation in the space while adsorbing radioactive cesium in the soil. Further, by using it as a soil conditioner, it is possible to promote the growth of plants, increase the yield, improve the taste, and suppress the outbreak of diseases. In addition, the soil fertility can be improved, and the amount of fertilizer and pesticide input can be reduced. Furthermore, it is possible to suppress the transfer of heavy metals such as cadmium and cesium in the soil to plants. In addition, the amount of radiation in the space can be reduced. Furthermore, since the weight is heavy, it can be fixed on the ground and the effect as a soil conditioner can be enhanced.
また、鉄を成分として含む被覆物として赤土を用いるようにすれば、安価に入手することができ、かつ、炭化物に容易に付着させることができる。 Further, if red clay is used as a coating material containing iron as a component, it can be obtained at low cost and can be easily adhered to carbides.
更に、炭化物に鉄分を多く含むコーンコブ炭化物を用いるようにすれば、より高い効果を得ることができる。 Further, if a corn bump carbide containing a large amount of iron is used as the carbide, a higher effect can be obtained.
以下、本発明の実施の形態について図面を参照して詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
図１は、本発明の一実施の形態に係る炭化物複合材料１０の構成を表すものである。この炭化物複合材料１０は、粒子状の炭化物１１に、鉄を成分として含む粒子状の被覆物１２が付着された構成を有している。なお、図１は炭化物複合材料１０の構成を概念的に表したものであり、被覆物１２は、例えば、炭化物１１の表面の少なくとも一部を覆っていればよく、炭化物１１の全体を覆っている必要はない。また、炭化物１１は個別に被覆物１２が付着していてもよいが、複数個が集まり、その周りに被覆物１１が付着していてもよい。更に、図１に示した炭化物１１及び被覆物１２の大きさいは実際の大きさを表すものではなく、また、大きさの比率も実際の比率を表しているわけではない。 FIG. 1 shows the structure of the carbide composite material 10 according to the embodiment of the present invention. The carbide composite material 10 has a structure in which a particulate coating 12 containing iron as a component is attached to the particulate carbide 11. Note that FIG. 1 conceptually shows the structure of the carbide composite material 10, and the covering 12 may cover at least a part of the surface of the carbide 11, for example, and covers the entire surface of the carbide 11. You don't have to be. Further, the carbides 11 may have the coating material 12 attached individually, but a plurality of carbides 11 may be gathered and the covering material 11 may be attached around the carbides 11. Further, the sizes of the carbide 11 and the coating 12 shown in FIG. 1 do not represent the actual size, and the ratio of the sizes does not represent the actual ratio.
炭化物１１は特に限定されず、どのようなものでもよいが、鉄分を多く含むコーンコブを焼成して炭化したコーンコブ炭化物を含むことが好ましい。コーンコブ炭化物は、コーンコブ特有の微細空間の多い多孔質構造を有し、優れた吸着特性を得ることができると共に、炭化物が内包する鉄分が放射性セシウムからの放射線を減衰させる機能を有するからである。炭化物１１の大きさは、例えば、５ｍｍ〜１０ｍｍ程度のものが好ましい。この大きさは炭化物を被覆物で覆うためには最適の大きさであり、得られる炭化物複合材料を土壌改良剤として土壌に投入する場合の作業性の容易さ、および土壌とのなじみのよさにその大きさは関係している。よって、目的となる炭化物複合材料の用途に応じた炭化物の大きさを決めるのが好ましい。 The carbide 11 is not particularly limited and may be any one, but it is preferable to contain the carbide of corn hump obtained by calcining corn hump containing a large amount of iron. This is because the corn hump carbide has a porous structure with a lot of fine spaces peculiar to corn hump, can obtain excellent adsorption characteristics, and the iron contained in the corn hump has a function of attenuating radiation from radioactive cesium. The size of the carbide 11 is preferably, for example, about 5 mm to 10 mm. This size is the optimum size for covering the carbide with a coating, and it is easy to work when the obtained carbide composite material is put into the soil as a soil conditioner, and it has good compatibility with the soil. Its size is relevant. Therefore, it is preferable to determine the size of the carbide according to the intended use of the carbide composite material.
