JP6554191B2 - Marine Fertilizer Using Nitrogen-Containing Waste Liquid And Method For Producing The Same - Google Patents
Marine Fertilizer Using Nitrogen-Containing Waste Liquid And Method For Producing The Same Download PDFInfo
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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
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Description
本発明は、例えば、廃棄された電子部品から貴金属を回収する際、或いは、半導体製造装置を洗浄する際に排出される硝酸やアンモニア等の窒素含有廃液を利用した海洋施肥材に関し、海洋を汚染することなく、海域の貧栄養化による水産資源の減少・品質低下の問題、特には、海苔の色落ちを効果的に抑制することができる、窒素含有廃液を利用した、海洋施肥材及びその製造方法に関する。 The present invention relates to, for example, marine fertilizing materials using nitrogen-containing waste liquid such as nitric acid or ammonia discharged when recovering precious metals from discarded electronic parts or cleaning semiconductor manufacturing equipment, and contaminates the ocean. Marine fertilizing material and its production using nitrogen-containing waste liquid, which can effectively suppress the problem of reduction and deterioration of fishery resources due to poor nutrition of the sea area, in particular, discoloration of seaweed without Regarding the method.
廃棄された電子部品から貴金属（金、銀、白金、パラジウムなど）を回収する際や、半導体製造装置を洗浄する際などには、大量の硝酸やアンモニア等が使用されており、排出される廃液には窒素が数千から数万ｍｇ／Ｌ含まれる。排出される廃液は、無害化処理後、下水に放流されるが、同処理では窒素の除去が十分でないため、窒素排出基準を満たすべく、生物処理・焼却等の別途の処理を行う必要がある。
しかし、上記廃液には高濃度の窒素や塩分が含まれるため、生物処理の場合、前処理として希釈が必要であったり、焼却の場合は、排出されるＮＯｘガスを除去する必要があったりと、いずれも処理が煩雑となっていた。
When recovering precious metals (gold, silver, platinum, palladium, etc.) from discarded electronic parts, or when cleaning semiconductor manufacturing equipment, a large amount of nitric acid, ammonia, etc. is used, and waste liquid discharged Contains several thousand to several tens of thousands mg / L of nitrogen. Effluent wastes are discharged to sewage after detoxification treatment, but it is necessary to carry out separate treatment such as biological treatment and incineration in order to meet nitrogen emission standards because nitrogen removal is not sufficient in the treatment. .
However, since the above-mentioned waste liquid contains high concentration nitrogen and salt, in the case of biological treatment, it is necessary to dilute as pretreatment, or in case of incineration, it is necessary to remove the exhausted NO x gas. In both cases, the processing was complicated.
以上のように、廃液の処理には追加のコストが発生するため、廃液の有効活用が急務となっている。ところで、高度経済成長期以降、沿岸域において富栄養化による赤潮の発生件数が増加していたが、排水規制が強化されたことで、その件数は減少し、さらに、ダム建設による河川からの栄養塩負荷量の減少や沿岸地開発による地形変化により、「貧栄養化（海水中の窒素等が減少）」が進行し、磯焼け、藻場の減少、海苔の色落ち、生物種や個体数の減少等の問題が起こるようになった。 As described above, since the cost of waste liquid treatment is additional, effective use of the waste liquid is urgently needed. By the way, since the high economic growth period, the number of occurrences of red tide due to eutrophication has increased in the coastal area, but the number has decreased due to the strengthening of drainage regulations, and further, the nutrition from the river by the dam construction “Ethrotrophic (reduction of nitrogen etc. in seawater)” progresses due to decrease of salt load and landform change by coastal area development, and firewood burns, decrease of seaweed bed, discoloration of seaweed, species and population Problems such as a decrease in
貧栄養化の対策として、施肥（栄養となる薬品を海に散布する行為）が広まり、全国で一定の成果を上げている（特許文献１）。海苔の色落ち（黒色から緑〜黄色に変化）も貧栄養化によって引き起こされる現象の一つであり、色落ちは、海苔の品質(単価)を下げるため、海苔養殖業者に大きな損害を与えている。海苔の色落ち対策として、海水に硝安を溶かして散布する等、の施肥方法が知られている（特許文献２〜４）。 As measures against malnutrition, fertilization (the act of applying nutrient medicines to the sea) has become widespread and has achieved certain results throughout the country (Patent Document 1). The coloration of nori (color changing from black to green to yellow) is also one of the phenomena caused by malnutrition, and the coloration causes the quality of seaweed (price) to be reduced, causing significant damage to nori fish farmers. Yes. As a measure against discoloration of the seaweed, fertilization methods such as dissolving ammonium nitrate in seawater and spraying are known (Patent Documents 2 to 4).
