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JP7580141B2 - Fish meal production method - Google Patents
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JP7580141B2 - Fish meal production method - Google Patents

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JP7580141B2
JP7580141B2 JP2023027161A JP2023027161A JP7580141B2 JP 7580141 B2 JP7580141 B2 JP 7580141B2 JP 2023027161 A JP2023027161 A JP 2023027161A JP 2023027161 A JP2023027161 A JP 2023027161A JP 7580141 B2 JP7580141 B2 JP 7580141B2
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大輔 中山
智 沖村
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株式会社リジェンワークス
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Description

本発明はサメ類を原料とした魚粉の製造方法に関する。 The present invention relates to a method for producing fish meal using sharks as a raw material.

魚粉すなわち魚類を原料とした粉末は、乾燥物としてあるいは更に粉砕された性状で各種食品の直接的あるいは間接的な材料として利用されている。また魚粉は、畜産業、漁業などにおける飼料としても有用な材料である。 Fish meal, that is, powder made from fish, is used as a direct or indirect ingredient in various foods, either dried or pulverized. Fish meal is also useful as feed in the livestock and fishing industries.

近年、魚粉の価格高騰などに対応するために、魚粉を高効率且つ低コストで製造する方法が求められている。 In recent years, in response to rising fish meal prices, there is a demand for methods to produce fish meal efficiently and at low cost.

例えば特許文献1には、魚粉の生産方法として、真空または減圧条件下にて、魚類の原料を撹拌および切断しながら乾燥する工程を用いてアジ、イワシなどの魚粉を生産する技術が開示されている。 For example, Patent Document 1 discloses a method for producing fish meal, which uses a process of stirring, cutting and drying raw fish material under vacuum or reduced pressure conditions to produce fish meal from horse mackerel, sardines and other fish.

特開2012-170411号公報JP 2012-170411 A

本発明者らは、この減圧条件下での魚類の原料の乾燥という技術に着目し、サメ類を原料とした魚粉の製造を試みたところ、サメ類のコラーゲンの多さに起因して、コラーゲン成分が製造装置内に固着等する結果、減圧条件下での魚類の原料の乾燥が達成されず、魚粉の製造が良好にできないという問題に直面した。 The inventors focused on this technology of drying fish raw materials under reduced pressure and attempted to produce fish meal using sharks as a raw material. However, due to the high collagen content of sharks, the collagen components stuck to the inside of the production equipment, and as a result, they were faced with the problem that drying of the fish raw materials under reduced pressure conditions could not be achieved and fish meal could not be produced satisfactorily.

サメ類は一部の部位を除き、経時等によるアンモニア臭の発生などを理由として、市場での活用は低調であるが、動物性タンパク質の供給源として有用な材料である。 With the exception of some parts, sharks are not widely used in the market due to factors such as the ammonia odor that develops over time, but they are still a useful source of animal protein.

発明者らは鋭意検討の結果、コラーゲン部分のタンパク質が分解されやすくなるように、タンパク質の構造を変化させるための所定の酵素処理を行ったうえで、タンパク質を分解する酵素処理を行い、これらの処理を経た部材を減圧条件下で乾燥させることで、良好な魚粉を製造できるとの新規な知見を得た。 After extensive research, the inventors have come to the novel discovery that good fish meal can be produced by first carrying out a specific enzymatic treatment to change the protein structure so that the protein in the collagen portion is more easily broken down, then carrying out an enzymatic treatment to break down the protein, and then drying the material that has undergone these treatments under reduced pressure conditions.

本発明は上記の新規な知見に基づいてなされたものであり、サメ類を原料とした魚粉を効率よく製造する方法を提供することを目的とする。 The present invention was made based on the above new findings, and aims to provide a method for efficiently producing fish meal using sharks as a raw material.

