TWI688345B - Manufacturing method of processed fish scales - Google Patents

Abstract

The present invention provides a method for producing a fish scale processed product that can efficiently reduce the fish scale to a low molecular weight to obtain a fish scale processed product.

The method for manufacturing a fish scale processed product of the present invention is characterized by including the steps of blasting the fish scale under pressure steaming treatment under saturated steam, then releasing to atmospheric pressure. By changing the conditions of the pressure cooking treatment, different processed fish scales can be obtained. In this case, the processing temperature of the pressure cooking process may be fixed to change the processing time, or the processing time may be fixed to change the processing temperature.

Description

Manufacturing method of processed fish scales

The invention relates to a method for manufacturing processed fish scales composed of gelatin, glycoprotein, polysaccharide and collagen peptide.

Collagen is the main protein that constitutes the body of animals, and is composed of three polypeptide chains (α chains) with a molecular weight of about 100,000. Gelatin is used to modify collagen by heating, and collagen peptide is used to further reduce the molecular weight of gelatin. These collagen, gelatin and collagen peptides are increasingly used in the medical field, cosmetics, food and health food fields.

The raw materials for industrial production of gelatin and collagen peptides are mainly animal-derived materials such as cow bone, cowhide, pig skin, and chicken bone. However, due to the occurrence of BSE (mad cow disease) problems, etc., in recent years, attention has been focused on raw materials derived from fish.

Patent Document 1 discloses a method for producing gelatin using fish scales as a raw material, and Patent Document 2 discloses a method for producing collagen peptides using fish scales as a raw material.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-59568

[Patent Document 2] Japanese Patent Laid-Open No. 2006-89

Patent Document 1 discloses a method for manufacturing gelatin. After wet-pulverizing fish scale raw materials, it is not subjected to decalcification treatment, but is immersed in water at a temperature of less than 100°C to extract the gelatin in the fish scale. However, this method requires a long time.

Patent Document 2 discloses a method for producing collagen peptides after decalcification treatment and enzyme decomposition. However, this method also has a problem that the time required for enzyme decomposition must be several hours to tens of hours.

Therefore, the present invention has been completed to solve the above-mentioned problems, and an object thereof is to provide a method for manufacturing a fish scale processed product, which can efficiently reduce the fish scale to obtain a fish scale processed product in a short time.

In order to achieve the above object, the present invention has the following configuration.

That is, the method for manufacturing a fish scale processed product of the present invention is characterized by including the steps of decomposing the fish scales under saturated steam under pressure and then releasing to atmospheric pressure to perform explosion (hereinafter also referred to as cooking explosion).

The fish scales may be decalcified in advance, or the fish scales (raw scales) that have not been decalcified may be directly subjected to cooking and crushing treatment.

By changing the conditions of the pressure cooking treatment, different processed fish scales can be obtained. In this case, it is possible to change the processing time by setting the processing temperature of the pressure cooking process to be fixed or changing the processing temperature by setting the processing time to be fixed.

By relaxing the conditions of the pressure cooking treatment (shortening the treatment time when the treatment temperature is fixed or reducing the treatment temperature when the treatment time is fixed), gelatin can be obtained.

Glycoproteins can be obtained by setting the conditions of the pressure cooking process to a moderate level (the processing time is set to a moderate level when the processing temperature is fixed, or the processing temperature is set to a moderate level when the processing time is fixed) And polysaccharides.

In addition, by strictly setting the conditions of the pressure cooking process (the treatment temperature is increased when the treatment temperature is fixed or the treatment temperature is increased when the treatment time is fixed), the fish scale can be reduced in molecular weight to obtain a collagen peptide.

According to the present invention, by processing the fish scales by cooking and crushing, a low-molecular-weight processed fish scale product of gelatin, glycoprotein, polysaccharide or collagen peptide can be obtained in a short time.

10‧‧‧Steaming and bursting treatment device

12‧‧‧Boiler

13‧‧‧ water purifier

14‧‧‧Pump

15‧‧‧Reactor

16‧‧‧Feed hopper

17, 18, 19‧‧‧ valve

20‧‧‧ tube

21‧‧‧Receiving slot

22‧‧‧Muffler

23‧‧‧ Take the exit

[Figure 1] An explanatory diagram showing the outline of a cooking and crushing treatment device.

