JP4671203B2 - Method for removing heavy metals from fish sauce - Google Patents
Method for removing heavy metals from fish sauce Download PDFInfo
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- JP4671203B2 JP4671203B2 JP2008106532A JP2008106532A JP4671203B2 JP 4671203 B2 JP4671203 B2 JP 4671203B2 JP 2008106532 A JP2008106532 A JP 2008106532A JP 2008106532 A JP2008106532 A JP 2008106532A JP 4671203 B2 JP4671203 B2 JP 4671203B2
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/60—Salad dressings; Mayonnaise; Ketchup
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
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Description
本発明は魚醤油中に含まれる重金属類を除去し、魚醤油の安全性を高めかつ魚醤油の特徴を（旨味等の有用成分）損なうことのない食品とすることができる魚醤油の重金属除去方法に関する。 The present invention removes heavy metals contained in fish soy sauce, increases the safety of fish soy sauce, and removes heavy metals from fish soy sauce that can be used as a food that does not impair the characteristics of fish soy sauce (useful ingredients such as umami). Regarding the method.
イワシ、イカ等の魚類の内蔵等を利用する魚醤油中には重金属類が多量に含有されていることがある。
しかし、今日まで生産地域住民の食習慣として、恒常的に斯かる魚醤油を摂取してきたものであるが、特定疾患（イタイタイ病のような公害）の発症例は今までのところ報告されていない。
Fish soy sauce that uses a built-in fish such as sardines and squids may contain a large amount of heavy metals.
However, until now, as a habit of local residents in production areas, such fish soy sauce has been ingested constantly, but there have been no reports of cases of specific diseases (pollution such as Itai Thai disease). .
このような理由で、従来から魚醤油は重金属の除去処理が施されることなく商品化されているのが実情である。
しかしながら、魚醤油の有用成分の活用、調味料としての全国展開・海外輸出など消費拡大を目指すに際し、食の安全・安心の観点から重金属の含有が問題となり、その除去処理が必要となってくると予想されるのである。
For these reasons, fish soy sauce has been commercialized without being subjected to heavy metal removal treatment.
However, when aiming to expand consumption, such as the use of useful ingredients in fish soy sauce, nationwide expansion as a seasoning, and overseas exports, the inclusion of heavy metals becomes a problem from the viewpoint of food safety and security, and its removal treatment is required It is expected.
ところで、魚醤油等の水産加工品から重金属類を除去することに着目した先行技術文献は発見されない。
水産加工品自体ではないけれど、帆立貝やイカ等の内臓残渣を廃棄処分することなく有効利用するために、内臓残渣からの重金属の除去方法が次の文献に開示されている。
Although not a processed fish product itself, in order to effectively use visceral residues such as scallops and squid without being disposed of, methods for removing heavy metals from the visceral residues are disclosed in the following documents.
上記の例えば特許文献１には、蟻酸、乳酸、酢酸等の有機酸や、塩酸、硫酸、リン酸等の鉱酸を用いてｐＨ３〜３．５の弱酸性とし、更に蛋白質分解酵素の作用によって重金属と結合した蛋白質を分解して重金属を蛋白質から解離させて重金属を酸処理液中に溶出させ、溶出した水溶液中の重金属類をキレート剤等によって分離する方法が記載されている。
しかし、魚醤油などの水産加工品の場合、含有する重金属類を酸処理液中に溶出させる特許文献１の方法では、重金属類の除去効率を高めるためにｐＨ３〜３．５という低ｐＨ
で処理することが必要となり、低ｐＨで処理すると魚醤油中の蛋白質が可溶化して溶出し、味が変化するためそのまま調味料として使用できない。
For example, in Patent Document 1 described above, a weak acid having a pH of 3 to 3.5 is obtained by using an organic acid such as formic acid, lactic acid or acetic acid, or a mineral acid such as hydrochloric acid, sulfuric acid or phosphoric acid, and further by the action of a proteolytic enzyme. A method is described in which a protein bound to a heavy metal is decomposed to dissociate the heavy metal from the protein, the heavy metal is eluted in an acid treatment solution, and the heavy metal in the eluted aqueous solution is separated by a chelating agent or the like.
However, in the case of processed fishery products such as fish soy sauce, in the method of Patent Document 1 in which the contained heavy metals are eluted in the acid treatment solution, a low pH of 3 to 3.5 in order to increase the removal efficiency of heavy metals.
