RU2808050C1 - Method for obtaining protein hydrolyzate from atlantic cod processing waste - Google Patents

Abstract

FIELD: food industry.

SUBSTANCE: used to obtain protein hydrolyzate from Atlantic cod processing waste. A method for obtaining protein hydrolyzate from Atlantic cod processing waste has been proposed. The method involves grinding raw materials, processing the crushed raw materials with a 0.5-1.0% solution of acetic acid or citric acid at a temperature of 15 - 20°C and the mass ratio of the raw material and the acid solution is 1:4, separating the precipitate and washing it with cold water to neutral pH values of the wash water and subsequent hydrolysis under the action of the protozyme - proteolytic enzyme preparation, taken in an amount of no more than 0.5% by weight of the original raw material, at a temperature of +60°C. Upon completion of hydrolysis, the reaction mixture is heated to a temperature of +90°C to inactivate the enzyme preparation, the resulting hydrolyzate is filtered, dried, then crushed and packaged.

EFFECT: utilizing Atlantic cod processing waste and obtaining a protein supplement consisting of biologically active peptides with a molecular weight of 30-60 kDa.

4 cl, 2 dwg, 4 ex

Description

The invention relates to the fishing industry and is aimed at obtaining an enzymatic protein hydrolyzate from Atlantic cod processing waste and can be used in the production of protein hydrolyzate for food, cosmetics, feed mills and other industries.

When processing fish raw materials, a large amount of protein-containing waste is generated when performing operations such as cutting, cleaning, and portioning. When cutting fish into skinless fillets, the waste includes heads, cartilage with the remains of muscle fragments, skin, and fins. Currently, this waste is little used for food purposes; most of it is used to produce feed products.

There is a known method for producing hydrolysates from waste from meat, poultry and fish processing industries (RF Patent No. 2272418, published on March 27, 2006), including hydrolysis of raw materials with water and hydrochloric acid, followed by neutralization with sodium hydroxide, removal of fat and suspended solids particles, homogenization and drying of the resulting hydrolyzate. This method of obtaining hydrolysates is carried out in three stages: aqueous hydrolysis for 4-5 hours at a temperature of 100-120°C and a mass ratio of raw materials and water of 1:2-1:3, separation of the liquid fraction of hydrolyzate 1, followed by cleaning and drying, solid the sediment is subjected to acid hydrolysis with a 1-2% solution of hydrochloric acid for 4-5 hours at a temperature of 100-120°C, the liquid fraction hydrolyzate 2 is again separated, which is neutralized with sodium hydroxide, purified and dried, and the solid bone residue is re-subjected to acid hydrolysis 3 -4% hydrochloric acid solution for 4-5 hours at a temperature of 120-140°C, the resulting mixture of hydrolyzate 3 is neutralized with sodium hydroxide, homogenized and dried. The disadvantages of this method are the duration of the technological process of 15-20 hours, the use of high temperatures +100°C+140°C and fairly concentrated acid solutions, 2 - 4% hydrochloric acid solutions. Under such harsh technological conditions, thermolabile amino acids are destroyed and fats are oxidized, which deteriorates the quality of the final product and reduces its nutritional value. The need to neutralize the resulting hydrolysates with sodium hydroxide leads to the formation of a large amount of table salt, which also limits the possibilities of their use in food products.

There is a known method for producing amino acid hydrolyzate for food purposes (RF Patent No. 2277795, published on June 20, 2006) involving cutting and homogenization of fish raw materials, the formation of a reaction medium by treating the homogenate with an enzymatic complex isolated from fish raw materials, enzymatic hydrolysis of the reaction mixture, inactivation enzymes by heating the reaction mixture, centrifugation of the reaction mixture to isolate the hydrolyzate, its clarification and drying to form a dry product. The disadvantage of this method is the use of the contents of the wombs of cut-up fish raw materials as a source of the enzymatic complex, which leads to an increase in the labor intensity of the process due to the need for constant monitoring of the technological parameters of the process: regulation of the pH of the reaction medium and control of the amine nitrogen content, because the enzyme complex used is not standardized (proteolytic activity 50-300 units per 1 g of fish raw material homogenate) and the required depth of hydrolysis is achieved by increasing the duration of enzymolysis from 8 to 15 hours.

