JP2017001005A - Environment cleaning material using calcium - Google Patents

Environment cleaning material using calcium Download PDF

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JP2017001005A
JP2017001005A JP2015124224A JP2015124224A JP2017001005A JP 2017001005 A JP2017001005 A JP 2017001005A JP 2015124224 A JP2015124224 A JP 2015124224A JP 2015124224 A JP2015124224 A JP 2015124224A JP 2017001005 A JP2017001005 A JP 2017001005A
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enzyme
organic matter
environmental purification
cured product
calcium oxide
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JP6638931B2 (en
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治彦 豊原
Haruhiko Toyohara
治彦 豊原
敦政 佐藤
Atsumasa Sato
敦政 佐藤
翔 中森
Sho Nakamori
翔 中森
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Gaia Technology Co Ltd
Kyoto University NUC
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Kyoto University NUC
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Abstract

PROBLEM TO BE SOLVED: To provide a method for removing efficiently a residual organic matter without accompanying a work for moving/recovering the residual organic matter, having a heavy workload, and applicable to high functionalization of agricultural soil or to processing of organic waste liquid from a food factory or the like.SOLUTION: Enzyme is adsorbed by a hardening body produced from calcium oxide obtained by firing shells or limestone, plaster of Paris, olivine and water, and a residual organic matter can be decomposed/removed efficiently by action of the enzyme, with excellent adsorptivity of organic matter degrading enzyme.SELECTED DRAWING: None

Description

本発明は、汚泥処理、水処理、養殖場の環境浄化、土壌改良において有機物分解機能を備える、環境浄化材であって、酸化カルシウム焼成物の硬化体を含有し、酵素の存在下で使用するものであることを特徴とする環境浄化材に関するものである。  The present invention is an environmental purification material having an organic matter decomposition function in sludge treatment, water treatment, environmental purification of aquaculture, and soil improvement, containing a cured product of calcined calcium oxide, and used in the presence of an enzyme. It is related with the environmental purification material characterized by being.

養殖場等において、残餌や排泄物などによるヘドロ化や水質悪化が進行し、ヘドロ化や水質悪化の原因となる残存有機物の効率的な除去が強く求められるようになっており、残存有機物の除去方法としては、各種の方法が知られている。
特許文献1には、タンパクを、海洋生物の皮膚を焼却して得られる残渣物とキチン・キトサンを含むろ過材でろ過する方法が示されている。
特許文献2には、養殖場等で発生する有機性廃水を、活性汚泥法等で生物によって処理し、余剰有機性汚泥をゴカイ等の底生生物の養殖水槽に移し、余剰有機性汚泥を底生生物の飼料とする方法が示されている。
特許文献3には、有機物とリン酸イオンを含む排水に、700℃以上で焼成された貝殻の粉末を添加し、有機物を凝集させて肥料とする方法が示されている。
しかし、特許文献1〜3で例示されるいずれの方法も、分離した残存有機物を移動・回収する工程を伴うものであった。そして、分離した残存有機物を移動・回収することなく残存有機物を除去する方法は今までに知られていない。
In farms, etc., sludge formation and water quality deterioration due to residual food and excrement progress, and efficient removal of residual organic substances that cause sludge formation and water quality deterioration is strongly demanded. Various methods are known as removal methods.
Patent Document 1 discloses a method of filtering proteins with a filter medium containing a residue obtained by incineration of marine organism skin and chitin / chitosan.
In Patent Document 2, organic wastewater generated in aquaculture farms, etc. is treated by living organisms using the activated sludge method, etc., surplus organic sludge is transferred to aquaculture tanks of benthic organisms such as sandworms, and surplus organic sludge is bottomed. It shows how to make livestock feed.
Patent Document 3 discloses a method in which shellfish powder baked at 700 ° C. or higher is added to wastewater containing organic matter and phosphate ions to agglomerate the organic matter into fertilizer.
However, any of the methods exemplified in Patent Documents 1 to 3 involve a step of moving and collecting the separated residual organic matter. And the method of removing a residual organic substance is not known until now, without moving and collect | recovering the separated residual organic substance.

