JP4600974B2 - Recycling method for fishery processing residue - Google Patents

Recycling method for fishery processing residue Download PDF

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JP4600974B2
JP4600974B2 JP2004238563A JP2004238563A JP4600974B2 JP 4600974 B2 JP4600974 B2 JP 4600974B2 JP 2004238563 A JP2004238563 A JP 2004238563A JP 2004238563 A JP2004238563 A JP 2004238563A JP 4600974 B2 JP4600974 B2 JP 4600974B2
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residue
processing
fishery
processing residue
acid
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智 塚原
裕彦 吉田
和彦 桑田
晁暎 松本
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Miyoshi Oil and Fat Co Ltd
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本発明は水産加工残滓中に含まれる重金属類を除去し、水産加工残滓を食用資源として利用可能に処理することができる水産加工残滓の再生処理方法に関する。   The present invention relates to a method for reclaiming fishery processing residue that can remove heavy metals contained in the fishery processing residue and make the fishery processing residue usable as an edible resource.

ホタテ貝の内蔵、イカの内蔵等の水産加工残滓中には重金属類が多量に含有されていることがあり、従来このような水産加工残滓は利用されることなく焼却、埋立等の廃棄処分をされていた。しかしながら水産加工残滓も貴重な蛋白資源であり、近年、資源の有効利用や環境保全の観点から重金属類を除去して水産加工残滓を有効利用することが必要となってきている。   A large amount of heavy metals may be contained in fishery processing residues such as scallops and squid, and such aquatic processing residues have not been used before and have been disposed of by incineration or landfill. It had been. However, seafood processing residue is also a valuable protein resource, and in recent years, it has become necessary to effectively use the seafood processing residue by removing heavy metals from the viewpoint of effective use of resources and environmental conservation.

水産加工残滓から重金属類を除去する方法として、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pH=3〜3.5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。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。   As a method for removing heavy metals from the seafood processing residue, Patent Document 1 discloses a weak pH of 3 to 3.5 using organic acids such as formic acid, lactic acid and acetic acid, and mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid. Produce acid, further decompose protein bound to heavy metal by the action of proteolytic enzyme, dissociate heavy metal from protein and elute heavy metal in acid treatment solution, separate heavy metal in eluted aqueous solution with chelating agent etc. A method is described. Patent Document 2 describes a method of eluting heavy metals by contacting an aqueous solution of phosphoric acid, an organic acid, hydrochloric acid, nitric acid, boric acid or sulfuric acid.

特開2001−137810号公報JP 2001-137810 A 特開平12−296389号公報JP-A-12-296389

水産加工残滓中の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pH=3〜3.5という低pHで処理することが必要であるが、低pHで処理すると水産加工残滓中の蛋白質が可溶化して溶出し、残滓回収率が低下する。また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発酵食品原料として利用することができなくなり、水産加工残滓の有効利用範囲が狭まるという問題がある。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した問題点は更に大きくなり、特許文献1に記載されているような方法は、水産加工残滓を安全に廃棄するための前処理方法か、水産加工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、発酵食品等の食品加工原料として利用するための処理方法としては適用し得なかった。また特許文献2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、残滓回収率が低下し、さらに酵素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った。   In the method of Patent Document 1 in which heavy metals in a fishery processing residue are eluted in an acid treatment solution, it is necessary to perform treatment at a low pH of 3 to 3.5 in order to increase the removal efficiency of heavy metals. When treated at a low pH, the protein in the fishery processing residue is solubilized and eluted, and the residue recovery rate decreases. In addition, since the enzyme activity also decreases in the protein that remains without elution, it cannot be used as a raw material for fermented foods even though it can be used as a fishery extract, and the effective use range of fishery processed residue is narrowed. is there. In particular, when the treatment is performed in combination with a low pH acid treatment solution and a proteolytic enzyme as in the method described in Patent Document 1, the above-described problem is further increased. The processing method for using as a food processing raw material such as fermented food, because it is limited to a pretreatment method for safely disposing of fishery processing residue or a processing method when using fishery processing residue as feed or fertilizer Could not be applied. Moreover, although the removal rate of cadmium is good when the acid concentration to be used is high in the method described in Patent Document 2, there is a possibility that the residue recovery rate is lowered and the enzyme activity may be lost. When it is low, there are disadvantages such as a low removal rate of cadmium.

本発明は上記従来の課題に鑑みなされたもので、効果的に水産加工残滓中の重金属類を除去して水産加工残滓の含有するタンパク等の成分を食品として有効利用することのできる水産加工残滓の再生処理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 can effectively remove the heavy metals in the fishery processing residue and effectively use the components such as proteins contained in the fishery processing residue as food. An object of the present invention is to provide a reproduction processing method.