When it is processed at a low pH, the protein in the fish soy sauce is solubilized and eluted, and the taste changes, so it cannot be used as it is as a seasoning.
すなわち、溶出しないで残存した蛋白質においても酵素活性が低下するため、水産エキスとしての利用は可能であっても、魚醤油のような発酵食品自体に対して利用すると、商品の品質低下を来たすという問題がある。
特に特許文献１に記載の方法のように、低ｐＨの酸処理液と蛋白質分解酵素と併用して処理すると上記問題点は更に大きくなり、斯かる方法は、魚醤油残滓を安全に廃棄するための前処理方法か、魚醤油残滓を飼料や肥料等として利用する場合の処理方法に限られてしまい、発酵食品である魚醤油として利用するための処理方法としては適用し得ないものである。
In other words, since the enzyme activity decreases even in proteins that remain without elution, it can be used as a marine extract, but if used for fermented foods such as fish soy sauce, the quality of the product is reduced. There's a problem.
In particular, when the treatment is carried out in combination with a low pH acid treatment solution and a proteolytic enzyme as in the method described in Patent Document 1, the above problem is further increased, and such a method is for safely discarding fish soy residue. This method is not limited to the above-mentioned pretreatment method or the treatment method in the case where fish soy residue is used as feed or fertilizer, and cannot be applied as a treatment method for use as fish soy sauce which is a fermented food.
また、特許文献２には、リン酸水溶液、有機酸、塩酸、硝酸、ホウ酸又は硫酸の水溶液を接触させ重金属を溶出させる方法が記載されている。
特許文献２や同様の特許文献３に記載の方法は、使用する酸濃度が高い場合はカドミウムの除去率は良いが、食品に食品添加物外の酸を混入させることになり食品としての安全性の再評価が必要となる。
さらに、有効成分である酵素の活性が失われる虞があることや、使用する酸濃度が低い場合はカドミウムの除去率が低いなどの欠点があり、魚醤油には採用できない方法である。
Patent Document 2 describes a method of eluting heavy metals by bringing an aqueous solution of phosphoric acid, an organic acid, hydrochloric acid, nitric acid, boric acid or sulfuric acid into contact with each other.
Although the method described in Patent Document 2 and similar Patent Document 3 has a high removal rate of cadmium when the acid concentration used is high, the food is mixed with an acid outside of the food additive and is safe as food. Re-evaluation is required.
Furthermore, there is a possibility that the activity of the enzyme, which is an active ingredient, may be lost, and when the acid concentration used is low, there are disadvantages such as a low removal rate of cadmium, and this method cannot be adopted for fish soy sauce.
そして、特許文献４に記載の方法では、食品を直接食品添加物であるゼオライトに接触させ除去する手法であり、有用成分まで同時に除去されることが予想され、また、ゼオライトと接触させる前にｐＨ調整を行うのに苛性ソーダー等を用いることから調味料としての味覚が変化することや、食品の安全性の問題から魚醤油には採用できない方法である。 And in the method of patent document 4, it is the method of making food contact the zeolite which is a food additive directly, and removing it, it is anticipated that a useful component will be removed simultaneously, Moreover, before making it contact with a zeolite, it is pH. This method is not applicable to fish soy sauce due to the change in taste as a seasoning due to the use of caustic soda or the like for adjustment and the problem of food safety.
本発明は上記従来の課題に鑑みなされたもので、魚醤油の含有するタンパク等の旨味成分を損なうことなく、効果的に魚醤油中の重金属類を除去し、調味料として、或いはこれを原料にして有効利用を図ることのできる魚醤油の重金属除去方法を提供することを目的とする。 The present invention has been made in view of the above-described conventional problems, and effectively removes heavy metals in fish soy sauce without damaging umami components such as protein contained in fish soy sauce, as a seasoning or as a raw material. It is an object of the present invention to provide a method for removing heavy metals from fish soy sauce that can be effectively used.
請求項１の本発明の魚醤油中の重金属除去方法は、魚醤油に食品添加物のタンニン又はタンニンを含む食品添加物を添加し、固液分離をして、うまみ成分等の有用成分が損なわれることなく、魚醤油から固形物を除去することを特徴とするものである。 The method for removing heavy metals in fish soy sauce according to the first aspect of the present invention is such that food additives containing tannin or tannin as a food additive are added to fish soy sauce, solid-liquid separation is performed, and useful ingredients such as umami ingredients are impaired. Without removing solids from the fish soy sauce.