[Figure 2] is a flow chart for the production of objects (gelatin, glycoproteins, polysaccharides, collagen peptides) from fish scales.

[Forms for carrying out the invention]

Hereinafter, embodiments of the present invention will be described in detail.

The form of the present embodiment is as described above, and includes the steps of blasting the fish scales under saturated steam under pressure and then releasing them to atmospheric pressure for blasting . In this way, the fish scale is reduced in molecular weight by cooking and crushing the fish scale, so that the processed fish scale can be obtained in a short time.

Steaming and bursting treatment refers to the process of putting fish scales in a pressure vessel, cooking with high-pressure and high-temperature steam, and after pressurizing and heating, the pressure is instantly released to atmospheric pressure. As a result, the water vapor that has penetrated into the fish scale tissue under high temperature and high pressure will expand rapidly when released to atmospheric pressure, causing the fish scale to shatter. The characteristic of this cooking and blasting treatment is that it can achieve finer than mechanical crushing. The raw fish scales will become watery during the pressure cooking process. Depending on the conditions of this pressure cooking process, the fish scale becomes a gel, viscous liquid, or liquid.

FIG. 1 is an explanatory diagram showing the outline of the cooking and crushing processing device 10. The cooking and crushing treatment apparatus 10 may be well-known, so the following is a brief description.

12 is a boiler, and water (tap water) from which impurities such as sodium, potassium, calcium, and magnesium are removed by the water purifier 13 is fed by a pump 14 to be vaporized into high-temperature and high-pressure steam. 15 is a reactor, and fish scales as raw materials are fed into the feed hopper 16.

At this time, the valve 17 is opened, and the valves 18 and 19 are closed.

When a predetermined amount of fish scales is put into the reactor 15, the valve 17 is closed and the valve 18 is opened, high-temperature and high-pressure steam is introduced into the reactor 15, and pressure cooking is performed within a predetermined time.

After the pressure cooking process is performed within a predetermined time, the valve 18 is closed and the valve 19 is opened, and the fish scale is rapidly discharged into the receiving tank 21 through the tube 20. The fish scale is suddenly placed under the atmosphere in the receiving tank 21 and explodes. In addition, 22 is a silencer. The scales after cooking and crushing are taken out from the outlet 23.

The fish scale is preferably one that has been previously subjected to decalcification treatment (treatment for chemically removing calcium components and the like contained in the fish scale), but it is also possible to use fish scale (raw scale) that has not been subjected to decalcification treatment.

If the treatment temperature of the pressure cooking treatment is too high, the discoloration due to scorching will increase. Conversely, if the treatment temperature is too low, the decomposition of fish scales becomes insufficient. When experimenting with fish scales that have been decalcified in advance and changing the treatment temperature, the best results can be obtained when the temperature of the saturated steam is set at 200°C (pressure about 1.5 MPa). In addition, when experiments were performed using fish scales (raw scales) that were not subjected to decalcification treatment as the raw materials and changing the treatment temperature, when the temperature of the saturated steam was set at 190°C (pressure is about 1.3 MPa), the best results were obtained. In the course of this experiment, it was found that different target objects (gelatin, glycoprotein, polysaccharide, collagen peptide) can be obtained from the same material (fish scale) as long as the processing time of the pressure cooking treatment is changed.

Furthermore, it was found that the same result can be obtained even if the processing time of the pressure cooking process is fixed and the temperature of the saturated steam is changed.

Specifically, when the processing time of the pressure cooking treatment is set to be fixed, it is known to shorten the processing time when extracting gelatin, as long as the processing time is moderate when extracting glycoproteins and polysaccharides, and to extract collagen In the case of protein peptides, it is only necessary to extend the processing time.

In addition, when the processing time of the pressure cooking treatment is set to be fixed, it is known that as long as the processing temperature is lowered when extracting gelatin, as long as the processing temperature is set to a moderate level when extracting glycoproteins and polysaccharides, when extracting collagen peptide Just increase the processing temperature.