特開2005−087440号公報Japanese Patent Laying-Open No. 2005-087440 特開2005−74420号公報JP 2005-74420 A 特開2007−130545号公報JP 2007-130545 A

本発明の課題は、作業負担の大きい、残存有機物の移動・回収の作業を伴うことなく、残存有機物の除去を効率的に行うと共に、農業用土壌の高機能化、食品工場などの有機廃液の処理にも応用しうる方法の提供を目的とするものである。  The object of the present invention is to efficiently remove the remaining organic matter without involving the work of moving and collecting the remaining organic matter, which has a large work load, and to enhance the functionality of agricultural soil, The object is to provide a method that can also be applied to processing.

本発明は、酸化カルシウム焼成物の硬化体が、酵素、特に、有機物分解酵素の吸着性に優れ、その酵素の作用により残存有機物を効率良く分解・除去できるとの発見に基づくものである。
すなわち、第1の発明は、酸化カルシウム焼成物の硬化体を含有し、酵素の存在下で使用することを特徴とする環境浄化材の発明である。
The present invention is based on the discovery that the cured product of calcined calcium oxide is excellent in the adsorptivity of enzymes, particularly organic substance-degrading enzymes, and can efficiently decompose and remove residual organic substances by the action of the enzymes.
That is, the first invention is an invention of an environmental purification material characterized by containing a cured product of a calcined product of calcium oxide and used in the presence of an enzyme.

第2の発明は、第1の発明における硬化体が、貝殻や石灰石を焼成して得られる酸化カルシウムと焼石膏とカンラン石と水とで製造される硬化体であることを特徴とする環境浄化材の発明である。  2nd invention WHEREIN: The hardening body in 1st invention is a hardening body manufactured with the calcium oxide obtained by baking shellfish and limestone, calcined gypsum, olivine, and water, The environmental purification | cleaning characterized by the above-mentioned It is an invention of the material.

第3の発明は、第1又は第2の発明における環境浄化材が、酵素を含有するものであることを特徴とする環境浄化材の発明である。  3rd invention is invention of the environmental purification material characterized by the environmental purification material in 1st or 2nd invention containing an enzyme.

第4の発明は、第1、第2又は第3の発明おける酵素が、トリプシン及び/又はアミラーゼであることを特徴とする環境浄化材の発明である。  4th invention is invention of the environmental purification material characterized by the enzyme in 1st, 2nd or 3rd invention being trypsin and / or amylase.

第5の発明は、第1乃至第4のいずれかの発明における環境浄化材が、養殖場で添加・使用されるものであることを特徴とする環境浄化材の発明である。  A fifth invention is an invention of an environmental purification material, characterized in that the environmental purification material in any of the first to fourth inventions is added and used in a farm.

なお、前記「酵素」は、トリプシンやアミラーゼ等のタンパク質で構成される有機物を分解する周知の酵素であり、前記「吸着」は、吸着される成分の濃度をその周囲よりも増加する状態であり、前記「硬化体」は、外形には限定されず、酵素吸着成分として機能するに足りる粒状、塊状、多孔体等の全ての大きさや態様を含むものであり、「焼成」は、酸化カルシウムを生成する限りにおいて、任意の加熱処理であり、600℃〜1000℃の加熱処理が好ましく、前記「酸化カルシウム焼成物」は、前記焼成により得られる酸化カルシウムを含む焼成物であり、前記「環境浄化材」は、前記酵素の存在下で、ろ過材として使用される場合を含むものである。  The “enzyme” is a known enzyme that decomposes organic substances composed of proteins such as trypsin and amylase, and the “adsorption” is a state in which the concentration of the adsorbed component is increased from the surroundings. The “cured body” is not limited to the outer shape, and includes all sizes and forms such as granular, lump, and porous bodies sufficient to function as an enzyme adsorbing component. As long as it produces | generates, it is arbitrary heat processing, and the heat processing of 600 to 1000 degreeC is preferable, and the said "calcium oxide baked product" is a baked product containing the calcium oxide obtained by the said baking, and said "environmental purification" The “material” includes the case where it is used as a filter medium in the presence of the enzyme.

第1の発明は、その硬化体が有機物分解酵素等の酵素に対して優れた吸着性を示すことから、残留有機物と接触させれば、硬化体の表面に酵素が濃縮・吸着された状態で残存有機物と接触することとなり、残留有機物を酵素により効率的に分解・除去することができる。  In the first invention, since the cured product exhibits excellent adsorptivity to enzymes such as organic matter degrading enzymes, the enzyme is concentrated and adsorbed on the surface of the cured product if it is brought into contact with residual organic matter. It comes in contact with the remaining organic matter, and the remaining organic matter can be efficiently decomposed and removed by the enzyme.