請求項２の発明は、タンニンの量は、魚醤油１に対して重量比０．００１〜０．５の割合で添加することを特徴とするものである。 The invention of claim 2 is characterized in that the amount of tannin is added at a weight ratio of 0.001 to 0.5 with respect to the fish soy sauce 1.
請求項３記載の発明は、請求項１乃至２において、固液分離を膜分離又は遠心分離或いはフィルターろ過で行うことを特徴とするものである。 A third aspect of the invention is characterized in that, in the first or second aspect, the solid-liquid separation is performed by membrane separation, centrifugation, or filter filtration.
本発明方法によって魚醤油を処理すると、魚醤油中の重金属類を効率よく所定濃度以下に低減化することができると共に、重金属類を除去した後の魚醤油は旨味を示すアミノ酸を損なうことなく品質を維持し、より安全性を高めた魚醤油として商品化することができる効果を有する。 When processing fish soy sauce by the method of the present invention, heavy metals in fish soy sauce can be efficiently reduced to a predetermined concentration or less, and the fish soy sauce after removing heavy metals has a quality without damaging amino acids showing umami. And has the effect of being able to be commercialized as fish soy sauce with improved safety.
また、より安全性を高めた魚醤油としての調味料のみならず、これを原料に利用したサプリメント等への広範囲な利用が期待できる効果も有する。
そして、本発明方法は、ｐＨを調整する必要もない等の処理条件が少ない簡易な処理方法となり、食品添加物を利用するため製品の安全性にも問題がなく、本方法の利用促進が図れる効果を有する。
Moreover, it has the effect that it can be expected to be used not only for seasoning as fish soy sauce with higher safety, but also for supplements using this as a raw material.
The method of the present invention is a simple processing method with few processing conditions such as no need to adjust the pH, and there is no problem in product safety because of the use of food additives, and the use of this method can be promoted. Has an effect.
本発明方法は、上記のように魚醤油を、タンニン又はタンニンを含む食品添加物と混合させて処理した後、魚醤油中の沈殿物を分離し、除去した液を調味料とするものである。
ただし、タンニンの量は呈味性を損なわない程度であることが必要で、魚醤油１に対して重量比で０．００１〜０．５の割合で添加するのが好ましく、０．０５〜０．１倍がより好適である。
タンニンを含む食品添加物には、例えば柿渋が考えられる。
In the method of the present invention, fish soy sauce is mixed with tannin or a food additive containing tannin as described above, and then the precipitate in fish soy sauce is separated and the removed liquid is used as a seasoning. .
However, the amount of tannin needs to be in a level that does not impair the taste, and it is preferably added at a ratio of 0.001 to 0.5 by weight with respect to fish soy sauce 1 and 0.05 to 0. .Times.1 is more preferable.
Examples of food additives containing tannin include strawberry astringency.
魚醤油と、ろ過助剤とを接触させる時間は数分〜１日程度であるが、１２時間〜２４時間が好ましく、処理温度は有用成分が失われない温度で行なうことが必要であり、−１０〜９０℃の温度範囲内であればいずれの温度でも良い。
−１０℃以下では、魚醤油の凍結による品質低下が顕著に生じること、９０℃以上では風味の低下が生じるためである。
また、適宜に攪拌することで凝集反応を早めることができるのは言うまでもない。
The time for contacting the fish soy sauce with the filter aid is about several minutes to 1 day, but preferably 12 hours to 24 hours, and the treatment temperature should be such that no useful components are lost, Any temperature may be used as long as it is within a temperature range of 10 to 90C.
This is because at −10 ° C. or lower, the quality of the fish soy sauce is significantly reduced due to freezing, and at 90 ° C. or higher, the flavor is reduced.
Needless to say, the agglutination reaction can be accelerated by appropriate stirring.
ろ過助剤を添加した魚醤油から沈殿物を除去するための具体的な方法としては、凍結融解法、濾布等による濾過法、高速遠心分離機による方法等が挙げられるが、濾布による濾過することが好ましい。
凍結熔解、遠心分離では、魚醤油の必要成分も除去してしまう虞も考えられ、濾布はろ過助剤添加により生じた沈殿成分のみを除去できる確実性があり、さらに、これらのろ別方法の中で、濾布が最も安価となる利点も有する。
Specific methods for removing precipitates from fish soy sauce with added filter aid include freeze-thaw method, filtration method using filter cloth, etc., method using high-speed centrifuge, etc. It is preferable to do.