上記の目的を達成するための本発明は、
サメ類の肉を粉砕する粉砕工程と、
前記粉砕工程を経た部材に、コラーゲンが分解されやすくなるようにチオールプロテアーゼを添加しつつ加熱撹拌して、60℃以下で1~3時間、pH7~9で酵素反応させる予備酵素処理工程と、
前記予備酵素処理工程を経た部材にプロテアーゼを加えて撹拌し、60℃以下で1~3時間、ゲージ圧で-85kPa以下で酵素反応させる酵素処理工程と、
前記酵素処理工程を経た部材を更に加熱する酵素失活工程と、
前記酵素失活工程を経た部材を減圧下で乾燥させる乾燥工程と
を備えることを特徴とする魚粉の製造方法である。
In order to achieve the above object, the present invention provides:
a grinding step for grinding the shark meat;
a preliminary enzyme treatment step in which the material that has been subjected to the crushing step is heated and stirred while adding thiol protease so as to facilitate decomposition of collagen , and the enzymatic reaction is carried out at 60° C. or less for 1 to 3 hours at a pH of 7 to 9 ;
an enzyme treatment step of adding protease to the material that has been subjected to the preliminary enzyme treatment step, stirring the mixture, and carrying out an enzyme reaction at 60° C. or less for 1 to 3 hours at a gauge pressure of −85 kPa or less ;
an enzyme deactivation step of further heating the member that has been subjected to the enzyme treatment step;
This is a fish meal production method characterized by including a drying process in which the material that has undergone the enzyme deactivation process is dried under reduced pressure.

サメ類を原料とする魚粉の製造にあたって、減圧下で酵素反応を行うことでタンパク質の比較的低温での分解が可能となり、それが高品質な魚粉の高効率且つ低コストな製造につながる。その酵素反応に先んじてコラーゲンが分解されやすいタンパク質構造にしておくことによって、魚粉製造の効率をより向上させることができる。 When producing fish meal from sharks, enzyme reactions can be carried out under reduced pressure, which allows proteins to be broken down at relatively low temperatures, leading to the efficient and low-cost production of high-quality fish meal. By giving collagen a protein structure that is easily broken down prior to the enzyme reaction, the efficiency of fish meal production can be further improved.

チオールプロテアーゼを添加することで、酵素処理工程におけるコラーゲン分解の効率が向上する。 The addition of thiol protease improves the efficiency of collagen decomposition in the enzyme treatment process.

また、予備酵素処理工程においては、第1酵素に加えて緩衝剤を加えることが好ましい。 In addition, in the preliminary enzyme treatment step, it is preferable to add a buffer in addition to the first enzyme.

このことによって予備酵素処理工程が中性からアルカリ性の状態となり、第1酵素によるタンパク質の構造変化が促進される。 This results in a neutral to alkaline state during the preliminary enzyme treatment process, accelerating structural changes in proteins caused by the first enzyme.

本発明による魚粉の製造工程を示す図である。FIG. 1 is a diagram showing the process for producing fish meal according to the present invention.

本発明におけるサメ類とは、サメ目のネズミザメ上目あるいはツノザメ上目のいずれかに属する魚類であり、具体的には、例えばヨシキリザメのほか、ネコザメ、ホオジロザメ、シュモクザメなどが挙げられる。また、サメ類の肉とは、生のあるいは冷凍のサメ類のヒレ以外の部分をいう。 In the present invention, sharks refer to fishes belonging to either the superorder Lamniformes or the superorder Squamata of the order Scallops, and specific examples include the blue shark, the cat shark, the great white shark, and the hammerhead shark. Shark meat refers to raw or frozen parts of sharks other than the fins.

粉砕工程(図1/S11)は、サメ類の肉を粉砕する工程である。粉砕方法は必要に応じて公知の諸方法を採用すればよく、粉砕するサイズにも特に制限はないが、次工程を考慮して混合撹拌しやすいサイズまで粉砕すればよい。 The grinding process (Fig. 1/S11) is a process for grinding shark meat. Any known grinding method may be used as necessary, and there is no particular restriction on the size of the ground material, but it is sufficient to grind the material to a size that is easy to mix and stir, taking into account the next process.

予備酵素処理工程(図1/S13)では、粉砕工程(図1/S11)を経た部材に、コラーゲンが分解されやすくなるようにタンパク質の構造を変化させる第1酵素を添加しつつ加熱撹拌して酵素反応させる。加熱撹拌に際しては、必要に応じて加水を行っても構わない。 In the preliminary enzyme treatment step (S13 in Fig. 1), the material that has been through the crushing step (S11 in Fig. 1) is heated and stirred while adding a first enzyme that changes the protein structure so that collagen can be easily decomposed, to cause an enzymatic reaction. When heating and stirring, water may be added as necessary.