そして、酵素が吸着されているから、酵素により継続して残留有機物を分解・除去できるという効果を有する。さらに、その環境浄化材を残留有機物のろ過材として使用すれば、ろ過と同時に残留有機物の分解・除去することができ、より効率的であるという効果を有する。  And since the enzyme is adsorb | sucked, it has the effect that a residual organic substance can be decomposed | disassembled and removed continuously by an enzyme. Furthermore, if the environmental purification material is used as a filter material for residual organic matter, the residual organic matter can be decomposed and removed simultaneously with the filtration, which has the effect of being more efficient.

第2の発明は、第1の発明の効果に加えて、硬化体が、水に溶けず頑丈で多孔質であるという効果、及び、養殖現場で大量に発生する貝殻や我が国に多く産する石灰岩を原料とするから、原料が容易に入手できるという効果を有する。  In addition to the effects of the first invention, the second invention has an effect that the hardened body does not dissolve in water and is strong and porous, and shells generated in large quantities at aquaculture sites and limestone produced in Japan in large numbers As a raw material, the raw material can be easily obtained.

第3の発明は、第1又は第2の発明の効果に加えて、酵素が不足または存在しない状態であっても、残留有機物との接触により、残留有機物を効率的に分解・除去できるという効果を有する。  In addition to the effects of the first or second invention, the third invention has the effect that the residual organic matter can be efficiently decomposed / removed by contact with the residual organic matter even when the enzyme is insufficient or does not exist. Have

第4の発明は、第1、第2又は第3の発明の効果に加えて、硬化体がトリプシン及び/又はアミラーゼに優れた吸着性を示すので、デンプン及び/又はタンパクの分解に効率的に使用できるという効果を有する。特に、トリプシンの存在下で使用する場合は、硬化体が顕著なトリプシン吸着能を示し、タンパク質の分解に優れるという効果を有する。  In the fourth invention, in addition to the effects of the first, second or third invention, the cured product exhibits an excellent adsorptivity to trypsin and / or amylase, so that the starch and / or protein can be efficiently decomposed. It has the effect that it can be used. In particular, when used in the presence of trypsin, the cured product exhibits a remarkable ability to adsorb trypsin and has an effect of being excellent in protein degradation.

第5の発明は、第1乃至第4のいずれかの発明の効果に加えて、養殖場における残留餌や排泄物の分解を効率的に分解・除去できるという効果を有する。  In addition to the effects of any one of the first to fourth inventions, the fifth invention has an effect that the decomposition of residual feed and excrement in the farm can be efficiently decomposed and removed.

実施例2における酵素アミラーゼの吸着率を示す。  The adsorption rate of the enzyme amylase in Example 2 is shown. 実施例2における酵素トリプシンの吸着率を示す。  The adsorption rate of the enzyme trypsin in Example 2 is shown. 実施例3及び比較例2におけるエビ餌分解能を示す。  The shrimp bait resolution in Example 3 and Comparative Example 2 is shown.

以下、本発明を実施するための最良の形態について説明するが、本発明は、これらに限定されるものではない。  Hereinafter, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.

本実施例は、硬化体の製造例を示すものである。
酸化カルシウム(1,000℃焼成)と焼石膏とカンラン石と蒸留水を1:3:1:40%、及び1:2:2:40%となるように混合し、55℃、2時間加温、1cmΦ程度の粒状に粉砕し本発明の硬化体を製造した。得られた硬化体は、水に溶けず頑丈で多孔質であった。
The present example shows a production example of a cured body.
Calcium oxide (calcined at 1,000 ° C), calcined gypsum, olivine and distilled water were mixed at 1: 3: 1: 40% and 1: 2: 2: 40%, and heated at 55 ° C for 2 hours. The cured product of the present invention was produced by pulverizing into a granule having a temperature of about 1 cmΦ. The obtained cured product was strong and porous without dissolving in water.