被覆物１２は特に限定されず、成分として鉄イオンを含んでいればどのようなものでもよいが、赤土を含むものが好ましい。それらは安価に入手することができ、かつ、炭化物１１に容易に付着させることができるからである。被覆物１２の大きさは、例えば、できるだけ紛体（１ｍｍ以下であればよいが微粒子である必要はない）であることが好ましい。あるいは、湿式、乾式を問わず炭化物の表面に均一に付着できるくらいの大きさであればよく粒径は問わない。すなわち湿式、乾式の方法を問わず被覆する工程で支障なく炭化物が被覆される大きさであればよい。 The coating material 12 is not particularly limited, and any material may be used as long as it contains iron ions as a component, but those containing red clay are preferable. This is because they can be obtained at low cost and can be easily attached to the carbide 11. The size of the coating material 12 is preferably, for example, as much as possible powder (1 mm or less, but not necessarily fine particles). Alternatively, the particle size may be any size as long as it can be uniformly adhered to the surface of the carbide regardless of whether it is wet or dry. That is, the size may be such that carbides can be coated without any trouble in the coating process regardless of the wet or dry method.
炭化物１１と被覆物１２との割合は、湿式、乾式を問わず炭化物の表面に均一に付着できる割合であればよい。たとえば湿式で被覆する場合、重量比で水：被覆物（この場合赤土）：炭化物（この場合コーンコブ炭化物）＝１００：１５〜２５：１０〜２０、一例を挙げれば、重量比で水：被覆物（この場合赤土）：炭化物（この場合コーンコブ炭化物）＝１００：２０：１５で容易に炭化物を被覆することできる。乾式の場合は炭化物内部には浸透せず表面のみに付着するので被覆物の割合は湿式よりも高い方が好ましい。すなわち湿式、乾式の方法を問わず被覆する工程で支障なく炭化物が被覆される割合であればどのような条件でもよい。 The ratio of the carbide 11 to the coating 12 may be any ratio as long as it can uniformly adhere to the surface of the carbide regardless of whether it is wet or dry. For example, in the case of wet coating, water: coating (red soil in this case): carbide (carbide in this case) = 100: 15-25: 10-20 by weight ratio, for example, water: coating by weight ratio. (Red soil in this case): Carbide (Corncob carbide in this case) = 100: 20: 15, and the carbide can be easily coated. In the case of the dry type, the ratio of the coating material is preferably higher than that of the wet type because it does not penetrate into the carbide and adheres only to the surface. That is, any condition may be used as long as the ratio of carbides coated without any problem in the coating step regardless of the wet or dry method.
この炭化物複合材料１０は、例えば、土壌改良剤として好ましく用いることができる。本実験の形態によれば粒子状の炭化物１１に、鉄イオンを成分として含む被覆物１２を付着させているので、炭化物の多孔質構造内に含まれる鉄イオンとその表面に付着している被覆物に含まれる鉄イオンとの相乗効果により植物の成長を促進し、収穫量を増産させることができると共に、食味も向上させることができかつ、病気の発生を抑制することができる。また、土壌の地力を向上させることができ、肥料や農薬の投入量を低減することができる。これは鉄分を多く含む多孔質体（この場合炭化物）構造が微生物の繁殖を促すことによる。 The carbide composite material 10 can be preferably used as, for example, a soil conditioner. According to the form of this experiment, since the coating material 12 containing iron ions as a component is attached to the particulate carbide 11, the iron ions contained in the porous structure of the carbides and the coating attached to the surface thereof. By the synergistic effect with iron ions contained in the substance, the growth of the plant can be promoted, the yield can be increased, the taste can be improved, and the outbreak of the disease can be suppressed. In addition, the soil fertility can be improved, and the amount of fertilizer and pesticide input can be reduced. This is because the iron-rich porous structure (carbide in this case) promotes the growth of microorganisms.