即ち本発明は、
(1)水産加工残滓をリンゴ酸酸性処理液と20〜30℃で接触させ、残滓を酸性処理液で処理している時のpHが、pH=4.2〜5.0となるように調整して残滓中の重金属を酸性処理液中に溶出させる工程を複数回繰り返し、水産加工残滓中の重金属類を除去することを特徴とする水産加工残滓の再生処理方法、
(2)水産加工残滓中の重金属類を酸性処理液中に溶出させる工程を2〜5回繰り返し行う上記(1)記載の水産加工残滓の再生処理方法、
を要旨とする。
That is, the present invention
(1) The fishery processing residue is brought into contact with malic acid acidic treatment solution at 20 to 30 ° C., and the pH when the residue is treated with the acidic treatment solution is adjusted to be pH = 4.2 to 5.0 Then, the process of eluting heavy metal in the residue into the acid treatment liquid is repeated a plurality of times, and the heavy metal in the fishery process residue is removed.
(2) The method for reclaiming fishery processing residue according to (1) above, wherein the step of eluting heavy metals in the fishery processing residue into the acidic treatment liquid is repeated 2 to 5 times,
Is the gist.

本発明方法によって水産加工残滓を処理すると、水産加工残滓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ともに、重金属類を除去した後の水産加工残滓はタンパクを含有し、食品加工原料や飼料、肥料等の広範囲に利用することができ、従来利用価値の少なかった水産加工残滓を有効に利用することができる。   When the processed fishery residue is processed by the method of the present invention, the heavy metals in the processed fishery residue can be efficiently reduced to a predetermined concentration or less, and the processed fishery residue after removing the heavy metals contains protein, It can be used in a wide range of processed raw materials, feeds, fertilizers, etc., and fishery processing residue that has been less useful in the past can be used effectively.

本発明方法において水産加工残滓中の重金属類を溶出させる処理を、pH=4.2〜5.0で行うが、pH=4.2〜4.5で行うことが好ましい。水産加工残滓を処理液に添加すると処理液のpHは変化する場合がある。上記pHは、水産加工残滓を処理している時の酸性処理液のpHを意味するものであり、予め酸性処理液のpHを4.2〜5.0に調整することを意味するものではない。重金属除去後の水産加工残滓を食品として利用する場合、リンゴ酸を用いると風味が良好となるので好ましい。 The process eluting the heavy metals in the fish processing residue in the process of the present invention, pH = 4.2 ~5. Although it is carried out at 0 , it is preferably carried out at pH = 4.2 to 4.5. When the fishery processing residue is added to the treatment liquid, the pH of the treatment liquid may change. The above-mentioned pH means the pH of the acidic treatment liquid when processing the fishery processing residue, and does not mean adjusting the pH of the acidic treatment liquid to 4.2 to 5.0 in advance. . When utilizing fish processing residue after heavy metal removal as food, preferred because flavor is improved the use of apple acid.

水産加工残滓を酸性処理液と接触させるための具体的な方法としては、処理液中に浸漬静置して処理する方法、攪拌しながら処理する方法等が挙げられるが、攪拌することが好ましい。水産加工残滓を酸性処理液と接触させる時間は数分〜1日程度であるが、30分〜1時間が好ましく、酸性処理液による処理温度は酵素活性が失われない温度で行なうことが必要であり、20〜30℃で行う。また水産加工残滓の質量1に対して、0.5〜100倍量程度の処理液を用いるのが好ましいが、重金属除去処理工程を考慮すると、3〜20倍量がより好ましい。 Specific methods for bringing the seafood processing residue into contact with the acidic treatment liquid include a method of immersion and treatment in the treatment liquid, a method of treatment with stirring, and the like. The time for contacting the seafood processing residue with the acidic treatment solution is about several minutes to one day, but preferably 30 minutes to 1 hour, and the treatment temperature with the acidic treatment solution should be such that the enzyme activity is not lost. Oh is, it carried out in 2 0~30 ℃. Moreover, although it is preferable to use about 0.5-100 times amount processing liquid with respect to the mass 1 of a fishery processing residue, 3-20 times amount is more preferable when a heavy metal removal process process is considered.

