CN112753998B - Method for preparing seafood sauce by utilizing squid leftovers - Google Patents
Method for preparing seafood sauce by utilizing squid leftovers Download PDFInfo
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- CN112753998B CN112753998B CN202110184330.0A CN202110184330A CN112753998B CN 112753998 B CN112753998 B CN 112753998B CN 202110184330 A CN202110184330 A CN 202110184330A CN 112753998 B CN112753998 B CN 112753998B
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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
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/21—Synthetic spices, flavouring agents or condiments containing amino acids
- A23L27/215—Synthetic spices, flavouring agents or condiments containing amino acids heated in the presence of reducing sugars, e.g. Maillard's non-enzymatic browning
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/26—Meat flavours
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Abstract
The invention relates to a method for preparing seafood sauce by utilizing squid leftovers, which comprises the following steps: s1: mashing squid viscera and squid skin and homogenizing; s2: adding enzyme into the slurry containing squid viscera and squid skin for enzymolysis, inactivating enzyme, performing solid-liquid separation, and collecting supernatant; the enzymolysis conditions are as follows: the enzyme is a mixed enzyme of alkaline protease and flavourzyme, the addition amount is 0.6-1.6%, the enzymolysis time is 4.5-6h, and the enzymolysis temperature is 50-58 ℃; s3: maillard aroma generation reaction: after the supernatant is subjected to active carbon oscillation adsorption treatment, centrifuging to obtain a clear solution, adjusting the pH, adding a certain amount of D-xylose or/and D-glucose and L-glutamic acid, stirring, and performing Maillard aroma-producing reaction in an oil bath; s4, removing heavy metals; s5: adding adjuvants, blending, stirring, steaming and concentrating; s6: and (5) subpackaging and sterilizing. The invention takes squid viscera and squid skin as raw materials, removes heavy metals through biological enzymolysis and Maillard flavor enhancement reaction, and then is cooked by being matched with auxiliary materials to prepare seasonings such as seafood sauce and the like which have unique flavor and rich nutrition and meet the national standard of heavy metals.
Description
Technical Field
The invention relates to the technical field of food processing, in particular to a method for preparing seafood sauce by utilizing squid leftovers.
Background
The squid is a marine economic animal of mollusk cephalopoda, also called soft fish, and has the characteristics of short life cycle, strong fecundity, rapid resource recovery and the like. The squid is large in size, long in carcass, and similar to abalone in meat color and flavor. The squid is rich in high protein and a plurality of essential amino acids, and is a low-fat aquatic product. The statistical data shows that the squid capture amount in China is 29.2 ten thousand tons. A large amount of leftovers such as internal organs of the squid, which account for about 15 percent of the fresh weight of the squid, are produced in the processing process of the squid, and the direct discarding not only wastes resources, but also causes environmental pollution. The squid viscera are rich in nutrition, and each 100g of squid viscera contains 21.15g of fat, 21.24g of protein, 51.46mg of calcium, 609.07 mu g of iron and 95.88 mu g of phosphorus; the fatty acid of squid visceral fat contains 10.58% of EPA and 15.23% of DHA. In addition, the squid skin is rich in protein, and contains various vitamins, mineral elements and amino acids.
From the body weight of the squid, the squid meat accounts for about 50 percent of the body weight, the head and feet account for about 25 percent, and the squid skin and viscera account for about 25 percent. Although the internal organs of the squids have rich nutrient components, the internal organs of the squids have the problems of fishy smell, high putrefaction and stink, and the concentration of heavy metals and biogenic amines in the internal organs is increased when the internal organs of the squids are singly fermented to prepare foods or auxiliary seasonings. These reasons make the processing and application of squid viscera difficult, and the squid viscera are often buried in the ground as useless waste. And the squid skin is dried and crushed into fish meal which is used as cat food and the like. The two methods have extremely low processing utilization rate and cannot bring higher value to related enterprises.
Therefore, the novel squid flavor sauce product which is delicious in flavor, reduced in fishy smell, rich in nutrition and free of heavy metal exceeding standard is developed through a novel process.