As mentioned above, by strictly setting the pressure cooking process The conditions can make the fish scales break down to lower molecules, and liquid collagen peptides can be obtained. By subjecting this liquid substance to freeze-drying, for example, a solid collagen peptide can be obtained.

As described above, by gently setting the conditions of the pressure cooking process, the degree of decomposition of the fish scale is reduced, and a gel-like substance can be obtained. Liquid gelatin can be obtained by adding water to this gel and heating to make a liquid, and removing solid components from the liquid. By subjecting this liquid gelatin to, for example, freeze drying, it can be made into solid gelatin. In addition, when raw scales that have not been subjected to decalcification treatment are used, by performing pressure cooking treatment and blasting treatment, a precipitate and a liquid substance can be obtained. By removing solid components from this liquid, liquid gelatin can be obtained. By subjecting this liquid gelatin to, for example, freeze drying, it can be made into solid gelatin.

As described above, by setting the conditions of the pressure cooking treatment to moderate conditions, a highly viscous liquid substance can be obtained. Alcohol is added to this viscous liquid to generate a precipitate, and after taking out this precipitate, for example, freeze-drying can obtain a solid glycoprotein.

Different from person to person, the composition of the protein will be the cause of allergies, so it is more desirable to separate the protein from the glycoprotein.

Therefore, water is added to the above-mentioned precipitate to make a solution, and an organic solvent or calcium chloride is added to the resulting solution and mixed, and the mixed solution is centrifuged to separate into at least two layers of a polysaccharide solution layer and a protein layer. Take out part of this polysaccharide solution layer to obtain polysaccharide solution. The polysaccharide solution thus taken out can be freeze-dried, for example, to obtain a solid polysaccharide.

[Example]

The following shows an example of extracting gelatin, glycoproteins, polysaccharides and collagen peptides using fish scales of barramundi (scientific name Lates calcarifer ) as fish scales.

Barramundi is a large carnivorous fish distributed in the tropical region of the Indian Pacific. The adult fish has a total length of 2m and is cultivated in Southeast Asia for food purposes.

[Example 1]

The following is an example in which the temperature of the pressure cooking treatment is fixed at 200°C and the treatment time is changed. In addition, in Examples 1 to 3, the scales of barramundi were washed and decalcified and dried.

<gelatin>

The pressure cooking process time can be obtained within the range of 30 seconds to 1 minute to obtain gelatin.

For example, the sample obtained by performing the pressure cooking treatment for 30 seconds is gel-like immediately after the treatment. A 10-fold amount of distilled water was added to this sample, and heated at 60°C for 10 minutes, and then the liquid component was taken out by a centrifuge. When this liquid component is cooled to 4°C, it becomes a gel, and when returned to normal temperature, it becomes a liquid.

After the solid sample obtained by freeze-drying the above-mentioned liquid component was subjected to the pretreatment as described later, when the component was analyzed with an amino acid automatic analyzer (H-8900BH manufactured by Hitachi High-Tech Co., Ltd.), it was observed that the content was unique to collagen. Hydroxyproline acid of the amino acid. Furthermore, when the ratio of amino acids per 1000 residues was confirmed, glycine was about 1/3 of the whole, and the sum of alanine, hydroxyproline, and proline was about 1/3 of the whole , Showing the ratio specific to collagen. From these facts, it is determined To gelatin.

As gelatin, the liquid state can be maintained, but from the viewpoint of operability, it is preferably made in a solid state.

In addition, the pretreatment of the above-mentioned automatic analysis of amino acids is carried out as follows.

Add 20% hydrochloric acid to the sample for pretreatment and place it in an electric furnace at 110 ℃ for 24 hours. By this, the protein is decomposed into amino acids. This acid-decomposed sample was placed in an evaporator and dried (at this time, hydrochloric acid was removed). Next, 0.02N hydrochloric acid was added to make a 50 mL solution, followed by filtration with a 0.2 μm filter, and the above-mentioned amino acid analysis was performed using a solution obtained by removing impurities. The pretreatment in the automatic analysis of amino acids in the following examples is also performed in the same manner as described above.