先述した、貴金属の抽出や半導体製造装置の洗浄の際に排出される廃液は、窒素濃度が非常に高いため、海水で希釈して散布すれば、硝安と同じ効果が期待される。一方、高塩分のため、陸上肥料としては使用することができない。そこで、廃液の再利用の一環として、窒素含有廃液を使用した海苔の色落ちを抑制するための施肥材の研究開発を開始した。なお、別の廃材の再利用として、鉄鋼スラグ、水産資源の生育環境改善のために、コンクリート廃材等を利用する技術が開示されている（特許文献５）。 Since the waste liquid discharged at the time of extraction of precious metals and cleaning of a semiconductor manufacturing apparatus mentioned above has very high nitrogen concentration, the same effect as ammonium nitrate is expected if diluted with seawater and dispersed. On the other hand, because of high salinity, it can not be used as land fertilizer. Therefore, as part of the recycling of waste liquid, research and development of fertilization materials to suppress discoloration of laver using nitrogen-containing waste liquid was started. In addition, the technology which utilizes concrete waste material etc. is disclosed for the growth environment improvement of steel slag and marine resources as another reuse of waste material (patent document 5).
有価金属の抽出や半導体製造装置の洗浄などの際には、窒素成分を含む、硝酸やアンモニア等が使用される。その後に排出される廃液は高濃度の窒素を含み、その廃液を処理する方法として、イオン交換、電解処理、溶媒抽出、触媒分解、生物処理等が知られている。しかしながら、高濃度の窒素含有廃液に対しては、上記処理はコストが嵩み、実用的でなく、高濃度の窒素含有廃液を既存の技術で一律に処理することは困難であった。 In the extraction of valuable metals, cleaning of the semiconductor manufacturing apparatus and the like, nitric acid, ammonia and the like containing a nitrogen component are used. The waste liquid discharged after that contains nitrogen of high concentration, and ion exchange, electrolytic treatment, solvent extraction, catalytic decomposition, biological treatment and the like are known as methods for treating the waste liquid. However, for high concentration nitrogen-containing waste liquid, the above-mentioned treatment is costly and impractical, and it has been difficult to uniformly treat high concentration nitrogen-containing waste liquid by the existing technology.
一方、海洋においては、全国的に栄養素が不足する貧栄養化の問題が発生しており、例えば、貧栄養化による漁業生産の低下、磯焼け、藻場の減少等様々な問題が生じている。海苔の色落ちの問題も貧栄養化が原因であり、栄養が不足した海苔は色素を十分に作ることができず、色が薄くなって、品質を低下させるという問題が生じる。そして、現在、色落ち防止のため、硝安や硫安等を用いた施肥が全国的に行われている。 On the other hand, in the ocean, there is a problem of malnutrition, which lacks nutrients all over the country, and various problems such as decline in fishery production due to malnutrition, burnout and decrease in seaweed beds have occurred. . The problem of discoloration of the seaweed is also due to poor nutrition, and the nourished seaweed can not make sufficient pigment, resulting in a problem that the color becomes pale and the quality is degraded. Currently, fertilization using ammonium nitrate, ammonium sulfate, or the like is performed nationwide to prevent discoloration.
本発明は、上記問題を解決するものであって、窒素含有廃液から得られる海洋施肥材であって、貧栄養化の問題、特に、海苔の色落ちを抑制することができる、海洋施肥材及びその製造方法を提供することを課題とする。さらに、重金属等の有害物質が排出基準を満たし、また、海洋において肥効を維持するために、施肥方法に応じた、液状、固体状、ゲル状、或いは粉末状の施肥材を提供することを課題とする。 The present invention solves the above problems and is a marine fertilizer application material obtained from a nitrogen-containing waste liquid, which can suppress the problem of poor nutrition, in particular, discoloration of nori seaweed, and An object of the present invention is to provide a method of manufacturing the same. Furthermore, to provide a liquid, solid, gel or powder fertilizer according to the method of fertilization in order that harmful substances such as heavy metals will meet emission standards and maintain fertilization in the ocean. Let it be an issue.