ここで第1酵素としては、コラーゲンが分解されやすくなるようにタンパク質の構造を変化させる種々の酵素が用いられてよいが、チオールプロテアーゼが好ましく、特にパパイン、フィシン、ブロメラインなどが好ましい。また、コラゲナーゼも第1酵素として採用可能である。第1酵素の添加量は、粉砕工程(図1/S11)を経た部材の重量に対して0.2~15wt%であることが好ましい。 As the first enzyme, various enzymes that change the protein structure so that collagen can be easily decomposed may be used, but thiol proteases are preferred, and papain, ficin, bromelain, and the like are particularly preferred. Collagenase can also be used as the first enzyme. The amount of the first enzyme added is preferably 0.2 to 15 wt % of the weight of the material that has been subjected to the crushing step (Fig. 1/S11).

また予備酵素処理工程(図1/S13)では、粉砕工程(図1/S11)を経た部材にpH調整剤としての緩衝剤を加えてもよい。緩衝剤としては公知の材料が採用可能であり、例えば、酢酸、クエン酸、酒石酸、フマル酸、乳酸ナトリウム、炭酸水素ナトリウムなどから選択すればよい。 In the preliminary enzyme treatment step (S13 in FIG. 1), a buffering agent may be added as a pH adjuster to the material that has been through the grinding step (S11 in FIG. 1). Known materials may be used as the buffering agent, and may be selected from, for example, acetic acid, citric acid, tartaric acid, fumaric acid, sodium lactate, sodium bicarbonate, etc.

予備酵素処理工程(図1/S13)は60℃以下で1~3時間、pHを7~9程度として行なうことが好ましい。 The preliminary enzyme treatment step (Fig. 1/S13) is preferably carried out at 60°C or less for 1 to 3 hours at a pH of about 7 to 9.

予備酵素処理工程(図1/S13)を経た部材は必要に応じて、更に加熱して第1酵素を失活させても構わない(予備酵素失活工程(図1/S15))。 If necessary, the material that has undergone the preliminary enzyme treatment step (Fig. 1/S13) may be further heated to inactivate the first enzyme (preliminary enzyme inactivation step (Fig. 1/S15)).

予備酵素失活工程(図1/S15)を行う場合は70~90℃、0.5~3分間程度行うことが好ましくその後自然放冷等の方法にて冷却される。 If a preliminary enzyme inactivation step (Fig. 1/S15) is performed, it is preferable to carry out the step at 70-90°C for about 0.5-3 minutes, after which the mixture is cooled naturally or by other methods.

予備酵素処理工程(図1/S13)および予備酵素失活工程(図1/S15)は、減圧乾燥器などの、減圧可能な処理機器内で行っても構わないが、予備酵素失活工程(図1/S15)後に部材の液体成分などを分離した方が以降の工程において好ましい場合は、減圧可能な処理機器以外の装置内にて処理した後、遠心分離法などの方法にて部材を固液分離し、固体分濃度を調整しても構わない(固液分離工程(図1/S16))。 The preliminary enzyme treatment step (Fig. 1/S13) and the preliminary enzyme inactivation step (Fig. 1/S15) may be carried out in a processing device capable of reducing pressure, such as a vacuum dryer. However, if it is preferable to separate the liquid components of the material after the preliminary enzyme inactivation step (Fig. 1/S15) in the subsequent steps, the material may be treated in a device other than a processing device capable of reducing pressure, and then the material may be subjected to solid-liquid separation by a method such as centrifugation to adjust the solid concentration (solid-liquid separation step (Fig. 1/S16)).

予備酵素処理工程(図1/S13)(および予備酵素失活工程(図1/S15))を経た部材は、必要に応じて加水されて減圧可能な処理機器に投入され、タンパク質を分解する第2酵素を加えて撹拌し、減圧下で酵素反応させる(酵素処理工程(図1/S17))。 The material that has undergone the preliminary enzyme treatment step (Fig. 1/S13) (and the preliminary enzyme deactivation step (Fig. 1/S15)) is added with water as necessary and placed in a processing device that can reduce pressure, where a second enzyme that breaks down proteins is added and stirred to cause an enzymatic reaction under reduced pressure (enzyme treatment step (Fig. 1/S17)).