Table 1 presents the gelatin yield due to the time of pressure cooking. When the treatment time is 15 seconds, the decomposition of fish scales is insufficient, and the yield of gelatin is also poor. Conversely, if the treatment time is longer than 1 minute, it is presumed that the mixing ratio of glycoproteins increases.

The decalcified fish scales are subjected to cooking and crushing treatment, and distilled water is added to the treatment to extract gelatin.

[Example 2]

<glycoprotein and polysaccharide>

Glycoproteins and polysaccharides can be obtained when the processing time of pressure cooking is in the range of 2 minutes to 15 minutes.

For example, a sample obtained by pressure cooking and bursting for 5 minutes is a viscous liquid at the end of the treatment. It does not gel even after cooling to 4°C, so a precipitate is obtained after adding ethanol. After performing the above pretreatment on this sample, when analyzing the components with an amino acid automatic analyzer (L-8900BH manufactured by Hitachi High-Tech Co., Ltd.), hydroxyproline containing amino acids unique to collagen was observed . Furthermore, when the ratio of amino acids per 1000 residues is confirmed, glycine is about 1/3 of the whole, and the sum of alanine, hydroxyproline, and proline is about 1/3 of the whole , Showing the ratio specific to collagen.

Ethanol is added to the high-viscosity liquid after cooking and crushing, and a precipitate is obtained by a centrifugal device. Distilled water was added to the resulting precipitate to make an aqueous solution. An organic solvent (a mixed solvent of chloroform 4:butanol 1) is added to this aqueous solution and mixed. Use this to separate proteins. Separate the mixture into polysaccharide solution/protein/organic by centrifugal device Three layers of solvent. The portion of the polysaccharide solution was taken out and freeze-dried to become a solid.

In addition, you can also use calcium chloride instead of organic solvents, and add about 5% of the weight of the aqueous solution to isolate the protein. At this time, if the mixture is separated by a centrifugal device, it is separated into two layers of polysaccharide solution/protein. It is sufficient to take out part of this polysaccharide solution and freeze-dry it into a solid state.

After pretreatment of this solid sample, the molecular weight distribution was investigated by size exclusion chromatography. The molecular weight (number average molecular weight) of this sample is in the range of hundreds to tens of thousands. From these facts, polysaccharides can be judged.

As the polysaccharide, the liquid state can be maintained, but from the viewpoint of operability, it is preferably made into a solid state.

Furthermore, in the above step, the protein before protein separation is a glycoprotein. Ethanol is added to the highly viscous liquid after cooking and blasting, and the resulting precipitate is taken out by a centrifugal device and freeze-dried, whereby a solid glycoprotein can be obtained.

Table 2 presents the molecular weight distribution of polysaccharides.

Table 3 shows the yield of glycoproteins caused by the pressure cooking time.

The decalcified fish scales are subjected to cooking and crushing treatment, ethanol is added to the treatment and glycoprotein is extracted.

[Example 3]

<Collagen peptide>

Collagen peptides can be obtained when the treatment time of pressure cooking is in the range of 20 minutes to 30 minutes.

For example, a sample obtained by pressure cooking for 30 minutes is liquid at the end of the treatment. It does not gel even after cooling to 4°C. Moreover, even if ethanol is added, a precipitate cannot be obtained.

After this sample was subjected to the above-mentioned pretreatment, when the components were analyzed with an amino acid automatic analyzer (L-8900BH manufactured by Hitachi High-Tech Co., Ltd.), hydroxyproline containing amino acids unique to collagen was observed. Furthermore, when the ratio of amino acids per 1000 residues was confirmed, glycine was about 1/3 of the whole, and the sum of alanine, hydroxyproline, and proline was about 1/of the whole 3. The ratio specific to collagen is shown.

Furthermore, when the molecular weight distribution of this sample is investigated by size exclusion chromatography, the molecular weight is in the range of hundreds to thousands (low molecular weight). From these facts, collagen peptides can be judged.

By directly drying the liquid after cooking and crushing, no Using chemical substances or enzymes such as hydrochloric acid or sodium hydroxide, a solid collagen peptide can be obtained.