Disclosure of Invention
Technical problem to be solved
In view of the defects and shortcomings of the prior art, the invention provides a method for preparing seafood sauce by utilizing squid leftovers, which solves the problems of waste of squid leftovers, low utilization efficiency, low economic value and the like.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a method for preparing seafood sauce by utilizing squid leftovers is characterized in that the squid viscera and squid skin are used as raw materials to prepare the seafood sauce, and the preparation process comprises the following steps:
s1: pulping:
mashing squid viscera and squid skin and homogenizing;
s2: enzymolysis:
adding enzyme into the slurry containing squid viscera and squid skin for enzymolysis, inactivating enzyme, performing solid-liquid separation, and collecting supernatant; the enzymolysis conditions are as follows: the enzyme is a mixed enzyme of alkaline protease and flavourzyme, the addition amount is 0.6-1.6% (mass fraction), the enzymolysis time is 4.5-6h, and the enzymolysis temperature is 50-58 ℃;
s3: maillard fragrance-producing reaction:
subjecting the supernatant obtained in the step S2 to active carbon oscillation adsorption treatment, centrifuging again to obtain a clear solution, adjusting pH, adding a certain amount of D-xylose or/and D-glucose and L-glutamic acid, stirring, and performing Maillard aroma-producing reaction in an oil bath;
s4, removing heavy metals from the Maillard fragrance reaction liquid by using an organic acid-diatomite combination method;
s5: adding adjuvants, blending, stirring, steaming, and concentrating;
s6: subpackaging and sterilizing to obtain the seafood sauce product.
According to a preferred embodiment of the invention, in step S1, the mass ratio of the internal organs to the skin of the squid is 3-1:1, the internal organs and the skin of the squid are mixed and mashed, and water is added according to the volume ratio of 1:0.8-1.2 (more preferably 1:1) to obtain the slurry used in step S2. Preferably, the mass ratio of the squid viscera to the squid skin is 1: 1.
according to a preferred embodiment of the present invention, in step S2, the mass ratio of the alkaline protease to the flavourzyme is 1-2: 1, more preferably 2: 1.
According to the preferred embodiment of the present invention, in step S2, the enzyme is added in an amount of 0.8-1.0%; more preferably 0.8%.
According to the preferred embodiment of the invention, in step S2, the enzymolysis time is 4.5-5h, and the enzymolysis temperature is 50-55 ℃; more preferably, the enzymolysis temperature is 55 ℃, and the enzymolysis time is 5 h; the enzymolysis pH is 7-8.5, preferably 7.
According to the preferred embodiment of the present invention, in step S3, the addition amount of D-xylose and D-glucose is 1-3%, the reaction pH is 7.0-9.0, the reaction time is 15-20min, the reaction temperature is 100-120 ℃, and the addition amount of L-glutamic acid is 1-3%.
According to the preferred embodiment of the present invention, in step S3, the amount of D-xylose and D-glucose added is 3%, the reaction pH is 7.0, the reaction time is 100min, the reaction temperature is 120 ℃, and the amount of L-glutamic acid added is 2%.
According to the preferred embodiment of the present invention, in step S4, the specific method is: mixing citric acid solid powder and diatomite at a mass ratio of 10-70:100, adding water, mixing, oven drying to obtain adsorbent cake, mixing Maillard reaction solution at a liquid-solid mass ratio of 20-200:1, oscillating at 30-60 deg.C and pH of 7-10 for 0.5-6 hr, and centrifuging.
Preferably, when the mixing mass of the citric acid solid powder and the diatomite is 10-30:100 and more preferably 10:100, the liquid-solid mass ratio of the citric acid solid powder and the Maillard reaction liquid is 200:1, when the adsorption temperature is 40 ℃ and the pH is 9 (the pH is adjusted by food-grade calcium hydroxide), the adsorption treatment is carried out for 4 hours, the removal rate of Cd in the Maillard reaction liquid reaches 99.71%, the content of Cd in the reaction liquid is as low as 71.84ppb, and the requirements of GB 2762-containing 2017 are met.
According to a preferred embodiment of the present invention, in step S5, the sterilization is microfiltration membrane filtration or ultra-high pressure sterilization; performing ultra-high pressure treatment (200 and 300Mpa, 15-20min) to complete sterilization.
In step S4, the auxiliary materials include edible salt, white granulated sugar, sodium glutamate, emulsifier, spice, potassium sorbate and the like. Other auxiliary seasonings can be added according to the specific types of the seasonings to be prepared.
Wherein the enzyme deactivation condition in step S2 is boiling, i.e. boiling at 100 deg.C for 3-6min, to complete the enzyme deactivation.