In freezing and centrifuging, there is a possibility that necessary components of fish soy sauce may be removed, and the filter cloth has certainty that it can remove only the precipitated components produced by the addition of filter aids. Among them, the filter cloth has the advantage of being the cheapest.
最終的には、魚醤油中の重金属類が１ｐｐｍ以下となるように処理することが好ましく、処理の繰り返し回数は、魚醤油中の重金属類の量、添加するろ過助剤の使用量等によっても異なるが２〜５回が好ましい。
また、処理後の魚醤油と沈殿物とを分離する方法としては、前記のように、遠心分離、デカンテーション、ろ過法など、一般的に処理残滓を処理液と分離できる方法であれば、どのような方法を用いても構わない。
Finally, it is preferable to treat so that the heavy metals in fish soy sauce is 1 ppm or less. The number of repetitions of the treatment also depends on the amount of heavy metals in fish soy sauce, the amount of filter aid used, etc. Although it is different, 2 to 5 times are preferable.
In addition, as a method for separating the processed fish soy sauce and the precipitate, any method can be used as long as it can generally separate the processing residue from the processing solution, such as centrifugation, decantation, and filtration. Such a method may be used.
上記のようにして、通常生産された魚醤油から重金属を除去した後、安全な調味料として市場へ出せるものとなる。
また、重金属を除去した魚醤油を乾燥させて、サプリメントや粉末調味料等の食品加工原料として利用することもできる。
魚醤油を乾燥させる場合、加熱乾燥すると味香りの呈味性が変化することや、魚醤油中の酵素活性が失われる虞があるため、真空乾燥や真空凍結乾燥等の加熱以外の方法で乾燥させることが好ましい。
As described above, after removing heavy metals from normally produced fish soy sauce, it can be put on the market as a safe seasoning.
Moreover, fish soy sauce from which heavy metals have been removed can be dried and used as food processing raw materials such as supplements and powder seasonings.
When drying fish soy sauce, it may be dried by methods other than heating, such as vacuum drying or vacuum freeze-drying, because it may change the taste of the flavor and taste and lose enzyme activity in fish soy sauce. It is preferable to make it.
本発明方法が処理対象とする魚醤油としては、重金属含有量が多く含んでいるために安全性が気遣われているイワシの内臓、イカの内臓、アジの内蔵、その他魚貝類の内蔵を原料とする魚醤油が挙げられるが、油脂の含量が多いものでも脱脂処理することなく利用が可能である。 The fish soy sauce to be treated by the method of the present invention is made from sardine internal organs, squid internal organs, built-in horse mackerel, and other built-in fish shellfish, which are considered to be safe because of their high heavy metal content. Fish soy sauce to be used can be used, but even oils with a high fat content can be used without degreasing.
魚醤油１０ｍＬに、タンニン水溶液（０.１、１.０、５.０％）、又は蒸留水、或いは５％グルコノデルタラクトン（ＧＤＬ）水溶液を１ｍＬを加え、撹拌した後、遠心分離（８０００ｒｐｍ、１５分）で固液分離した。
各処理後の上澄液および未処理の魚醤油１ｍＬに硝酸５ｍＬを加えて加熱分解した。
各処理を行った魚醤油からのＣｄの除去結果を表１に示す。
分解液のＣｄ濃度（ｐｐｍ）は、ＩＣＰ発光分析法にて測定した。
Ｃｄ除去率は、処理前後のＣｄ濃度から算出した。
1 mL of tannin aqueous solution (0.1, 1.0, 5.0%), distilled water, or 5% glucono delta lactone (GDL) aqueous solution is added to 10 mL of fish soy sauce, stirred, and then centrifuged (8000 rpm) , 15 minutes).
5 mL of nitric acid was added to 1 mL of the supernatant after each treatment and 1 mL of untreated fish soy sauce, followed by thermal decomposition.
Table 1 shows the results of Cd removal from fish soy sauce after each treatment.
The Cd concentration (ppm) of the decomposition solution was measured by ICP emission analysis.
The Cd removal rate was calculated from the Cd concentration before and after the treatment.