更に、炭化物１１により、土壌中のカドミウムやセシウム等の重金属を吸着し、植物に移行することを抑制することができる。加えて、被覆物１２に鉄の成分が含まれているので、コンプトン散乱により放射能を有するγ線を減衰させることができ、空間の放射線量を低減させることができる。更にまた、被覆物１２を付着させるので、炭化物複合材料１０の重さが重くなり、土壌と混ざり方もよくなり土壌改良材としての効果を高めることができる。 Further, the carbide 11 can suppress the adsorption of heavy metals such as cadmium and cesium in the soil and the transfer to plants. In addition, since the coating material 12 contains an iron component, γ-rays having radioactivity can be attenuated by Compton scattering, and the radiation amount in space can be reduced. Furthermore, since the coating material 12 is attached, the weight of the carbide composite material 10 becomes heavy, the mixture with the soil becomes good, and the effect as a soil conditioner can be enhanced.
（実施例１）
コーンコブを８００℃で焼成して得られたコーンコブ炭化物を使って、金属イオン（カチオン）を吸着させた実験例を図２に示す。金属イオンの吸着は、Ａｓ（ヒ素）イオン，Ｃｄ（カドミウム）イオン，Ｃｒ（クロム）イオン，Ｃｕ（銅）イオン，Ｍｎ（マンガン）イオン，Ｐｂ（鉛）イオン，Ｚｎ（亜鉛）イオンについてそれぞれ行った。各金属イオンの濃度は１ｐｐｍとし、吸着時間は３０分とした。図２に示したように、Ａｓ（ヒ素）イオン，Ｃｒ（クロム）イオン以外の環境汚染物質である重金属イオンは３０分間の吸着処理後には９５％以上が炭化物に吸着されていることから、コーンコブ炭化物が高い吸着性能を有することが確認できた。なお、コーンコブを８００℃で焼成して得られたコーンコブ炭化物の表面を鉄分の多い赤土で被覆処理したものについても同様の吸着実験を行ったところ、Ｃｄ（カドミウム）イオン，Ｃｕ（銅）イオン，Ｍｎ（マンガン）イオン，Ｐｂ（鉛）イオン，Ｚｎ（亜鉛）イオンについて９５％以上の吸着率が得られた。
(Example 1)
FIG. 2 shows an experimental example in which a metal ion (cation) was adsorbed using a carbide of corn hump obtained by firing corn hump at 800 ° C. Adsorption of metal ions is performed on As (arsenic) ion, Cd (cadmium) ion, Cr (chromium) ion, Cu (copper) ion, Mn (manganese) ion, Pb (lead) ion, and Zn (zinc) ion, respectively. Ion. The concentration of each metal ion was 1 ppm, and the adsorption time was 30 minutes. As shown in FIG. 2, 95% or more of heavy metal ions, which are environmental pollutants other than As (arsenic) ions and Cr (chromium) ions, are adsorbed on carbides after 30 minutes of adsorption treatment. It was confirmed that the carbide has high adsorption performance. A similar adsorption experiment was performed on the surface of the carbide of corn hump obtained by firing corn hump at 800 ° C. with red soil containing a large amount of iron. As a result, Cd (cadmium) ion, Cu (copper) ion, An adsorption rate of 95% or more was obtained for Mn (manganese) ion, Pb (lead) ion, and Zn (zinc) ion.