本実施例は、硬化体の酵素吸着性および有機質の分解・除去特性を示すものである。
実施例1で製造した硬化体約0.1gを、1μg/mlのアミラーゼ溶液1ml又は200μg/mlのトリプシン溶液1mlに混合し、30分間攪拌し、遠心分離(10,000×g、3分)し、人工海水での洗浄を3回行い、酵素を吸着した硬化体を得た。
得られた硬化体0.1gを、0.5%デンプン溶液1ml又は0.5%カゼイン溶液1mlに添加し、20分間撹拌し、遠心分離(10,000×g、3分)し、上清20μlをヨウ素比色法、又はLowry法により吸光度測定し、デンプン濃度又はタンパク濃度を算出した。得られたデンプン濃度又はタンパク濃度は、硬化体に吸着された酵素により分解されなかったデンプン濃度又はタンパク濃度を示すと考えられるから、その濃度を用いて酵素吸着率を次式により算出した。

Figure 2017001005
ここで、コントロールは、前記各酵素溶液0.5mlを0.5%デンプン溶液1ml又は0.5%カゼイン溶液1mlに添加し、20分間撹拌し、遠心分離(10000×g、3分)し、上清20μlをヨウ素比色法、又はLowry法により吸光度を測定し、デンプン濃度又はタンパク濃度を算出したものであり、ブランクは、0.5%デンプン溶液1ml又は0.5%カゼイン溶液1mlの上清20μlをヨウ素比色法、又はLowry法により吸光度を測定し、デンプン濃度又はタンパク濃度を算出したものである。算出された酵素吸着率を図1及び図2に示す。
図1及び図2から、本発明の硬化体は、アミラーゼ及びトリプシンに対して優れた吸着率を示し、デンプン及びタンパクに対して優れた分解・除去特性を示すことが明らかである。This example shows the enzyme adsorptivity and the organic decomposition / removal characteristics of the cured product.
About 0.1 g of the cured product produced in Example 1 was mixed with 1 ml of 1 μg / ml amylase solution or 1 ml of 200 μg / ml trypsin solution, stirred for 30 minutes, and centrifuged (10,000 × g, 3 minutes). Then, washing with artificial seawater was performed three times to obtain a cured body on which the enzyme was adsorbed.
0.1 g of the obtained cured product is added to 1 ml of 0.5% starch solution or 1 ml of 0.5% casein solution, stirred for 20 minutes, centrifuged (10,000 × g, 3 minutes), and the supernatant Absorbance of 20 μl was measured by iodine colorimetric method or Lowry method, and the starch concentration or protein concentration was calculated. Since the obtained starch concentration or protein concentration is considered to indicate the starch concentration or protein concentration that was not decomposed by the enzyme adsorbed on the cured product, the enzyme adsorption rate was calculated by the following equation using the concentration.
Figure 2017001005
Here, as a control, 0.5 ml of each enzyme solution was added to 1 ml of 0.5% starch solution or 1 ml of 0.5% casein solution, stirred for 20 minutes, and centrifuged (10000 × g, 3 minutes). Absorbance of 20 μl of the supernatant was measured by iodine colorimetric method or Lowry method, and the starch concentration or protein concentration was calculated. The blank was above 1 ml of 0.5% starch solution or 1 ml of 0.5% casein solution. Absorbance of 20 μl of Kiyoshi was measured by iodine colorimetric method or Lowry method, and the starch concentration or protein concentration was calculated. The calculated enzyme adsorption rate is shown in FIG. 1 and FIG.
From FIG. 1 and FIG. 2, it is clear that the cured product of the present invention exhibits an excellent adsorption rate with respect to amylase and trypsin, and exhibits an excellent decomposition / removal property with respect to starch and protein.

比較例1Comparative Example 1

実施例1の硬化体の製造における酸化カルシウムを、焼成しない酸化カルシウム、酸化アルミニウム、水酸化アルミニウム、酸化マンガン、酸化鉄(III)、酸化マグネシウムに代えた硬化体について、実施例2と同様の方法で酵素吸着率を算出した。
算出された酵素吸着率を図1及び図2に示す。
図1及び図2の結果から、いずれの硬化体においても、前記本発明の硬化体に比して、アミラーゼ及びトリプシンに対する吸着率が低く、特に、トリプシンの吸着率についてはその傾向が強く、本発明の実施例2に記載の効果と比較すると、デンプン及びタンパクの分解・除去特性において劣ることが明らかである。
About the hardening body which replaced calcium oxide in manufacture of the hardening body of Example 1 with calcium oxide which is not baked, aluminum oxide, aluminum hydroxide, manganese oxide, iron (III) oxide, and magnesium oxide, the same method as Example 2 Then, the enzyme adsorption rate was calculated.
The calculated enzyme adsorption rate is shown in FIG. 1 and FIG.
From the results shown in FIG. 1 and FIG. 2, in any of the cured bodies, the adsorption rate to amylase and trypsin is lower than that of the cured body of the present invention. Compared with the effect described in Example 2 of the invention, it is clear that the degradation and removal properties of starch and protein are inferior.