There is a known method for producing fish collagen hydrolyzate (RF Patent No. 2665589, published on August 31, 2018), including the preparation and analysis of raw materials (commercial fish skins), enzymatic isolation of collagen hydrolyzate, obtaining an acidic dispersion of collagen hydrolyzate, and the formation of a dry form of collagen hydrolyzate. The preparation of raw materials is carried out by cleaning fish skins, washing them with water four times, freezing, grinding and mixing. Enzymatic isolation of collagen hydrolyzate is carried out by washing the prepared homogenized product with water, pouring a 1-3% solution of a proteolytic enzyme preparation at a hydromodulus of 1:2-1:5, and incubating for 5 hours. Next, the product is filtered from impurities and an acidic dispersion is obtained by acidifying the solution with a solution of acetic acid to pH 5.5-6.5. The dry form is formed by evaporating water from the filtrate without heating at temperatures above 50°C. The disadvantage of this method is the presence of a significant amount of wash water at the stage of raw material preparation and the high consumption of the enzyme preparation of at least 20 g per 1 kg of raw material, because When enzymatically processing 1 kg of raw material, it is necessary to prepare at least 2 liters of a 1% solution of the enzyme preparation.

There is a known method for producing protein hydrolyzate from secondary fish raw materials (RF Patent No. 2711915, published on January 23, 2020, including the following operations: washing the raw materials with running water t = 12°C for 2-6 hours; soaking the raw materials in water for 24 hours and repeated washing; degreasing with an alcohol-ether mixture for 2-4 hours; demineralization with a 3% acetic acid solution for 12-24 hours at t=+18°C +25°C, followed by neutralization with a 2.5% sodium hydroxide solution to pH 5.8-6.2, by washing and grinding the raw material; then the resulting mass is hydrolyzed with a solution of collagenase with an activity of 60 units/g in an amount of 0.3% by weight of the raw material for 12-24 hours at t = 37°C; thermal inactivation of the enzyme followed by centrifugation of the hydrolyzate; the resulting hydrolyzate is dried and crushed. The disadvantage of this method is the duration of the technological process and a large amount of wash water that must be disposed of.

There is a known method for producing a protein food product (A.S. USSR No. 1171003, publ. 08/07/1985), including grinding fish, treating it with acetic acid, dividing the mass into fractions and drying. To simplify the method, reduce its duration, increase the yield of the product and improve its quality, before processing the fish, citric acid is added to acetic acid, and the solid fraction is mixed with pork fat before drying and the mixture is dried at 103°C -130°C, after drying, pressing is carried out. As a result of the absence of losses of protein substances caused by the influence of alkaline solutions at high pH values, an increased protein content is ensured. The protein product imitates fish meat products. However, this known method only uses fillets or unprocessed lean fish.

There is a known method for producing hydrolysates (A.S. USSR No. 1559466, published on October 27, 1996), which involves grinding fish or their processing waste, mixing with water in a ratio of 2:1-1:1, heating the mixture to +40°C+45 °C, adding the proteolytic enzyme G3x protosubtilin, carrying out hydrolysis for 0.5 hours -2.5 hours, filtration and freeze-drying or spray drying. The invention is aimed at increasing the yield of the target product and improving its quality. Thanks to mild temperature treatment, a large amount of fat-soluble vitamins A and E is preserved.

There is a known method for producing water-soluble feed fish protein concentrate (A.S. USSR No. 1 238 748, publ. 06/23/1986), including grinding of raw materials, enzymatic hydrolysis, inactivation of enzymes by heating, separation of the hydrolyzate from the undissolved residue, degreasing of the hydrolyzate by separation, concentration by evaporation and Spray drying of the hydrolyzate. To improve the quality of the hydrolyzate after grinding, the raw material is boiled at 90°C - 100°C for 20 minutes, then divided into liquid and solid parts, the pressed solid part is subjected to hydrolysis with the enzyme composition protosubtilin G20X and protolichenin G 20X at a ratio of 1:1 at pH 7 .7 - 8.0 using 1 n. NaOH solution for 3 hours - 4 hours with constant stirring; at the end of hydrolysis, the mixture is neutralized with a 1N solution. hydrochloric acid HCl. The liquid part is degreased and added to the hydrolyzate before concentration. The non-hydrolyzed residue is washed with water in a 1:1 ratio and then sent for the production of feed flour. The invention is aimed at improving the quality of the target product. The resulting water-soluble protein concentrate is used as a substitute for whole milk for feeding agricultural animals. In the known method, fish of low nutritional value is used, incl. fat.

The technical task is to develop an effective method for producing protein hydrolyzate from Atlantic cod processing waste with increased biological and nutritional value.