第2酵素としては、魚類のタンパク質(すなわち、予備酵素処理工程にてコラーゲンが分解されやすい状態とした後のタンパク質)を分解できるものであればいずれの酵素でも構わないが、プロテアーゼ、特に酸性プロテアーゼ、中性プロテアーゼが好ましく、また、スミチームAP、スミチームFP(新日本化学工業株式会社)、プロテアックス、酸性プロテアーゼUF「アマノ」SD、プロテアーゼM「アマノ」SD(天野エンザイム株式会社)といった酵素などを用いてもよい。(「スミチーム」、「プロテアックス」は登録商標。)ここで、第2酵素として使用する酵素を適宜選択することによって、魚粉製品の栄養成分、臭い、味などに様々な特性を与えることができる。第2酵素の添加量は、予備酵素処理工程(図1/S13)を経て必要に応じて加水された部材の重量に対して0.05~5wt%であることが好ましい。 The second enzyme may be any enzyme capable of decomposing fish proteins (i.e., proteins after collagen has been rendered easily decomposable in the preliminary enzyme treatment process), but proteases, particularly acidic proteases and neutral proteases, are preferred. Enzymes such as Sumiteam AP, Sumiteam FP (Shin Nippon Chemical Industry Co., Ltd.), Proteax, Acidic Protease UF "Amano" SD, and Protease M "Amano" SD (Amano Enzyme Co., Ltd.) may also be used. ("Sumiteam" and "Proteax" are registered trademarks.) By appropriately selecting the enzyme used as the second enzyme, various characteristics can be imparted to the nutritional content, odor, taste, etc. of the fish meal product. The amount of the second enzyme added is preferably 0.05 to 5 wt % of the weight of the material that has been subjected to the preliminary enzyme treatment process (Fig. 1/S13) and water added as necessary.

酵素処理工程(図1/S17)は60℃以下で1~3時間、装置内の圧力をゲージ圧で-85kPa以下として行うことが好ましい。また、pHは特に調整する必要はなく、2~9程度として行なわれる。 The enzyme treatment step (Fig. 1/S17) is preferably carried out at 60°C or less for 1 to 3 hours with the pressure inside the apparatus at a gauge pressure of -85 kPa or less. There is no need to adjust the pH, and it is carried out at a value of around 2 to 9.

酵素処理工程(図1/S17)を経た部材は更に加熱して第2酵素を失活させる(酵素失活工程(図1/S19))。 The material that has undergone the enzyme treatment step (Fig. 1/S17) is further heated to inactivate the second enzyme (enzyme inactivation step (Fig. 1/S19)).

酵素失活工程(図1/S19)は60~80℃、3~15分間程度行うことが好ましくその後自然放冷等の方法にて冷却される。 The enzyme inactivation step (Fig. 1/S19) is preferably carried out at 60-80°C for about 3-15 minutes, after which the mixture is cooled naturally or by other methods.

酵素失活工程(図1/S19)を経た部材は減圧下で撹拌されながら乾燥される(乾燥工程(図1/S21))。乾燥時間は投入された部材の重量などに依存する。乾燥温度は、35~70℃、装置内の圧力をゲージ圧で-85kPa以下として乾燥を行うことが好ましく、乾燥温度は35~40℃であることがより好ましい。 The materials that have undergone the enzyme deactivation step (S19 in Fig. 1) are dried while being stirred under reduced pressure (drying step (S21 in Fig. 1)). The drying time depends on the weight of the materials that have been put in, etc. It is preferable to perform drying at a drying temperature of 35 to 70°C and with a gauge pressure inside the device of -85 kPa or less, and it is more preferable for the drying temperature to be 35 to 40°C.

以下、図面を参照して、本発明のサメ類を原料とした魚粉の製造方法の一実施形態について説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 Below, one embodiment of the method for producing fish meal using sharks as a raw material according to the present invention will be described with reference to the drawings, but the scope of the present invention is not limited to these examples.

(実施例)
解凍したヨシキリザメのフィレ肉100kgを粗切断してスーパーミキサーに投入し、100rpmで1分間、その後500rpmで1分間処理して粉砕した(図1/S11)。
(Example)
100 kg of thawed blue shark fillet was roughly cut and placed in a super mixer, where it was pulverized by processing at 100 rpm for 1 minute and then at 500 rpm for 1 minute (FIG. 1/S11).