(III) advantageous effects
The invention has the technical effects that
(1) According to the invention, squid viscera and squid skin are used as raw materials, the protein rich in the raw materials is hydrolyzed into amino acid by a biological enzymolysis method, then Maillard aroma enhancement reaction is carried out, and then auxiliary materials are added for stewing, so that the seafood flavor seasoning with unique flavor and rich nutrition is developed, and a new technical approach is provided for reducing the environmental pollution of squid processing by-products, promoting the comprehensive utilization of squid leftovers and improving the technical level of deep processing of squids. The seafood sauce is prepared by compounding the flavor of the squid skin and the viscera, so that the fishy smell of the viscera can be reduced to a certain extent, the flavor is blended, the factors of high concentration of heavy metal and biogenic amine and the like caused by single use of viscera fermentation are avoided, and meanwhile, the squid skin is utilized to supplement vitamins, so that the nutrition of the product is coordinated, the waste of squid resources can be greatly reduced, and the utilization efficiency and the economic value of the squid can be improved. The enzymolysis liquid is subjected to Maillard flavor-producing reaction, so that fishy smell and bitter taste after enzymolysis are removed, and meat flavor is added.
(2) The quality and flavor of the squid leftover enzymolysis products can be influenced by the characteristics of different hydrolases. The alkaline protease has strong capability of decomposing protein, and especially has superiority in decomposing aquatic products such as squid. The flavor protease is used in a compounding way under the condition of using the alkaline protease, so that the effects of masking bitter taste and reducing fishy smell can be achieved. In addition, the protease can completely lose activity when being inactivated at high temperature, thereby being beneficial to the stepwise production. Tests and comparisons prove that the alkaline protease and the flavourzyme are compounded, and the enzymolysis efficiency is better.
(3) When the mass ratio of the alkaline protease to the flavourzyme is 1-2: 1 (more preferably 2:1), the enzymolysis time is 4.5-5h (more preferably 5h), the enzymolysis temperature is 50-58 ℃ (more preferably 55 ℃), the protein in the substrate of the pulp can be almost completely decomposed into free amino acid, and the content of free amino nitrogen reaches the highest value.
(4) In the Maillard flavor-generating reaction, the addition amount of reducing sugar is 1-3% (more preferably 3%), the reaction pH is 7.0-9.0 (more preferably 7.0), the reaction time is 15-25min (more preferably 20min), the reaction temperature is 100-, crab flavor is improved remarkably in the overall flavor.
(5) For Maillard aroma-producing reaction liquid, removing heavy metals by adopting an organic acid-diatomite combined method, compounding citric acid powder and diatomite according to the mass ratio of 10-70:100, adding water for homogenizing, drying to prepare an adsorbent cake, adding the adsorbent cake and the Maillard aroma-producing reaction liquid according to a certain proportion (the liquid-solid mass ratio is 20-200: 1), and carrying out oscillating adsorption at a certain temperature (30-60 ℃), for 0.5-6h and at pH, wherein the removal rate of Cd can reach more than 77%; further optimizing the conditions of mass ratio of citric acid powder to diatomite, pH value, temperature and the like, wherein the removal rate of Cd can reach more than 99.7 percent, so that the content of Cd in Maillard reaction liquid is lower than 100ppb, and obtaining the aquatic seasoning meeting the national standard GB2762-2017 after centrifugation treatment and seasoning by adding seasonings.
The Maillard reaction solution processed by the steps is black, bright and clear in color, rich in burnt flavor and fresh and fragrant in taste, and a high-quality seafood sauce product is obtained after the auxiliary materials are blended.
Drawings
FIG. 1 is a graph showing the change in the content of amino nitrogen in the enzymatic hydrolysate (supernatant) of example 1 and comparative examples 1 to 7.
FIG. 2 is a graph showing the change in the content of amino nitrogen in the enzymatic hydrolysate (supernatant) of example 2 and comparative examples 8 to 11.
FIG. 3 is a graph showing the change in the content of amino nitrogen in the enzymatic hydrolysate (supernatant) of example 3 and comparative examples 14 to 17.
FIG. 4 is a histogram showing the content of amino nitrogen in the enzymatic hydrolysates (supernatants) of example 4 and comparative examples 18 to 21.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention by way of the following detailed description.