The technical result is the production of a protein hydrolyzate with a fairly high biological value from Atlantic cod processing waste with a short duration of the technological process.

To achieve a technical result in the method of obtaining protein hydrolyzate from Atlantic cod processing waste, including grinding the raw material, enzymatic hydrolysis, inactivation of the enzyme preparation by heating, separation of the hydrolyzate from the undissolved sediment and drying, after grinding the raw material is mixed with a 0.5% - 1.0% solution organic acid in a ratio of 1:4 and kept at a temperature of +15°C +20°C for 30 minutes with constant stirring, then the mixture is filtered, the resulting precipitate is washed with cold water until the pH of the wash water is at least 5.0, after washing the precipitate mixed with water in a ratio of 1:2, add a solution of sodium hydroxide to pH 8.3, heat to +60°C, add the enzyme preparation protozyme in an amount of 2 g - 4 g / kg of the original crushed raw material and carry out hydrolysis at +60°C for 2-4 hours with constant stirring, after drying, the hydrolyzate is crushed and packaged.

Acetic or citric acid is used as an organic acid. Inactivation of the enzyme preparation is carried out at a temperature of +90°C for 10 minutes. The hydrolyzate is dried to a moisture content of no more than 8% using freeze drying.

To obtain protein hydrolyzate, Atlantic cod filleting waste is used (ridges with remains of muscle fragments, tails, fins), which are crushed and treated with a solution of organic acid - acetic or citric - to improve the organoleptic characteristics of the final product; processing of already crushed secondary fish waste can significantly reduce the duration operations by increasing the exchange surface. Enzymatic hydrolysis of protein-containing raw materials is carried out under conditions optimal for the operation of the enzyme preparation Protozyme, which is approved for use in food production, has high proteolytic activity (50,000 units/g) and provides a deep degree of protein breakdown at low concentrations (no more than 0.5% based on the mass of crushed raw materials).

The proposed method for producing protein hydrolyzate from Atlantic cod processing waste is illustrated by the tables presented in Fig. 12.

In fig. Figure 1 shows the chemical composition of the feedstock from Atlantic cod processing waste, including fish ridges with fragments of muscle tissue, fins, and tails; FIG. 2- quality indicators of protein hydrolyzate.

The method was carried out as follows.

Secondary fish raw materials, Atlantic cod processing waste - ridges with remains of muscle fragments, tails, fins, crushed on a grinder with a grid hole diameter of 5 mm, mixed with a 0.5 - 1.0% solution of organic acid, acetic or citric, in a mass ratio raw materials: acid solution 1:4 and kept at a temperature of +15°C +20°C and constant stirring for 30 minutes. Then the resulting mixture is filtered, the precipitate, which represents minced meat, is washed with cold tap water until the pH of the wash water is at least 5.0 units. After washing, the minced meat is mixed with water at a raw material: water ratio of 1:2, the pH of the reaction medium is adjusted to 8.3 units. sodium hydroxide solution, heated to a temperature of +60°C and the enzyme preparation (EP) protozyme is added in an amount of 2 g - 4 g per 1 kg of initial crushed raw materials. The time of FP administration is considered the beginning of hydrolysis. Hydrolysis is carried out for 2-4 hours at a temperature of +60°C and constant stirring. At the end of the process, the reaction mixture is heated to a temperature of +90°C to inactivate the EP, maintained at this temperature for 10 minutes and filtered to remove the unhydrolyzed residue, consisting of 2 parts: approximately 1/3 gray suspension and 2/3 crushed ridges . The gray creamy mass can be sent back for hydrolysis, but not much of it, or disposed of. The crushed ridges, which are a white sediment, can be washed, crushed and used as a mineral feed additive rich in phosphorus and calcium. The filtrate, a clear, purified hydrolysate, is dried to a moisture content in the product of no more than 8% using freeze drying. The dried hydrolyzate is crushed, packaged and sent for storage. Enzymatic protein hydrolyzate is a homogeneous fine powder of white or light yellow color, highly soluble in water. The quality indicators of the resulting hydrolyzate are presented in the table (Fig. 2).

The advantage of this method is that the processing of secondary fish raw materials with a solution of organic acid is carried out after grinding the fish waste, which reduces the duration of the operation by increasing the exchange surface and helps improve the quality of the product. It was previously found that treating crushed fish waste for 30 minutes with dilute solutions of organic acids does not lead to the destruction of protein molecules, which means that protein losses during processing and subsequent washing are insignificant. Enzymatic hydrolysis is carried out under conditions optimal for the operation of the enzyme preparation. The selected protozyme enzyme retains its activity in a wide range of pH values of the reaction medium - pH _optimal = 6.0 - 10.0, which simplifies the process of regulating technological parameters. In addition, a higher processing temperature of +60°C, at which the protozyme is stable, makes it possible to reduce the duration of hydrolysis by increasing the reaction rate.