（実施例２）
同様にコーンコブを５００℃、６００℃、７００℃、８００℃、９００℃、又は、１０００℃で焼成して得られたコーンコブ炭化物を使って、Ｃｄ（カドミウム）イオンを吸着させた実験例を図３に示す。図３において、破線が５００℃、６００℃、及び、７００℃の結果であり、実線が８００℃、９００℃、及び、１０００℃の結果である。また、ナラを８００℃で焼成して得られたナラ炭化物、及び、スギを８００℃で焼成して得られたスギ炭化物についても、Ｃｄ（カドミウム）イオンを吸着させた結果を図３に合わせて示す。吸着時間は、コーンコブ炭化物については５分、１０分、２０分、３０分とし、ナラ炭化物及びスギ炭化物については２０分とした。Ｃｄ（カドミウム）イオンの濃度は１ｐｐｍである。図３に示したように、ナラ炭化物及びスギ炭化物では２０分の吸着時間で約８０％吸着されたのに対して、コーンコブ炭化物は５分間の吸着時間後には９０％以上が炭化物に吸着されている。このことからもコーンコブ炭化物が高い吸着性能を有することが確認できた。
(Example 2)
Similarly, FIG. 3 shows an experimental example in which Cd (cadmium) ions were adsorbed using the carbide of corn hump obtained by firing corn hump at 500 ° C., 600 ° C., 700 ° C., 800 ° C., 900 ° C., or 1000 ° C. Shown in. In FIG. 3, the broken lines are the results of 500 ° C., 600 ° C., and 700 ° C., and the solid lines are the results of 800 ° C., 900 ° C., and 1000 ° C. In addition, the results of adsorbing Cd (cadmium) ions on the carbides of oak obtained by firing oak at 800 ° C and the carbides of sugi obtained by firing sugi at 800 ° C are shown in FIG. Shown. The adsorption time was 5 minutes, 10 minutes, 20 minutes, and 30 minutes for corn cob carbide, and 20 minutes for oak carbide and sugi carbide. The concentration of Cd (cadmium) ions is 1 ppm. As shown in FIG. 3, oak carbide and sugi carbide were adsorbed by about 80% in a adsorption time of 20 minutes, whereas corn cob carbide was adsorbed by 90% or more after an adsorption time of 5 minutes. There is. From this, it was confirmed that the corn cob carbide has high adsorption performance.
（実施例３）
同様にコーンコブを４００℃、６００℃、又は、９００℃で焼成して得られたコーンコブ炭化物を使って、Ｃｓ（セシウム）イオンを吸着させた実験例を図４に示す。また、中華人民共和国遼寧省大連で作られたコーンコブ炭化物（焼成温度約５００℃）、及び、ナラを６００℃で焼成して得られたナラ炭化物についても、Ｃｓ（セシウム）イオンを吸着させた結果を図４に合わせて示す。吸着時間は、コーンコブ炭化物については１０分、２０分、３０分、６０分とし、ナラ炭化物については６０分とした。Ｃｓ（セシウム）イオンの濃度は１ｐｐｍである。なお、図４においてＣＣというのはコーンコブ炭化物を表し、ＣＣ大連というのは中華人民共和国遼寧省大連で作られたコーンコブ炭化物を表し、ナラというのはナラ炭化物を表している。図４に示したように、６００℃で焼成したナラ炭化物と比較して、いずれの炭化温度で焼成されたコーンコブ炭化物も吸着率が高いことがわかる。このように、鉄イオンを多く含むコーンコブから得られた炭化物は高い吸着性能を示し、他の炭化物と比較して水系あるいは土壌中の環境浄化用炭化物として効果的に働くことが確認できた。また、コーンコブ炭化物の表面を赤土で被覆処理したものについても同様の吸着実験を行ったところ、同様の結果が得られた。
(Example 3)
Similarly, FIG. 4 shows an experimental example in which Cs (cesium) ions were adsorbed using the carbide of corn hump obtained by firing corn hump at 400 ° C., 600 ° C., or 900 ° C. In addition, Cs (cesium) ions were adsorbed on corn cob carbide (calcination temperature of about 500 ° C) made in Dalian, Liaoning Province, People's Republic of China, and oak carbide obtained by calcining oak at 600 ° C. Is shown in accordance with FIG. The adsorption time was 10 minutes, 20 minutes, 30 minutes, and 60 minutes for corn cob carbide, and 60 minutes for oak carbide. The concentration of Cs (cesium) ions is 1 ppm. In FIG. 4, CC represents corn cob carbide, CC Dalian represents corn cob carbide made in Dalian, Liaoning Province, People's Republic of China, and nara represents nara carbide. As shown in FIG. 4, it can be seen that the corn cob carbide calcined at any carbonization temperature has a higher adsorption rate than the oak carbide calcined at 600 ° C. As described above, it was confirmed that the carbide obtained from the corn hump containing a large amount of iron ions showed high adsorption performance and worked more effectively as a carbide for environmental purification in the water system or soil as compared with other carbides. Further, when the same adsorption experiment was performed on the corn cob carbide whose surface was coated with red clay, the same result was obtained.