タンニン水溶液を添加した魚醤油のＣｄの除去結果は、蒸留水、或いはグルコノデルタラクトン（ＧＤＬ）水溶液を添加した魚醤油に比べて顕著な効果が認められた。 The Cd removal result of the fish soy sauce to which the tannin aqueous solution was added showed a remarkable effect as compared with the fish soy sauce to which distilled water or glucono delta lactone (GDL) aqueous solution was added.
また、処理後の魚醤油の全窒素、遊離アミノ酸量、乳酸量、抗酸化性を測定した結果を未処理の場合と比較して表２に示す。
その結果から本発明に係る処理による機能性の顕著な変化は確認されなかった。
In addition, Table 2 shows the results of measuring the total nitrogen, free amino acid content, lactic acid content, and antioxidant property of the fish soy sauce after the treatment, compared with the case of untreated.
As a result, a significant change in functionality due to the treatment according to the present invention was not confirmed.
魚醤油１０ｍＬに、柿タンニン（株式会社三桝嘉七商店製 強力スミオール）０．１ｍＬ、０．５ｍＬ、１ｍＬ、３ｍＬを加え、撹拌した後、遠心分離（８０００ｒｐｍ、１５分）で固液分離した。
各処理後の上澄液および未処理の魚醤油１ｍＬに硝酸５ｍＬを加えて加熱分解した。
各処理を行った魚醤油からのＣｄの除去結果を表３に示す。
分解液のＣｄ濃度（ｐｐｍ）は、ＩＣＰ発光分析法にて測定した。
Ｃｄ除去率は、処理前後のＣｄ濃度から算出した。
To 10 mL of fish soy sauce, 0.1 mL, 0.5 mL, 1 mL, and 3 mL of salmon tannin (manufactured by Mitsumata Kachichi Shoten Co., Ltd.) were added and stirred, followed by solid-liquid separation by centrifugation (8000 rpm, 15 minutes).
5 mL of nitric acid was added to 1 mL of the supernatant after each treatment and 1 mL of untreated fish soy sauce, followed by thermal decomposition.
Table 3 shows the results of removing Cd from the fish soy sauce after each treatment.
The Cd concentration (ppm) of the decomposition solution was measured by ICP emission analysis.
The Cd removal rate was calculated from the Cd concentration before and after the treatment.
柿タンニンにおいても、魚醤油に添加して固液分離することで、実施例１と同様のＣｄの除去効果がえられることが確認された。 It was confirmed that the same Cd removal effect as in Example 1 can be obtained by adding shark tannin to fish soy sauce and solid-liquid separation.
Claims (3)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008106532A JP4671203B2 (en) | 2008-04-16 | 2008-04-16 | Method for removing heavy metals from fish sauce |
| PCT/JP2009/054992 WO2009128311A1 (en) | 2008-04-16 | 2009-03-10 | Method of removing heavy metals from fish sauce |
| TW098110737A TW200946031A (en) | 2008-04-16 | 2009-03-31 | Method of removing heavy metals from fish sauce |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008106532A JP4671203B2 (en) | 2008-04-16 | 2008-04-16 | Method for removing heavy metals from fish sauce |
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| JP4671203B2 true JP4671203B2 (en) | 2011-04-13 |
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| CN102786578A (en) * | 2011-07-25 | 2012-11-21 | 中国科学院烟台海岸带研究所 | Method for removing heavy metal in marine animal protein enzymed liquid |
| JP6464011B2 (en) * | 2015-03-27 | 2019-02-06 | 株式会社ホクコン | Environmentally improved concrete block |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06106155A (en) * | 1992-09-09 | 1994-04-19 | Mutsumi Shoji | Removal of heavy metals from amino acid solution of fishes and shellfishes |
| JP2007282572A (en) * | 2006-04-17 | 2007-11-01 | Hokkaido Univ | Method for removing heavy metal from organic substance containing heavy metal, and method for producing food obtained by the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06106155A (en) * | 1992-09-09 | 1994-04-19 | Mutsumi Shoji | Removal of heavy metals from amino acid solution of fishes and shellfishes |
| JP2007282572A (en) * | 2006-04-17 | 2007-11-01 | Hokkaido Univ | Method for removing heavy metal from organic substance containing heavy metal, and method for producing food obtained by the same |
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| WO2009128311A1 (en) | 2009-10-22 |
| JP2009254274A (en) | 2009-11-05 |
| TW200946031A (en) | 2009-11-16 |
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