本発明方法は、上記のようにして水産加工残滓を酸性処理液と接触させて処理した後、水産加工残滓と酸性処理液とを分離し、再び上記と同様にして酸性処理液による処理を繰り返す。本発明方法は、水産加工残滓中の重金属類が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、酸処理液のpH、水産加工残滓中の重金属類の量、水産加工残滓に対する酸処理液の使用量等によっても異なるが2〜5回が好ましい。処理後の水産加工残滓と酸性処理液とを分離する方法としては、遠心分離、デカンテーション、ろ過法など、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。水産加工残滓処理後の処理液は、通常の方法により重金属を除去後、食品加工原料、飼料、肥料として利用出来る。   In the method of the present invention, after processing the fishery processing residue in contact with the acidic treatment liquid as described above, the fishery processing residue and the acidic treatment liquid are separated, and the treatment with the acidic treatment liquid is repeated again in the same manner as described above. . The method of the present invention is preferably processed so that the heavy metals in the fishery processing residue are 1 ppm or less, and the number of repetitions of treatment is the pH of the acid treatment solution, the amount of heavy metals in the fishery processing residue, the fishery processing residue. Depending on the amount of acid treatment solution used, etc., 2 to 5 times is preferable. Any method may be used as a method for separating the processed marine product residue and the acidic treatment liquid as long as the method can separate the treatment residue from the treatment liquid, such as centrifugation, decantation, and filtration. Absent. The treatment liquid after the processing of fishery processing residue can be used as a raw material for food processing, feed and fertilizer after removing heavy metals by an ordinary method.

上記のようにして処理を行った水産加工残滓は、そのまま、または適当な方法で乾燥後に食品加工原料、肥料等として利用することができる。乾燥してから利用する場合、加熱乾燥すると、残滓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。本発明方法が処理対象とする水産加工残滓としては、従来より重金属含有量が多いために廃棄されていた、ホタテ貝内臓、イカ内臓、たこの内蔵、その他魚貝類の内蔵等が挙げられるが、油脂の含量が多いものは脱脂処理後、酸性処理液で処理することが望ましい。脱脂を行なう場合も、酵素活性が失われないように熱をかけずに脱脂することが好ましい。熱をかけずに脱脂するには有機溶剤抽出等の方法が挙げられる。   The fishery processing residue processed as described above can be used as a raw material for food processing, fertilizer or the like as it is or after drying by an appropriate method. When using after drying, since the enzyme activity in the residue may be lost when heated and dried, it is preferably dried by a method other than heating, such as vacuum drying or vacuum freeze drying. Examples of fishery processing residues to be treated by the method of the present invention include scallop viscera, squid viscera, built-in octopus, other built-in fish and shellfish, etc., which have been discarded because of the heavy metal content. It is desirable to treat the oil and fat content with an acidic treatment solution after the degreasing treatment. Also when degreasing, it is preferable to degrease without heating so that enzyme activity may not be lost. In order to degrease without applying heat, a method such as organic solvent extraction can be used.

実施例1、参考例1〜2、比較例1〜3
ヘキサンにより脱脂したイカの肝臓100g(固形分66g相当)当たりに対し、水400mLを添加し、表1に示す酸で同表に示すpHに調整し、室温下で1時間攪拌した後、遠心分離(3500rpm×10分)して残滓と上澄みとを分離した。尚、比較例3は水を添加したのみで、酸によるpH調整を行わなかった。次いで回収した残滓に水400mLを加え、室温下で1時間攪拌後、遠心分離(3500rpm×10分)する工程を3回繰り返した。各処理工程時の酸性処理液のpH、各処理工程後に回収した残滓重量及び残滓回収率、回収した残滓中のカドミウム濃度及びカドミウム除去率を表1に示す。実施例1〜3において、処理1回ではカドミウム濃度が充分に低減されたとは言えず、4回目の処理で大部分のカドミウムを除去することが可能であり、食品加工原料や肥料として安全性の高い水産加工残滓を得ることができた。処理後の残滓を凍結乾燥させた乾燥残滓15g(乾燥重量)に、水85g、食塩10gを添加攪拌し、50℃で14日間静置熟成させ、下層の“いしる”層を回収し、90℃で10分加熱し、おりを濾過して魚醤油様調味料(いしる)を得た。対照として、ヘキサンにより脱脂したイカの肝臓を凍結乾燥させた脱脂乾燥物15g(乾燥重量)に、水85g、食塩10gを添加攪拌し、50℃で14日間静置熟成させ、下層の“いしる”層を回収し、90℃で10分加熱し、おりを濾過して対照品である魚醤油様調味料(いしる)を得た。得られた魚醤油様調味料の官能試験結果及び魚醤油様調味料中の残存カドミウム濃度を測定した結果を、未処理の残滓を用いて同様にして調製した対照品の場合と共に表1に示した。
Example 1 , Reference Examples 1-2, Comparative Examples 1-3
To 100 g of squid liver defatted with hexane (corresponding to a solid content of 66 g), 400 mL of water was added, adjusted to the pH shown in the same table with the acid shown in Table 1, stirred for 1 hour at room temperature, and then centrifuged. (3500 rpm × 10 minutes) to separate the residue and the supernatant. In Comparative Example 3, only water was added, and pH adjustment with acid was not performed. Next, 400 mL of water was added to the collected residue, and the process of stirring at room temperature for 1 hour and then centrifugation (3500 rpm × 10 minutes) was repeated three times. Table 1 shows the pH of the acidic treatment liquid at each treatment step, the residue weight and residue collection rate after each treatment step, the cadmium concentration and cadmium removal rate in the collected residue. In Examples 1 to 3, it cannot be said that the cadmium concentration was sufficiently reduced by one treatment, and most of the cadmium can be removed by the fourth treatment, which is safe as a food processing raw material and fertilizer. High seafood processing residue was obtained. 85 g of water and 10 g of sodium chloride were added to 15 g (dry weight) of the dried residue obtained by freeze-drying the treated residue, and the mixture was stirred and allowed to stand at 50 ° C. for 14 days to recover the lower “Iru” layer. After heating at ° C. for 10 minutes, the cage was filtered to obtain a fish soy sauce-like seasoning. As a control, 85 g of water and 10 g of sodium chloride were added to 15 g (dry weight) of a defatted dry product obtained by freeze-drying squid liver defatted with hexane, and the mixture was allowed to stand at 50 ° C. for 14 days. The layer was collected, heated at 90 ° C. for 10 minutes, and the cage was filtered to obtain a control fish soy sauce-like seasoning (Ishiru). The sensory test results of the obtained fish soy sauce-like seasoning and the results of measuring the residual cadmium concentration in the fish soy sauce-like seasoning are shown in Table 1 together with the case of the control product prepared in the same manner using untreated residue. It was.