上記の課題を解決するために、本発明者らは鋭意研究を行った結果、窒素含有廃液を無害化処理し、施肥の対象に応じた成分の調整やｐＨを適切に調整することなどにより、例えば有価金属の抽出の際や半導体製造装置の洗浄の際から排出される、窒素含有廃液を海洋施肥材としての新たな活用を見出し、本発明を完成するに至った。この知見に基づき、本願は、以下の発明を提供する。 In order to solve the above problems, as a result of intensive research conducted by the present inventors, the nitrogen-containing waste liquid is detoxified, and adjustment of components according to the target of fertilization, pH is properly adjusted, etc. For example, the inventors have found a new use of a nitrogen-containing waste solution discharged from the time of extraction of valuable metals or cleaning of a semiconductor manufacturing apparatus as a marine fertilizing material, and the present invention has been completed. Based on this finding, the present application provides the following inventions.
１）製造業で排出される窒素含有廃液を原料として使用することを特徴とする施肥材の製造方法。
２）前記窒素含有廃液は、窒素濃度が１０００〜１０００００ｍｇ／Ｌであることを特徴とする上記１）記載の施肥材の製造方法。
３）窒素含有廃液を無害化処理及びｐＨ調整することを特徴とする上記１）又は２）に記載の施肥材の製造方法。
４）前記無害化処理は、水酸化物法、共沈法、置換法、硫化物法、フェライト法、金属還元法、活性炭吸着法、イオン交換法、アルカリ塩素法、紺青法、酸化分解法、電解酸化法、揮散法、生物処理法等により、水質汚濁防止法（海域）に記載される有害物質及びその他の物質を許容限度以下とすることを特徴とする上記１）〜３）のいずれか一に記載の施肥材の製造方法。
５）ｐＨ調整は、水酸化ナトリウム、水酸化カルシウム、水酸化マグネシウム、炭酸カルシウム、炭酸ナトリウム、アンモニア、塩酸、硫酸、硝酸、又は、有機酸を用いて行い、ｐＨを５以上９以下とすることを特徴とする上記１）〜４）のいずれか一に記載の施肥材の製造方法。
６）無害化処理後、窒素とリンの成分比率が、モル比でＮ／Ｐが５以上になるようにリン又はその化合物を添加することを特徴とする上記１）〜５）のいずれか一に記載の施肥材の製造方法。
７）無害化処理後、鉄又はその化合物とリンの成分比率が、モル比でＰ／Ｆｅ＝１０〜１００００となるように、鉄又はその化合物を添加することを特徴とする上記１）〜６）のいずれか一に記載の施肥材の製造方法。
８）無害化処理液を固化剤又はゲル化剤を使用して、固形又はゲル状に加工することを特徴とする上記１）〜７）のいずれか一に記載の施肥材の製造方法。
９）無害化処理液を蒸発乾固し粉末状にすることを特徴とする上記１）〜７）のいずれか一に記載の施肥材の製造方法。
１０）上記１）〜９）のいずれか一に記載の製造方法から得られた施肥材を用いて、海苔の色落ちを抑制する方法。
1) A method of producing a fertilizer applying material comprising using as a raw material a nitrogen-containing waste solution discharged in the manufacturing industry.
2) The method for producing a fertilizer according to 1) above, wherein the nitrogen-containing waste liquid has a nitrogen concentration of 1000 to 100,000 mg / L.
3) The method for producing a fertilizer according to 1) or 2) above, wherein the nitrogen-containing waste liquid is detoxified and the pH is adjusted.
4) The detoxification treatment includes hydroxide method, coprecipitation method, substitution method, sulfide method, ferrite method, metal reduction method, activated carbon adsorption method, ion exchange method, alkali chlorine method, bitumen method, oxidation decomposition method, Any of the above 1) to 3) characterized in that harmful substances and other substances described in the Water Pollution Control Law (sea area) are made below the allowable limit by electrolytic oxidation method, volatilization method, biological treatment method etc. The manufacturing method of the fertilization material as described in one.
5) pH adjustment is performed using sodium hydroxide, calcium hydroxide, magnesium hydroxide, calcium carbonate, sodium carbonate, ammonia, hydrochloric acid, sulfuric acid, nitric acid, or an organic acid to have a pH of 5 or more and 9 or less The manufacturing method of the fertilizing material as described in any one of said 1) -4 characterized by the above-mentioned.