（実施例４）
実施例１−３ではコーンコブ炭化物の高い吸着能力を示した。実施例４では、吸着した放射性セシウムに対するコーンコブ炭化物の防放射線能力についての実験事例を示す。すなわち通常市販している炭化物と、コーンコブ炭化物と、その表面を鉄分の多い赤土で表面を被覆処理したものを使い、放射性セシウムから発せられる放射線量を測定した。実験に用いた炭化物は中華人民共和国遼寧省大連で作られたコーンコブ炭化物、および岩手県内産の赤松炭である。これらはいずれも粒状（５〜１０ｍｍ）の形態をしている。放射性物質含む土壌は福島市内（サンプルＣ：約１２００〜１４００Ｂｑ／ｋｇ）から採取したものであり、赤土は中華人民共和国遼寧省大連のコーン生産場所からのものである。試料はＵ８容器に入れ、ゲルマニウム半導体検出装置で放射性セシウムのＣｓ１３４，Ｃｓ１３７を測定した。
(Example 4)
In Examples 1-3, the high adsorption capacity of corn cob carbide was shown. In Example 4, an experimental example of the radiation-proof ability of the corn cob carbide against the adsorbed radioactive cesium is shown. That is, the amount of radiation emitted from radioactive cesium was measured using normally commercially available carbides, corn cob carbides, and those whose surface was coated with red clay containing a large amount of iron. The carbides used in the experiment were corn cob carbide made in Dalian, Liaoning Province, People's Republic of China, and red pine charcoal produced in Iwate Prefecture. All of these are in the form of granules (5 to 10 mm). The soil containing radioactive substances was collected from Fukushima City (Sample C: about 1200 to 1400 Bq / kg), and the red soil was from the corn production site in Dalian, Liaoning Province, People's Republic of China. The sample was placed in a U8 container, and Cs134 and Cs137 of radioactive cesium were measured with a germanium semiconductor detector.
具体的には、コーンコブ炭化物、及び、岩手県内産の赤松炭については、次のようにして測定した。最初にＵ８容器に土壌試料を約５ｃｍの高さまでいれる。この時の土の状態は粉砕せずに通常の粒子状の状態である。これをゲルマニウム半導体検出装置で放射能を測定する。なお各試料数はｎ＝３である。試料Ｎｏ１,Ｎｏ２，Ｎｏ４，Ｎｏ５は、土壌試料の上に、コーンコブ炭化物（粒炭）又は赤松炭（軽く粉砕）を積層するように高さ５ｃｍまで入れたものである。試料Ｎｏ３、Ｎｏ６は、土壌試料の上に、コーンコブ炭化物（粒炭）又は赤松炭（軽く粉砕）を入れ、蓋をして何度も振とうして均一に混合させ、高さ５ｃｍなるようにしたものである。これらについて再びゲルマニウム半導体検出装置で放射性セシウムのＣｓ１３４，Ｃｓ１３７を測定した。それらの結果を表１及び表２に示す。 Specifically, corn cob carbide and red pine charcoal produced in Iwate prefecture were measured as follows. First, the soil sample is placed in a U8 container to a height of about 5 cm. The state of the soil at this time is a normal particulate state without being crushed. The radioactivity of this is measured with a germanium semiconductor detector. The number of each sample is n = 3. Samples No1, No2, No.4, and No.5 are prepared by stacking corn cob carbide (grain charcoal) or red pine charcoal (lightly crushed) on a soil sample up to a height of 5 cm. For samples No. 3 and No. 6, put corn cob carbide (grain charcoal) or red pine charcoal (lightly crushed) on the soil sample, cover and shake repeatedly to mix evenly so that the height becomes 5 cm. It was done. For these, Cs134 and Cs137 of radioactive cesium were measured again with a germanium semiconductor detector. The results are shown in Tables 1 and 2.