本実施例は、酵素を吸着させた硬化体によるエビ餌の分解例を示すものである。実施例1で製造した硬化体約2gに、1μg/mlのアミラーゼ溶液又は200μg/mlのトリプシン溶液20mlを添加し、1時間振盪し、沈殿物を人工海水で3回洗浄し、酵素を吸着した硬化体を得た。
前記酵素を吸着させた硬化体をエビ餌溶液20mlに投入し、30分間振盪し、その後、上清20μlをヨウ素比色法又はLowry法により呈色し、吸光度測定し、デンプン濃度又はタンパク濃度を測定し、実施例2と同様の方法で酵素吸着率を算出した。算出結果を図3に示す。これにより、エビ餌のデンプン及びタンパクが確実に分解されていることが明らかである。
In this example, shrimp bait is decomposed by a cured body on which an enzyme is adsorbed. To about 2 g of the cured product produced in Example 1, 20 ml of 1 μg / ml amylase solution or 200 μg / ml trypsin solution was added, shaken for 1 hour, the precipitate was washed with artificial seawater three times, and the enzyme was adsorbed. A cured product was obtained.
The cured body on which the enzyme has been adsorbed is put into 20 ml of shrimp bait solution, shaken for 30 minutes, and then 20 μl of the supernatant is colored by iodine colorimetry or Lowry, and the absorbance is measured to determine the starch concentration or protein concentration. Then, the enzyme adsorption rate was calculated in the same manner as in Example 2. The calculation results are shown in FIG. This clearly demonstrates that the starch and protein in the shrimp bait have been degraded.

比較例2Comparative Example 2

実施例1の硬化体に代えて、焼石膏とカンラン石を(3:1)及び(1:1)とし、酸化カルシウムを用いない硬化物を用いて、実施例3と同様の実験を行った。
結果を図3に示す。いずれの場合にも、実施例3におけるような、エビ餌のデンプン及びタンパクの分解は認められなかった。
In place of the cured body of Example 1, calcined gypsum and olivine were (3: 1) and (1: 1), and the same experiment as in Example 3 was performed using a cured product that did not use calcium oxide. .
The results are shown in FIG. In any case, starch and protein degradation of the shrimp bait as in Example 3 was not observed.

本発明に係る環境浄化材は、水産業、農業、環境分野などにおいて、底泥処理材、ろ過材、土壌改良材、バイオリアクター素材などとして利用可能であり、特に、養殖における残留餌の効率的分解、農業土壌の高機能化、食品工場などの有機廃液の効率的処理に有用である。  The environmental purification material according to the present invention can be used as a bottom mud treatment material, a filtration material, a soil improvement material, a bioreactor material, etc. in the fishery industry, agriculture, environmental fields, etc. It is useful for decomposition, enhancement of agricultural soil functionality, and efficient treatment of organic waste liquids in food factories.

Claims (5)

酸化カルシウム焼成物の硬化体を含有し、酵素の存在下で使用するものであることを特徴とする環境浄化材。  An environmental purification material containing a cured product of calcined calcium oxide and used in the presence of an enzyme. 硬化体が貝殻や石灰石を焼成して得られる酸化カルシウムと焼石膏とカンラン石と水とで製造される硬化体であることを特徴とする請求項1に記載の環境浄化材。  The environmental purification material according to claim 1, wherein the hardened body is a hardened body produced from calcium oxide, calcined gypsum, olivine, and water obtained by firing shells or limestone. 酵素を含有することを特徴とする請求項1又は2に記載の環境浄化材。  The environmental purification material according to claim 1 or 2, comprising an enzyme. 酵素がトリプシン及び/又はアミラーゼであることを特徴とする請求項1、2又は3に記載の環境浄化材。  The environmental purification material according to claim 1, 2 or 3, wherein the enzyme is trypsin and / or amylase. 養殖場で添加・使用されるものであることを特徴とする請求項1、2、3又は4に記載の環境浄化材。  The environmental purification material according to claim 1, 2, 3, or 4, which is added and used in a farm.
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Publication number Priority date Publication date Assignee Title
WO2021230355A1 (en) * 2020-05-14 2021-11-18 学校法人慶應義塾 Column filler for liquid chromatography, and method for producing same

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