粉砕したヨシキリザメのフィレ肉を開放の加熱容器に移し、同量の水を加え、チオールプロテアーゼ(2kg)及び緩衝剤(pH調整剤)として炭酸水素ナトリウムを加え、約50℃に調整して2時間加熱撹拌した(図1/S13)。その際のpHはおよそ8であった。 The crushed blue shark fillet was transferred to an open heating vessel, and the same amount of water was added, followed by thiol protease (2 kg) and sodium bicarbonate as a buffer (pH adjuster), and the mixture was adjusted to approximately 50°C and heated and stirred for 2 hours (Fig. 1/S13). The pH at that time was approximately 8.

その後、加熱容器を80℃で1分間保持してチオールプロテアーゼの失活を行い(図1/S15)、得られた流動体の部材を減圧乾燥機に投入した。 The heating vessel was then kept at 80°C for 1 minute to inactivate the thiol protease (Fig. 1/S15), and the resulting fluid component was placed in a vacuum dryer.

その後、第2酵素としての酸性プロテアーゼを200g加え、約55℃に調整して3時間加熱撹拌した(図1/S17)。その際の減圧乾燥機内の圧力はゲージ圧で-88~-98kPaであった。 200 g of acid protease was then added as the second enzyme, and the mixture was heated and stirred at approximately 55°C for 3 hours (Fig. 1/S17). The pressure inside the vacuum dryer at that time was -88 to -98 kPa in gauge pressure.

3時間の加熱撹拌後に、減圧乾燥機内を70℃に調整して10分間加熱し(図1/S19)、その後冷却させた。その間も減圧乾燥機内は同様の減圧が維持されたままで部材の撹拌を続け、5時間後に14.3kgのサメ類の魚粉を得た(図1/S21)。 After 3 hours of heating and stirring, the temperature inside the vacuum dryer was adjusted to 70°C and the material was heated for 10 minutes (Fig. 1/S19), after which it was cooled. During this time, the vacuum inside the vacuum dryer was maintained at the same reduced pressure and the material continued to be stirred, and after 5 hours, 14.3 kg of shark fish meal was obtained (Fig. 1/S21).

(比較例)
実施例において、予備酵素処理工程(図1/S13)および予備酵素失活工程(図1/S15)を省いた以外は同様にサメ類の肉の処理を行ったところ、乾燥工程(図1/S21)においてコラーゲン成分が減圧乾燥機内壁に固着し、魚粉を得ることはできなかった。
(Comparative Example)
In the examples, shark meat was processed in the same manner except for omitting the preliminary enzyme treatment step (Figure 1/S13) and the preliminary enzyme inactivation step (Figure 1/S15). However, collagen components adhered to the inner walls of the vacuum dryer during the drying step (Figure 1/S21), and fish meal could not be obtained.

このように、本発明によれば、減圧条件下でのサメ類の原料の乾燥に先んじて所定の酵素処理を行うことでコラーゲン部分のタンパク質の構造を変化させ、その後のタンパク質を分解する酵素処理においてコラーゲンを容易に分解できるようにしたため、それらの処理を経た部材を減圧条件下で乾燥させることによる良好な魚粉の製造が可能となった。 Thus, according to the present invention, the protein structure of the collagen portion is changed by carrying out a specific enzyme treatment prior to drying the raw shark material under reduced pressure conditions, making it easier to decompose the collagen in the subsequent enzyme treatment that breaks down the protein. This makes it possible to produce good fish meal by drying the material that has undergone these treatments under reduced pressure conditions.

なお、上記の実施例では、酵素失活工程(図1/S19)を経た部材は減圧下で撹拌されながら乾燥する方法(乾燥工程(図1/S21))のみを用いたが、必要な魚粉の形態、性状によっては、更に熱風乾燥などの方法で追乾燥工程を行っても構わない。 In the above example, the material that had undergone the enzyme deactivation process (Fig. 1/S19) was dried while being stirred under reduced pressure (drying process (Fig. 1/S21)). However, depending on the required form and properties of the fish meal, a further drying process may be carried out using a method such as hot air drying.