更に、コーンコブ炭化物（粒炭）を赤土で被覆した炭化物複合材料１０については、次のようにして測定した。まず、炭化物複合材料１０は、水：赤土：コーンコブ炭化物＝１００：２０：１５の重量比で湿式混合することにより作製した。次に、Ｕ８容器に土壌試料を１０ｇ入れ（粉砕せずに通常の粒子状の状態）、ゲルマニウム半導体検出装置で放射能Ｃｓ１３４，Ｃｓ１３７を測定した。続いて、土壌試料の上に、炭化物複合材料１０を積層するように入れ、再びゲルマニウム半導体検出装置で放射能Ｃｓ１３４，Ｃｓ１３７を測定した。試料Ｎｏ７は炭化物複合材料１０の量を１０ｇとし、試料Ｎｏ８は炭化物複合材料１０の量を２０ｇとしたものである。それらの結果を表３に示す。なお、表３ではＴ−Ｃｓ（Ｃｓ１３４，Ｃｓ１３７の値を合算した値）を示す。 Further, the carbide composite material 10 in which corn cob carbide (grain charcoal) was coated with red clay was measured as follows. First, the carbide composite material 10 was prepared by wet mixing at a weight ratio of water: red clay: corn cob carbide = 100: 20: 15. Next, 10 g of a soil sample was placed in a U8 container (in a normal particulate state without pulverization), and the radioactivity Cs134 and Cs137 were measured with a germanium semiconductor detector. Subsequently, the carbide composite material 10 was placed on the soil sample so as to be laminated, and the radioactivity Cs134 and Cs137 were measured again with the germanium semiconductor detector. Sample No. 7 has a carbide composite material 10 of 10 g, and Sample No. 8 has a carbide composite material 10 of 20 g. The results are shown in Table 3. Table 3 shows T-Cs (the sum of the values of Cs134 and Cs137).
表１及び表２に示したように、放射線量が約１２００〜１４００Ｂｑ／ｋｇの土壌をコーンコブ炭化物で被覆することにより、Ｔ−Ｃｓ（Ｃｓ１３４，Ｃｓ１３７の値を合算した値）の放射線量が４８．３％下がり、混合したものを含めてもＴ−Ｃｓで３８．７％下がった。一方、岩手産赤松炭で同様の実験を行った結果では、被覆した場合Ｔ−Ｃｓで２８．２％下がり、混合したものを含めるとＴ−Ｃｓで２３．９％下がった。また、表３に示したように、赤土で処理したコーンコブ炭化物についての実験では、放射線量が３８１０Ｂｑ／ｋｇの土壌の上に赤土で処理したコーンコブ炭化物を積層することにより、最終的には放射線量が８１２Ｂｑ／ｋｇまで低減し、約８０％放射線が下がった。この結果から、鉄分の多いコーンコブ炭化物でも約４８％の低減化が可能であり、さらに赤土で炭化物表面を処理したコーンコブ炭化物では約８０％も放射線を防御できることが確認された。 As shown in Tables 1 and 2, by coating soil with a radiation dose of about 1200 to 1400 Bq / kg with corn cob carbide, the radiation dose of T-Cs (the sum of the values of Cs134 and Cs137) is 48. It decreased by 3.3%, and even including the mixed one, it decreased by 38.7% in TCs. On the other hand, as a result of conducting a similar experiment with Akamatsu charcoal produced in Iwate, the T-Cs decreased by 28.2% when coated, and the T-Cs decreased by 23.9% when the mixed one was included. In addition, as shown in Table 3, in the experiment on the corn cob carbide treated with red soil, the corn cob carbide treated with red soil was laminated on the soil having a radiation amount of 3810 Bq / kg, and finally the radiation amount. Was reduced to 812 Bq / kg, and the radiation was reduced by about 80%. From this result, it was confirmed that even corn cob carbide having a high iron content can be reduced by about 48%, and that corn cob carbide whose carbide surface is treated with red clay can protect against radiation by about 80%.