6) After detoxification treatment, phosphorus or its compound is added such that the component ratio of nitrogen and phosphorus is 5 or more in molar ratio, any one of the above 1) to 5) characterized by The manufacturing method of the fertilization material as described in-.
7) After the detoxification treatment, iron or its compound is added such that the component ratio of iron or its compound and phosphorus is P / Fe = 10 to 10000 in molar ratio; The manufacturing method of the fertilization material as described in any one of 2.).
8) The method for producing a fertilizer according to any one of the above 1) to 7), wherein the detoxifying treatment liquid is processed into a solid or gel using a solidifying agent or a gelling agent.
9) The method for producing a fertilizer according to any one of 1) to 7) above, wherein the detoxification treatment liquid is evaporated to dryness to form a powder.
10) The method of suppressing discoloration of laver using the fertilizer obtained from the manufacturing method as described in any one of said 1) -9).
有価金属の抽出や半導体製造装置の洗浄などの際に排出される窒素含有廃液を、海洋生物の施肥材とすることにより、これまで排水処理が困難であった窒素含有廃液の有効的な活用を可能とし、海洋における貧栄養化の問題、特に、海苔の色落ち、を抑制することができるという優れた効果が得られる。これにより、海産物の品質を向上、従来に比べて施肥材のコスト削減が可能となる。また、本発明によって得られる施肥剤は、海苔の色落ち抑制以外にも、その他の藻類の品質向上や、貝類の生産性向上にも有効である。 Using nitrogen-containing waste liquid discharged during extraction of valuable metals, cleaning of semiconductor manufacturing equipment, etc., as a fertilizer for marine organisms, effective utilization of nitrogen-containing waste liquid that has been difficult to treat wastewater so far It is possible to obtain the excellent effect of being able to suppress the problems of malnutrition in the ocean, especially the discoloration of seaweed. This makes it possible to improve the quality of marine products and reduce the cost of fertilizers compared to conventional products. Moreover, the fertilizing agent obtained by this invention is effective also in the quality improvement of other algae, and the productivity improvement of shellfish besides the discoloration suppression of a seaweed.
有価金属の抽出や半導体製造装置の洗浄などの際、硝酸やアンモニア等が使用されるため、排出される廃液には高濃度の窒素が含まれる。本発明は、このような製造業で排出される窒素含有廃液を有効利用するものである。ここで、本発明の窒素含有廃液は、硝酸、アンモニア、又はこれらの化合物を混合したものを主成分とする溶液であって、窒素を１０００〜１０００００ｍｇ／Ｌ含有するものをいう。 Since nitric acid, ammonia and the like are used in extraction of valuable metals and cleaning of semiconductor manufacturing equipment, etc., the waste liquid to be discharged contains high concentration of nitrogen. The present invention effectively utilizes the nitrogen-containing waste solution discharged in such a manufacturing industry. Here, the nitrogen-containing waste solution of the present invention is a solution containing nitric acid, ammonia, or a mixture of these compounds as a main component, and containing 1000 to 100000 mg / L of nitrogen.
製造業で排出される窒素含有廃液には、通常、重金属等の有害物質が含まれるため、施肥材として利用するために無害化処理を行う。無害化処理は、水酸化物法、共沈法、置換法、硫化物法、フェライト法、金属還元法、活性炭吸着法、イオン交換法、アルカリ塩素法、紺青法、酸化分解法、電解酸化法、揮散法、生物処理法等を用いることができる。 Since nitrogen-containing waste solution discharged in the manufacturing industry usually contains harmful substances such as heavy metals, it is detoxified to be used as a fertilizer. Detoxification treatment includes hydroxide method, coprecipitation method, substitution method, sulfide method, ferrite method, metal reduction method, activated carbon adsorption method, ion exchange method, alkali chlorine method, bitumen method, oxidative decomposition method, electrolytic oxidation method , Volatilization methods, biological treatment methods, etc. can be used.
無害化処理を行うことで、表１に示す水質汚濁防止法（海域）に記載される有害物質及びその他の物質を許容限度以下まで低下させる（但し、窒素、リン及び鉄を除く）。 By performing detoxification treatment, harmful substances and other substances listed in the Water Pollution Control Act (sea area) shown in Table 1 are reduced to below the allowable limit (except for nitrogen, phosphorus and iron).