また、上記の実施例では、予備酵素失活工程(図1/S15)を行っているが、当該工程は必要に応じて行えばよい。すなわち例えば、第1酵素が、酵素処理工程における第2酵素の酵素反応の妨げとならないことがあらかじめ分かっている場合においては、予備酵素失活工程(図1/S15)は省略されてよい。この場合において第1酵素は、酵素失活工程(図1/S19)において、第2酵素とともに失活される。 In addition, in the above examples, a preliminary enzyme inactivation step (Fig. 1/S15) is performed, but this step may be performed as necessary. That is, for example, if it is known in advance that the first enzyme does not interfere with the enzymatic reaction of the second enzyme in the enzyme treatment step, the preliminary enzyme inactivation step (Fig. 1/S15) may be omitted. In this case, the first enzyme is inactivated together with the second enzyme in the enzyme inactivation step (Fig. 1/S19).

さらに、上記の実施例では、フィレ肉をサメ類の肉として用いた場合について説明したが、内臓、尾、頭、皮又は骨等を含むいわゆる「アラ」をサメ類の肉として用いてもよい。 In addition, in the above examples, fillet meat was used as shark meat, but so-called "fish tails" including organs, tails, heads, skin, and bones may also be used as shark meat.

また、得られた魚粉について更に、用途に合わせて粉砕・分級加工などを行ってもよい。 The resulting fish meal may then be further processed, such as crushed and classified, depending on the intended use.

Claims (2)

サメ類の肉を粉砕する粉砕工程と、
前記粉砕工程を経た部材に、コラーゲンが分解されやすくなるようにチオールプロテアーゼを添加しつつ加熱撹拌して、60℃以下で1~3時間、pH7~9で酵素反応させる予備酵素処理工程と、
前記予備酵素処理工程を経た部材にプロテアーゼを加えて撹拌し、60℃以下で1~3時間、ゲージ圧で-85kPa以下で酵素反応させる酵素処理工程と、
前記酵素処理工程を経た部材を更に加熱する酵素失活工程と、
前記酵素失活工程を経た部材を減圧下で乾燥させる乾燥工程と
を備えることを特徴とする魚粉の製造方法。
a grinding step for grinding the shark meat;
a preliminary enzyme treatment step in which the material that has been subjected to the crushing step is heated and stirred while adding thiol protease so as to facilitate decomposition of collagen , and the enzymatic reaction is carried out at 60° C. or less for 1 to 3 hours at a pH of 7 to 9 ;
an enzyme treatment step of adding protease to the material that has been subjected to the preliminary enzyme treatment step, stirring the mixture, and carrying out an enzyme reaction at 60° C. or less for 1 to 3 hours at a gauge pressure of −85 kPa or less ;
an enzyme deactivation step of further heating the member that has been subjected to the enzyme treatment step;
A method for producing fish meal, comprising a drying step of drying the material that has undergone the enzyme deactivation step under reduced pressure.
前記予備酵素処理工程において、前記第1酵素に加えて緩衝剤を加える
ことを特徴とする請求項に記載の魚粉の製造方法。
The method for producing fish meal according to claim 1 , characterized in that in the preliminary enzyme treatment step, a buffer is added in addition to the first enzyme.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006141409A (en) 2006-02-17 2006-06-08 Tottori Kanzume Kk Process for producing enzyme-treated fish meal and feed containing enzyme-treated fish meal
JP2012170411A (en) 2011-02-22 2012-09-10 Biolight Inc Method for producing meal of fish
CN103504360A (en) 2013-09-12 2014-01-15 韩山师范学院 Manufacture method of instant fish skin food rich in micromolecular collagen
CN105707905A (en) 2016-02-23 2016-06-29 浙江海洋学院 Application of high-F-value oligopeptides of shark meat
CN111567758A (en) 2020-05-26 2020-08-25 付鹏磊 Shark cartilage powder substitute and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006141409A (en) 2006-02-17 2006-06-08 Tottori Kanzume Kk Process for producing enzyme-treated fish meal and feed containing enzyme-treated fish meal
JP2012170411A (en) 2011-02-22 2012-09-10 Biolight Inc Method for producing meal of fish
CN103504360A (en) 2013-09-12 2014-01-15 韩山师范学院 Manufacture method of instant fish skin food rich in micromolecular collagen
CN105707905A (en) 2016-02-23 2016-06-29 浙江海洋学院 Application of high-F-value oligopeptides of shark meat
CN111567758A (en) 2020-05-26 2020-08-25 付鹏磊 Shark cartilage powder substitute and preparation method thereof

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