（実施例５）
実施例４ではコーンコブ炭化物および複合化されたコーンコブ炭化物による放射線の低減化を示したが、実施例５では複合化していない鉄分の多く含まれている炭化物１１（コーンコブ炭化物）を、水田に蒔き、耕したのち、田植えをして稲を育てた事例を示す。反当り６０Ｌの炭化物１１を３袋投入した水田と入れていない水田を比較した結果、コーンコブ炭化物を投入した水田の方が、反当りの収率が２０％向上した。さらに収穫した米の食味試験を行ったところ、コーンコブ炭化物を入れていない水田の米の食味値は７４、総合品質判定はＢであったのに対して、コーンコブ炭化物を入れた水田の米の食味値は８０であり、総合品質判定はＡに向上した。
(Example 5)
In Example 4, the reduction of radiation by the corn cob carbide and the compounded corn cob carbide was shown, but in Example 5, the carbide 11 (corn cob carbide) containing a large amount of uncomposited iron was sown in the paddy field. An example of growing rice by planting rice after plowing is shown. As a result of comparing the paddy field containing 3 bags of 60 L of carbide 11 and the paddy field not containing it, the yield of counter-hit was improved by 20% in the paddy field containing corn cob carbide. Furthermore, when the taste test of the harvested rice was conducted, the taste value of the rice in the paddy field without corn cob carbide was 74, and the overall quality judgment was B, whereas the taste of the rice in the paddy field with corn cob carbide was added. The value was 80, and the overall quality judgment improved to A.
（実施例６）
実施例５ではコーンコブ炭化物を、水田に蒔き、耕したのち、田植えをして稲を育てた事例を示したが、実施例６では収穫されたうるち米に含まれるカドミウムの量が０．２ｐｐｍであった水田に、コーンコブ炭化物を蒔き、耕して、稲を育てた。その結果、コーンコブ炭化物を蒔いた後に収穫されたうるち米に含まれるカドミウムの量は、測定限界以下、又は、０．１ｐｐｍ以下に減少させることができた。すなわち、コーンコブ炭化物を用いれば、カドミウム等の重金属が植物に移行することを抑制することができることが分かった。また、コーンコブ炭化物の表面を赤土で被覆処理した炭化物複合材料１０を水田に蒔き稲を育てたところ、収穫されたうるち米に含まれるカドミウムの量は測定限界以下であった。
(Example 6)
In Example 5, corn cob carbide was sown in paddy fields, cultivated, and then planted to grow rice. In Example 6, the amount of cadmium contained in the harvested glutinous rice was 0.2 ppm. Carbide corn cob was sown and cultivated in the paddy fields to grow rice. As a result, the amount of cadmium contained in the glutinous rice harvested after sowing the corn cob carbide could be reduced to below the measurement limit or to 0.1 ppm or less. That is, it was found that the use of corn cob carbide can suppress the transfer of heavy metals such as cadmium to plants. Further, when the carbide composite material 10 in which the surface of the carbide of corn cob was coated with red soil was sown in a paddy field to grow rice, the amount of cadmium contained in the harvested glutinous rice was below the measurement limit.
以上、実施の形態を挙げて本発明を説明したが、本発明は上記実施の形態に限定されるものではなく、種々変形可能である。例えば、上記実施の形態では、各構成要素について具体的に説明したが、全ての構成要素を備えていなくてもよく、また、他の構成要素を備えていてもよい。また、上記実施の形態では、用途として土壌改良材を例に挙げて説明したが、他の用途に用いることもできる。 Although the present invention has been described above with reference to embodiments, the present invention is not limited to the above embodiments and can be variously modified. For example, in the above-described embodiment, each component has been specifically described, but not all components may be provided, or other components may be provided. Further, in the above-described embodiment, the soil conditioner has been described as an example of use, but it can also be used for other uses.
土壌改良剤等に用いることができる。 It can be used as a soil conditioner or the like.
１０…炭化物複合材料、１１…炭化物、１２…被覆物 10 ... Carbide composite material, 11 ... Carbide, 12 ... Coating
Claims (1)
Particulate carbide having a size of 5 mm to 10 mm and having a size of 1 mm or less containing iron as a component, containing carbonized corn hump obtained by firing corn hump at 500 ° C. to 800 ° C. A method for producing a radiation-damping carbide composite material , wherein the coating material containing the coating material is adhered by a wet method by mixing it in a weight ratio of water: coating material: carbide = 100: 15-25: 10 to 20 .
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