さらに好ましくは、表２に示す環境基準の基準値及び要監視項目の指針値以下とする。 More preferably, it is below the standard value of the environmental standard shown in Table 2 and the guideline value of the item to be monitored.
これにより、海洋を汚染することなく、散布が可能となる。なお、無害化処理方法によって、無害化処理液中に０．１〜２０％程度の高濃度の塩分（塩化ナトリウム、塩化カルシウムなど）が含まれることがあり、塩害のおそれがあるため陸上肥料としては使用できない。 This allows for dispersion without polluting the ocean. In addition, depending on the detoxification treatment method, the detoxification treatment solution may contain high concentrations of salt (sodium chloride, calcium chloride, etc.) of about 0.1 to 20%, and there is a risk of salt damage, so as land fertilizer Cannot be used.
また、無害化処理後の液は、通常、無害化処理の方法により、ｐＨが強酸性や強アルカリ性になることがあるため、海洋施肥材として利用するためにｐＨ調整を行う。ｐＨ調整は、水酸化ナトリウム、水酸化カルシウム、水酸化マグネシウム、炭酸カルシウム、炭酸ナトリウム、アンモニア、塩酸、硫酸、硝酸又は有機酸などの中和剤を用いて、水質汚濁防止法（海域）に基づき、ｐＨを５以上９以下に調整することが好ましい。さらに好ましくは、環境基準に基づきｐＨを７．８以上８．３以下とする。
なお、酸処理材として使用する場合には、ｐＨを２程度に調整することが有効である。ここで、酸処理剤とは、ノリ葉体表面に付着してノリの成長を阻害したり、ノリの病気の原因となる、珪藻やバクテリアなどを除去したりするために用いる酸（通常、有機酸）を含む液剤で、希釈してｐＨ２程度で使用される。
In addition, since the liquid after the detoxification treatment may become strongly acidic or strongly alkaline depending on the detoxification treatment method, the pH is adjusted to be used as a marine fertilizer. pH adjustment is based on the Water Pollution Control Act (sea area) using neutralizing agents such as sodium hydroxide, calcium hydroxide, magnesium hydroxide, calcium carbonate, sodium carbonate, ammonia, hydrochloric acid, sulfuric acid, nitric acid or organic acids. , PH is preferably adjusted to 5 or more and 9 or less. More preferably, the pH is set to 7.8 or more and 8.3 or less based on environmental standards.
In addition, when using as an acid treatment material, it is effective to adjust pH to about 2. Here, the acid treatment agent is an acid used to remove diatoms, bacteria, etc. which are attached to the surface of the Nori leaf to inhibit the growth of the Nori, or to cause disease of the Nori (usually organic It is used at a pH of about 2 after being diluted with a solution containing acid.
また、本発明において、海洋生物の栄養となるように、リン（Ｐ）又はその化合物を添加してもよく、その場合、窒素とリンの成分比率がモル比でＮ／Ｐが５以上となるように調整することが好ましい。添加するリン化合物としては、オルトリン酸、リン酸ニアンモニウムなどが挙げられ、藻類が利用しやすい形態という理由から、無機リン酸を使用することが好ましい。 Furthermore, in the present invention, phosphorus (P) or a compound thereof may be added to provide nutrition for marine organisms, in which case the ratio of components of nitrogen and phosphorus is 5 or more in molar ratio N / P. It is preferable to adjust so that. As a phosphorus compound to be added, orthophosphoric acid, diammonium phosphate and the like can be mentioned, and it is preferable to use inorganic phosphoric acid because it is a form easy to use by algae.
さらに、本発明において、有機鉄（例えば、クエン酸鉄）又は無機鉄（例えば、塩化鉄）を添加して、鉄栄養素を付加することができる。その場合、鉄又はその化合物とリンの成分比率が、モル比でＰ／Ｆｅ＝１０〜１００００となるように、鉄又はその化合物を添加することが好ましい。またこのとき、ｐＨによっては、鉄が水酸化物を形成することがあるため、有機鉄を使用することが好ましい。なお、上述したリンや鉄などの成分調整は、ｐＨ調整の前或いは後のどちらでも構わないが、成分調整後のｐＨは５以上９以下になるようにする。 Furthermore, in the present invention, organic iron (eg, iron citrate) or inorganic iron (eg, iron chloride) can be added to add iron nutrients. In that case, it is preferable to add iron or its compound such that the component ratio of iron or its compound and phosphorus is P / Fe = 10 to 10000 in molar ratio. At this time, it is preferable to use organic iron because iron may form a hydroxide depending on the pH. In addition, although adjustment of components, such as phosphorus and iron which were mentioned above, may be any, before or after pH adjustment, pH after component adjustment is made to become 5 or more and 9 or less.