Figure 0004600974
Figure 0004600974

※:残滓回収率は、処理後に回収した残滓の乾燥重量の、処理前の残滓の乾燥重量に対する重量比を示す。
※:残滓中のCd濃度は残滓を乾燥して硝酸と過塩素酸で湿式分解した後、ICP発光分析法で測定した。また魚醤油様調味料中のCd濃度は、調味液を採取し、同様に硝酸と過塩素酸で湿式分解した後、ICP発光分析法で測定した。
※:官能試験は、10名のパネラーが対照品を比較として、旨み、香気性の有無を試験した。
旨みは
◎・・・特に旨い、旨いと評価した人が8人以上。
○・・・特に旨い、旨いと評価した人が5〜7人。
△・・・ほとんど旨味を感じなかった人が2〜4人。
×・・・旨みなしと評価した人が8人以上。
として評価した。
香気性は
◎・・・特によい香気と評価した人が8人以上。
○・・・特によい香気と評価した人が5〜7人。
△・・・ほとんど香気を感じなかった人が2〜4人。
×・・・香気なしと評価した人が8人以上。
として評価した。
*: The residue collection rate indicates the weight ratio of the dry weight of the residue collected after the treatment to the dry weight of the residue before the treatment.
*: Cd concentration in the residue was measured by ICP emission spectrometry after the residue was dried and wet-decomposed with nitric acid and perchloric acid. The Cd concentration in the fish soy sauce-like seasoning was measured by ICP emission spectrometry after collecting the seasoning liquid and similarly wet-decomposing it with nitric acid and perchloric acid.
*: In the sensory test, 10 panelists tested the presence of umami and fragrance by comparing the control product.
The taste is ◎ ... More than 8 people have evaluated it as particularly delicious.
○ ... 5-7 people who evaluated it as particularly delicious.
Δ: 2 to 4 people who hardly felt umami.
× ... 8 or more people evaluated as unacceptable.
As evaluated.
The fragrance is ◎ ・ ・ ・ 8 or more people evaluated as particularly good fragrance.
○ ... 5-7 people evaluated as particularly good fragrance.
Δ: 2 to 4 people who hardly felt fragrance.
X: Eight or more people evaluated that there was no fragrance.
As evaluated.

Claims (2)

水産加工残滓をリンゴ酸酸性処理液と20〜30℃で接触させ、残滓を酸性処理液で処理している時のpHが、pH=4.2〜5.0となるように調整して残滓中の重金属を酸性処理液中に溶出させる工程を複数回繰り返し、水産加工残滓中の重金属類を除去することを特徴とする水産加工残滓の再生処理方法。 PH at which fish processing residue is contacted with malic acid acidic treatment liquid and 20 to 30 ° C., and processing the residue with an acidic treatment liquid, residue and adjusted to pH = 4.2 to 5.0 A method for reclaiming aquatic processing residue, comprising removing a heavy metal in a marine processing residue by repeating a step of eluting heavy metal in the acidic processing solution a plurality of times. 水産加工残滓中の重金属類を酸性処理液中に溶出させる工程を2〜5回繰り返し行う請求項1記載の水産加工残滓の再生処理方法。 The method for reclaiming fishery processing residue according to claim 1, wherein the step of eluting heavy metals in the fishery processing residue into the acidic treatment liquid is repeated 2 to 5 times.
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JP4858828B2 (en) * 2006-07-03 2012-01-18 亮太 篠原 Methods for removing heavy metals from animal tissues or organs
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