In addition, as the collagen peptide, the liquid state can be maintained, but from the viewpoint of operability, it is preferably dried and made into a solid state.

Table 4 presents the molecular weight distribution of collagen peptides.

Table 5 shows the yield of collagen peptides caused by the pressure cooking time. When the treatment time is less than 20 minutes, it is presumed that the mixing ratio of glycoprotein increases. Furthermore, it is estimated that when the processing time exceeds 30 minutes, the coloration due to scorching will become darker.

The decalcified fish scales are digested and blasted to extract collagen peptides from the processed products.

Figure 2 shows the process of producing the target (gelatin, glycoprotein, polysaccharide, collagen peptide) from the decalcified fish scales. In each step, the steps up to the cooking and crushing process are the same, but depending on the conditions of the pressure cooking process, the obtained object will change. The steps after cooking and crushing treatment are as described above, so the description is omitted.

In addition, in the refining step, depending on the use of the final product, The purity is increased to the required level. Specifically, in the refining step, the following treatments are performed as necessary: use of hydrogen peroxide for the purpose of decolorization; or use of activated carbon for the purpose of decolorization and deodorization; or use of ion exchange resins for the purpose of removing impurities Wait. The target object is processed into a solid state in consideration of operability such as storage or transportation. However, if necessary, as described above, the product may be prepared in a state (liquid) before being solid. In the examples, the target was dried by freeze drying, but other drying methods (hot air drying, spray drying, etc.) may also be used.

Next, in Examples 4 to 6, the scales of barramundi were used only after washing. The water content of the raw scale is about 49%, so in calculating the yield, the equivalent weight when the raw scale is dried is taken as the basis. When raw scales are used as raw materials, the processed product after pressure cooking contains calcium phosphate, etc., which is the main component of fish scales. Therefore, compared with the case where dried fish scales that have been decalcified in advance are used as raw materials, the yield becomes worse. . In addition, the steps after the blasting treatment are slightly different from the treatment when using decalcified fish scales, but they are almost the same.

In the following, an example in which the temperature of the pressure cooking treatment is fixed at 190°C and the treatment time is changed is mainly presented.

[Example 4]

<gelatin>

The processing time of the pressure cooking treatment is in the range of 30 seconds to 2 minutes to obtain gelatin.

For example, the sample obtained by performing the pressure cooking process for 1 minute is liquid at the end of the process. The sample was heated at 60°C for 10 minutes, and then the liquid component was taken out by a centrifuge. When this liquid component is cooled to 4℃ It is gel-like and becomes liquid when it returns to normal temperature.

After the solid sample obtained by freeze-drying the above-mentioned liquid component was subjected to the pre-treatment as described later, when the component was analyzed with an amino acid automatic analyzer (L-8900BH manufactured by Hitachi High-Tech Co., Ltd.), it was observed that the content was collagen. Hydroxyproline, a unique amino acid. Furthermore, when the ratio of amino acids per 1000 residues was confirmed, glycine was about 1/3 of the whole, and the sum of alanine, hydroxyproline, and proline was about 1/of the whole 3. The ratio specific to collagen is shown. Judging from these facts, gelatin can be obtained.

As gelatin, the liquid state can be maintained, but from the viewpoint of operability, it is better to be a solid state.

In addition, the treatment before the automatic analysis of the amino acid was carried out as in Example 1 as follows.

Add 20% hydrochloric acid to the sample for pretreatment, put it in an electric furnace at 110 ℃, and leave it for 24 hours. By this, the protein is broken down into amino acids. The sample decomposed by this acid is placed in an evaporator and dried (at this time, hydrochloric acid is removed). Next, 0.02N hydrochloric acid was added to make a 50 mL solution, followed by filtration with a 0.2 μm filter, and the above-mentioned amino acid analysis was performed using the solution obtained by removing impurities. The pre-treatment in the automatic analysis of amino acids in the following examples is also carried out by the same treatment as described above.

Table 6 shows the molecular weight distribution of the obtained gelatin.

The yield (fixing the processing temperature and changing the processing time) is shown in Table 7.

Table 8 shows the yield when the treatment temperature was changed for a fixed treatment time.