以上の工程により得られる施肥材は、海洋生物における貧栄養化の問題、特に海苔の色落ちの問題を解消することができる。一方、液状の施肥材を海に散布した場合、海流によって拡散してしまい、施肥の効果が弱まることがある。したがって、固化剤、又はゲル化剤を用いて、固形又はゲル状とし、徐々に溶けるようにすることで、拡散防止に繋げることが可能となる。固化剤としては、石膏があり、ゲル化剤としては、寒天があるが、本発明は、これらの材料に限定されるものではない。 The fertilizing material obtained by the above process can solve the problem of poor nutrition in marine organisms, particularly the problem of discoloration of seaweed. On the other hand, when liquid fertilization material is sprayed to the sea, it spreads by the ocean current, and the effect of fertilization may be weakened. Therefore, by using a solidifying agent or a gelling agent, making it solid or gel-like and gradually dissolving it can lead to diffusion prevention. As a solidifying agent there is gypsum, and as a gelling agent there is agar, but the present invention is not limited to these materials.
さらに、液状の施肥材は容積が大きく、保管場所を多く必要とすることから、一度、これを加熱して水分蒸発、乾固させ、また、使用時には、海水又は淡水に再溶解することも有効である。これにより、保管や運搬を簡便に行うことが可能となり、大幅なコスト削減が可能となる。 Furthermore, since liquid fertilizers are large in volume and require a lot of storage places, it is also effective to heat them once to evaporate water, to make them dry, and to re-dissolve in seawater or fresh water at the time of use. It is. As a result, storage and transportation can be easily performed, and significant cost reduction can be achieved.
次に本発明の実施例及び比較例について説明する。なお、以下の実施例は、あくまで代表的な例を示しているもので、本発明は、これらの実施例に制限される必要はなく、明細書の記載される技術思想の範囲で解釈されるべきものである。 Next, Examples and Comparative Examples of the present invention will be described. The following examples are merely representative examples, and the present invention need not be limited to these examples, and is interpreted within the scope of the technical concept described in the specification. It should be.
（窒素含有廃液の無害化処理）
有価金属の抽出工程と半導体製造装置の洗浄工程などから排出された窒素含有廃液について、無害化処理とｐＨ調整を行った。無害化処理は、中和剤および硫化ソーダを用いるアルカリ沈殿法＋硫化物法にて重金属などの有害物質を除去した。なお、中和剤として苛性ソーダを用いることで、栄養素としてリンを添加した際に、沈殿が起きないようにすることができる。
上記無害化処理後の処理液は、強アルカリ性を示すことから、塩酸を用いてｐＨ調整を行った。この無害化処理及びｐＨ調整後の処理液について、成分分析を行った結果、表１及び表２に示すように、液中の環境規制項目（水質汚濁防止法（海域）に記載される有害物質及びその他の物質等、及び、環境基準及び要監視項目の指針）は、いずれも許容限度または指針値以下であった。
(Detoxification treatment of nitrogen-containing waste liquid)
Detoxification treatment and pH adjustment were performed on the nitrogen-containing waste liquid discharged from the extraction process of valuable metals and the cleaning process of semiconductor manufacturing equipment. In the detoxification treatment, harmful substances such as heavy metals were removed by an alkali precipitation method and a sulfide method using a neutralizing agent and sodium sulfide. By using caustic soda as a neutralizing agent, it is possible to prevent precipitation when adding phosphorus as a nutrient.
The treatment liquid after the above-mentioned detoxification treatment showed strong alkalinity, so pH adjustment was performed using hydrochloric acid. As a result of conducting component analysis about the processing liquid after this detoxification processing and pH adjustment, as shown in Table 1 and Table 2, the harmful substance described in the environmental regulation item (water pollution control method (sea area) in the liquid) And other substances, etc., and guidelines for environmental standards and items to be monitored) were all below acceptable limits or guideline values.