This method ensures the rational use of fish raw materials, allows us to obtain a product with high quality indicators, reduce the duration of its processing, and simplify the technology for obtaining hydrolyzate.

Examples of method implementation.

Example 1.

Secondary fish raw materials 1 kg (waste from the processing of Atlantic cod - ridges with the remains of muscle fragments, tails, fins) are crushed on a grinder with a grid hole diameter of 5 mm, mixed with a 0.5% solution of citric acid in a mass ratio of raw materials: acid solution 1:4 and kept at a temperature of +20°C and constant stirring for 30 minutes. Then the resulting mixture is filtered, the precipitate (minced meat) is washed with cold tap water until the pH of the wash water is at least 5.0 units. After washing, the minced meat is mixed with water in a mass ratio of raw material: water = 1:2, the pH of the reaction medium is adjusted to 8.3 units. sodium hydroxide solution, heated to a temperature of +60°C and the enzyme preparation (EP) protozyme is added in the amount of 2 g per 1 kg of initial crushed raw material. The time of FP administration is considered the beginning of hydrolysis. Hydrolysis is carried out for 2 hours at a temperature of +60°C and constant stirring. At the end of the process, the reaction mixture is heated to a temperature of +90°C to inactivate the EP, maintained at this temperature for 10 minutes and filtered to remove non-hydrolyzed raw materials. The filtrate, a clear, purified hydrolysate, is dried to a moisture content in the product of no more than 8% using freeze drying. The dried hydrolyzate is crushed, packaged and sent for storage.

Example 2.

The method was carried out similarly to example 1, except that the processing of the crushed raw materials was carried out with a 1.0% solution of acetic acid and kept at a temperature of +15°C.

Example 3.

The method was carried out similarly to example 1, except that enzymatic hydrolysis was carried out for 4 hours.

Example 4.

The method was carried out similarly to example 1, except that enzymatic hydrolysis was carried out for 4 hours, the concentration of the enzyme preparation was 4 g per 1 kg of initial crushed raw materials.

Waste from the processing of Atlantic cod (Gadus morhua), which consists of fish ridges with fragments of muscle tissue, fins, and tails, was used as raw material for the production of protein hydrolysates. The chemical composition of protein-containing raw materials is presented in the table (Fig. 1).

Organoleptic and physicochemical indicators of the quality of the protein hydrolyzate are presented in the table (Fig. 2). Analysis of the data showed that the resulting hydrolyzate is characterized by a high protein content and is a homogeneous fine powder of white or light yellow color, highly soluble in water.

The proposed method for obtaining protein hydrolyzate from Atlantic cod processing waste allows us to obtain a finished protein product consisting of biologically active peptides with a molecular weight of 30-60 kDa and with high quality indicators, reduce the duration of the technological cycle, and simplify the process of regulating technological parameters.

Claims (4)

1. A method for producing protein hydrolyzate from Atlantic cod processing waste, including grinding the raw material, enzymatic hydrolysis, inactivation of the enzyme preparation by heating, separating the hydrolyzate from the undissolved sediment and drying, characterized in that after grinding the raw material is mixed with 0.5% -1.0% solution of organic acid in a ratio of 1:4 and kept at a temperature of +15°C - +20°C for 30 minutes with constant stirring, then the mixture is filtered, the resulting precipitate is washed with cold water until the pH of the wash water is at least 5.0, after After washing, the sediment is mixed with water in a ratio of 1:2, a solution of sodium hydroxide is added to pH 8.3, heated to +60°C, the enzyme preparation protozyme is added in an amount of 2 g - 4 g / kg of the original crushed raw material and hydrolysis is carried out at +60 °C for 2-4 hours with constant stirring; after drying, the hydrolyzate is crushed and packaged. 2. The method according to claim 1, characterized in that acetic or citric acid is used as an organic acid. 3. The method according to claim 1, characterized in that the inactivation of the enzyme preparation is carried out at a temperature of +90°C for 10 minutes. 4. The method according to claim 1, characterized in that the hydrolyzate is dried to a moisture content of no more than 8% using freeze drying.

Images