[Example 5]

<polysaccharide>

The processing time of the pressure cooking treatment is in the range of 5 minutes to 10 minutes, and glycoproteins and polysaccharides can be obtained.

For example, the sample obtained by pressure cooking and bursting for 5 minutes is a viscous liquid at the end of the treatment. It does not gel even when cooled to 4°C, so a precipitate can be obtained when adding ethanol. After performing the above pretreatment on this sample, when analyzing the components with an amino acid automatic analyzer (L-8900BH manufactured by Hitachi High-Tech Co., Ltd.), observe To hydroxyproline containing amino acids unique to collagen. Furthermore, when the ratio of amino acids per 1000 residues was confirmed, glycine was about 1/3 of the whole, and the sum of alanine, hydroxyproline, and proline was about 1/of the whole 3. The ratio specific to collagen is shown.

The viscous liquid substance after the above cooking and crushing treatment is removed by a centrifugal device, and the liquid part is taken out. Ethanol was added to this liquid, and a precipitate was obtained by a centrifugal device. Distilled water was added to the resulting precipitate to make an aqueous solution. To this aqueous solution was added calcium chloride in an amount equivalent to 5% of the weight of the aqueous solution, and heated at 80°C for 1 hour. This separates the protein. This mixture was separated into two layers of polysaccharide solution/protein by a centrifugal device. This polysaccharide solution portion was taken out and freeze-dried to become a solid.

The yield (fixing the processing temperature and changing the processing time) is shown in Table 9.

Table 10 shows the yield when the treatment temperature and treatment time were changed.

[Example 6]

<Collagen peptide>

Collagen peptides can be obtained when the pressure cooking time is in the range of 20 minutes to 40 minutes.

For example, the sample obtained by pressure cooker treatment for 20 minutes It is liquid at the end. Even if this is cooled to 4°C, it does not gel, and even if ethanol is added, a precipitate cannot be obtained.

After this sample was subjected to the above-mentioned pretreatment, when the components were analyzed with an amino acid automatic analyzer (L-8900BH manufactured by Hitachi High-Tech Co., Ltd.), hydroxyproline containing amino acids unique to collagen was observed. Furthermore, when the ratio of amino acids per 1000 residues was confirmed, glycine was about 1/3 of the whole, and the sum of alanine, hydroxyproline, and proline was about 1/of the whole 3. The ratio specific to collagen is shown.

In addition, when the molecular weight distribution of this sample was investigated by size exclusion chromatography, the molecular weight was in the range of hundreds to thousands (low molecular weight). From these facts, collagen peptides can be judged.

The liquid substance after cooking and crushing treatment is used to remove the sediment by a centrifugal device, and the liquid part is taken out. By drying this liquid portion, a solid collagen peptide can be obtained.

In addition, as the collagen peptide, the liquid state can be maintained, but from the viewpoint of operability, it is preferably dried to be in a solid state.

The molecular weight distribution of the resulting collagen peptide is shown in Table 11.

The yield (fixing the processing temperature and changing the processing time) is shown in Table 12.

Table 13 shows the yield when the treatment temperature was changed for a fixed treatment time.

In the above embodiments, although the scales of barramundi are used as raw materials, various scales such as sea fish and sea bream may be used as raw materials.

Claims (4)

A method for manufacturing a fish scale processed product, the fish scale processed product is a glycoprotein, characterized in that the manufacturing method comprises: a pressure cooking process at a temperature of 190°C to 200°C, a pressure of 1.3 MPa to 1.5 MPa, and a treatment time of 2 In the range of 15 minutes to 15 minutes, the fish scales are subjected to pressure cooking, and then released to atmospheric pressure for the step of bursting; adding alcohol to the viscous liquid obtained by the bursting to form a precipitate Step; and the step of removing the precipitate. The method for manufacturing a processed fish scale according to claim 1 includes a drying step of drying the precipitate to obtain a solid glycoprotein. For the method of manufacturing processed fish scales according to claim 1 or 2, it uses pre-calcified fish scales. For the method of manufacturing processed fish scales according to claim 1 or 2, raw scales without decalcification treatment are used.

Images