（培養液の調整）
上記処理液について、ＤＩＮ（溶存無機窒素）濃度が、４００μＭ、８００μＭ、１６００μＭになるように、３％−人工海水（ｒｅｄ ｓｅａ ｓａｌｔ）で希釈した。希釈後、リン、鉄を添加して成分調整を行った。リンについては、Ｎ／Ｐ（モル比）が６．２５、１２．５、２５となるように、リン酸を添加した。鉄については、Ｐ：Ｆｅの比(モル比)が１：０．０１となるように、クエン酸鉄アンモニウムを添加した。成分調整後、苛性ソーダにてｐＨ８に調整して培養液とした。また、リン・鉄を添加しない培養液（ＤＩＮ濃度：４００μｍ、８００μＭ、１６００μＭ）、及び、参照用として３％−人工海水を用意した。
(Preparation of culture solution)
About the said process liquid, it diluted with 3%-artificial sea water (red sea salt) so that DIN (dissolved inorganic nitrogen) density | concentration might be set to 400 micromol, 800 micromol, and 1600 micromol. After dilution, phosphorus and iron were added to adjust the components. About phosphorus, phosphoric acid was added so that N / P (molar ratio) might be 6.25, 12.5, and 25. For iron, ammonium iron citrate was added so that the P: Fe ratio (molar ratio) was 1: 0.01. After adjusting the ingredients, the pH was adjusted to 8 with caustic soda to make a culture solution. Moreover, the culture solution (DIN density | concentration: 400 micrometers, 800 micrometers, 1600 micrometers) which do not add phosphorus and iron, and 3% -artificial seawater were prepared as reference.
（効果確認試験１）
２０１６年１２月に広島県福山市田島地区にて採取したスサビノリを使用し、屋内にて培養試験を行った。まず、ノリ葉体を１０ｍｍポンチで打ち抜いた後、３％−人工海水とともにビンに入れ、激しく振とうしてノリ葉体表面に付着する微生物を除去した。次に、表１の通りに、ＤＩＮ濃度、鉄・リン濃度を調整した培養液を用意し、減菌済みプラスチック培養容器（Greiner Bio-One、CELLSTAR Xell Culture Flask 658175、500ml）にそれぞれの培養液（５０ｍl）とノリサンプル６枚を入れた。その後、振とう培養器にて、５５ｒｐｍで振とうさせながら、照明付きインキュベータ内にて１５℃、３００μｍｏｌｍ−２・ｓ−１の光照射下（明：１２時間、暗：１２時間）で６日間培養した。
(Effect confirmation test 1)
A culture test was performed indoors using Susabinori collected in December 2016 in Tajima area, Fukuyama City, Hiroshima Prefecture. First, the Nori leaf was punched out with a 10 mm punch and then placed in a bottle with 3% artificial water and shaken vigorously to remove the microorganisms adhering to the surface of the Nori leaf. Next, as shown in Table 1, prepare culture solutions with adjusted DIN concentration and iron / phosphorus concentration, and put each culture solution in a sterilized plastic culture container (Greiner Bio-One, CELLSTAR Xell Culture Flask 658175, 500 ml). (50 ml) and 6 pieces of Nori sample were put. After that, while shaking at 55 rpm in a shaking incubator, in a lighted incubator at 15 ° C., under light irradiation of 300 μmol m- 2 · s −1 (light: 12 hours, dark: 12 hours), for 6 days Cultured.
６日経過後、ノリの直径、ノリの湿重量、及びＳＰＡＤ値（葉緑素量）を測定した。なお、ＳＰＡＤ値はノリサンプル３枚を重ねて測定した値である。その結果を表１に示す。表１に示す通り、実施例１−１〜１−１２について、３％−人工海水（参照例１−１）と比較すると、ノリサンプルのＳＰＡＤ値は、３％−人工海水（参照例１−１）に比べて実験区で全体的に高い値を示し、色落ち抑制効果が確認できた。また、ノリ葉体の湿重量は増加傾向が認められた。一方、直径（サイズ）は、３％−人工海水（参照例１）のほうが大きい場合があった。これは、いわゆる「徒長」という現象であり、サイズは大きくなるがノリ葉体が薄く弱くなったことを示唆している。 After 6 days, the diameter of the Nori, the wet weight of the Nori, and the SPAD value (chlorophyll content) were measured. Here, the SPAD value is a value obtained by overlapping three nori samples and measuring them. The results are shown in Table 1. As shown in Table 1, for Examples 1-1 to 1-12, when compared with 3% -artificial seawater (Reference Example 1-1), the SPAD value of Nori sample is 3% -Artificial seawater (Reference Example 1-) Compared to 1), the experimental area showed higher values overall, and the effect of suppressing discoloration was confirmed. In addition, the wet weight of the Nori leaf tended to increase. On the other hand, there were cases where the diameter (size) was 3%-artificial seawater (Reference Example 1) was larger. This is a so-called "veccular" phenomenon, suggesting that the size is increased but the Nori leaf is thin and weak.
（効果確認試験２）
２０１７年２月に広島県福山市田島地区にて採取したスサビノリ（ＳＰＡＤ値：０）を使用し、屋外にて培養試験を行った。円形水槽に海水１００Ｌとノリ葉体５００ｇを入れ、８９時間培養した。１日に３回海水の交換を行い、その際、海水中のＤＩＮ濃度が４００μＭ、８００μＭ、１６００μＭになるように上記処理液を添加した。リン、鉄については、海水中のＮ：Ｐ：Ｆｅ（モル比）が２５：１：０．０１になるように、リン酸およびクエン酸鉄アンモニウムを添加した。また、リン・鉄を添加しない水槽（ＤＩＮ濃度：４００μＭ、８００μＭ、１６００μＭ）と、参照用として、施肥材を添加しない海水のみの実験区を用意した。実験水槽は常にポンプ循環にて、海水にノリ葉体を浮遊させた状態で撹拌を行った。
(Effect confirmation test 2)
A culture test was conducted outdoors using susabino (SPAD value: 0) collected in February 2017 in Tajima, Fukuyama, Hiroshima Prefecture. In a circular water tank, 100 L of seawater and 500 g of Nori leaf were placed and cultured for 89 hours. The exchange of seawater was carried out three times a day, and at that time, the above-mentioned treatment solution was added so that the concentration of DIN in seawater became 400 μM, 800 μM, and 1600 μM. For phosphorus and iron, phosphoric acid and ammonium iron citrate were added such that N: P: Fe (molar ratio) in seawater was 25: 1: 0.01. In addition, a water tank (DIN concentration: 400 μM, 800 μM, 1600 μM) to which phosphorus and iron were not added and an experiment section of only seawater to which a fertilizer was not added were prepared as a reference. In the experimental water tank, stirring was always performed with the Nori leaf suspended in seawater by pump circulation.
８９時間経過後、ノリのＳＰＡＤ値を測定した。また、一部のサンプルを乾ノリ（板ノリ）に加工し、そのＳＰＡＤ値を測定した。なお、ＳＰＡＤ値はノリサンプル３枚を重ねて測定した値である。その結果を表２に示す。表２に示す通り、湿ノリ、乾ノリのＳＰＡＤ値について、実施例２−１〜２−６を参照例２−１と比較すると、いずれも高い値を示し、色落ち抑制効果が確認できた。 After 89 hours, the SPAD value of Nori was measured. Moreover, some samples were processed into dry nori (plate nori), and the SPAD value was measured. Here, the SPAD value is a value obtained by overlapping three nori samples and measuring them. The results are shown in Table 2. As shown in Table 2, with regard to the SPAD values of wet nori and dry nori, when each of Examples 2-1 to 2-6 was compared with Reference Example 2-1, the values were all high, and the effect of suppressing discoloration was confirmed .
本発明は、有価金属の抽出や半導体製造装置の洗浄などの際排出される窒素含有廃液を、海洋生物の施肥材とすることにより、これまで排水処理が困難であった窒素含有廃液の有効的な活用を可能とすることができる。本発明の施肥剤は、海洋における貧栄養化の問題、特に、海苔の色落ちを抑制することができ、また、海苔の色落ち抑制以外にも、その他の藻類の品質向上や貝類の生産性向上にも有効である。本発明は、窒素含有廃液処理の分野及び海洋施肥材の分野において、有用である。
The present invention makes it possible to effectively treat nitrogen-containing waste which has been difficult to treat with waste water, by using the waste liquid containing nitrogen discharged during extraction of valuable metals, cleaning of semiconductor manufacturing equipment, etc. as a fertilizer for marine organisms. Can be used. The fertilizer of the present invention can suppress the problem of malnutrition in the ocean, in particular, the color loss of seaweed, and in addition to the suppression of color loss of seaweed, other algae quality improvements and shellfish productivity It is also effective for improvement. The present invention is useful in the field of nitrogen-containing effluent treatment and in the field of marine fertilizers.
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