The technical idea of the invention is as follows: firstly, in order to fully utilize rich nutrient substances contained in squid viscera and avoid the defect of using the squid viscera independently, the squid viscera and the squid skin are used as raw materials for preparing the seafood sauce according to the mass ratio of 3-1: 1. Secondly, the purpose of completely hydrolyzing the proteins in the internal organs and the skin of the squid into free amino acids (measuring the content of free amino nitrogen) is achieved by using the optimized enzyme types, the enzyme addition amount and the ratio, the enzymolysis temperature and the enzymolysis time, and the content of the free amino acids in the enzymolysis liquid is increased. And thirdly, the optimized Maillard flavor-generating reaction is adopted for the enzymatic hydrolysate, so that the amine substances for reducing the flavor in the enzymatic hydrolysate are greatly reduced, the TMA and DMA which generate fishy smell become trace, the contents of aldehydes, ketones, furans, pyrazines and some sulfur-containing compounds for adding the flavor are increased to a certain extent after the Maillard reaction, wherein the increase range of the alkyl pyrazines which generate the baking flavor is the highest, the crab flavor in the total flavor is remarkably improved, the flavor components are rich, and the sensory evaluation score is high. Fourthly, compounding citric acid powder and diatomite according to a certain mass ratio to the Maillard fragrance-generating reaction liquid, adding the mixture and the Maillard fragrance-generating reaction liquid according to a certain proportion, and efficiently removing the heavy metal content in the reaction liquid under the action of certain temperature, pH and time oscillation. The citric acid has good chelating effect to remove heavy metals, has corrosion resistance, can play a role in corrosion resistance even if being remained in reaction liquid after centrifugation, and is non-toxic and harmless.
The Maillard reaction solution obtained by the process is black, bright and clear in color, rich in burnt flavor and fresh and fragrant in taste, meets the requirement of national standard on the heavy metal content of fish food flavoring agents, and has market prospect of being developed into seafood sauce.
Example 1
The embodiment provides a method for preparing seafood sauce by utilizing squid leftovers, which comprises the following steps:
(1) mashing internal organs and skin of the squid according to the mass ratio of 1:1, and adding water according to the volume ratio of 1:1 to obtain slurry.
(2) Adding enzyme into the slurry for enzymolysis, inactivating enzyme, performing solid-liquid separation, and collecting supernatant. The enzymolysis conditions are as follows: the enzyme is a mixed enzyme of alkaline protease and flavourzyme, the addition amount is 0.8 percent (mass fraction), the mass ratio of the alkaline protease to the flavourzyme is 2:1, the enzymolysis time is 5h, the enzymolysis temperature is 50 ℃, and the pH value is 7.0. After enzymolysis for 5.5h, heating to 100 deg.C and boiling for 6min to inactivate enzyme, filtering the enzymolysis solution, and collecting supernatant.
(3) Adjusting the pH value to 7.0, adding 3% of D-xylose and 2% of L-glutamic acid, stirring, and carrying out Maillard aroma-producing reaction in an oil bath; the reaction time is 15min, the reaction temperature is 120 ℃, and Maillard incense reaction liquid is obtained.
(4) Mixing citric acid powder according to the weight ratio of 50: homogenizing diatomite at a mass ratio of 100, drying to obtain adsorbent cake, mixing the adsorbent cake and Maillard reaction solution at a mass ratio of 1:200, adjusting pH to 8 with food-grade calcium hydroxide at 40 deg.C, shaking for 4 hr, centrifuging, and collecting supernatant.
(5) The obtained reaction liquid is brown, clear, transparent, rich in fish flavor, delicious, free of fishy smell, rich in burnt flavor and free of burnt flavor, and is added with auxiliary materials to prepare the flavor, stirred, cooked, concentrated, subpackaged and sterilized in a high-pressure sterilization kettle to obtain the seafood sauce product.
Comparative examples 1 to 7
Comparative examples 1 to 7 were conducted in the same manner as in example 1 except that the enzyme addition amount of 0.8% was changed to 0.1%, 0.2%, 0.4%, 1.0%, 1.5%, 2.0%, and 2.5%, respectively.
The influence of the enzyme addition amount on the enzymolysis efficiency was compared with the use of amino nitrogen as an evaluation index. The determination of the content of the amino nitrogen is carried out according to the standard GB/T5009.39-2003 by using a free amino acid analyzer.
The amounts of ammonia ground state nitrogen in the enzymatic hydrolysates of example 1 and comparative examples 1 to 7 (the supernatant of step (2)) were measured, and the results are shown in FIG. 1.
As can be seen from FIG. 1, the content of free amino nitrogen in the enzymatic hydrolysate first increased and then became stable as the amount of enzyme added increased. Indicating that the protein in the leftover can be almost completely hydrolyzed into free amino acid when the adding amount of the enzyme reaches 0.8 percent (mass fraction).
Example 2
The embodiment provides a method for preparing seafood sauce by utilizing squid leftovers, which comprises the following steps:
(1) mashing internal organs and skins of the squids according to the mass ratio of 1:1, and adding water according to the volume ratio of 1:1 to obtain slurry.
(2) Adding enzyme into the slurry for enzymolysis, inactivating enzyme, performing solid-liquid separation, and collecting supernatant. The enzymolysis conditions are as follows: the enzyme is a mixed enzyme of alkaline protease and flavourzyme, the addition amount is 0.8 percent (mass fraction), the mass ratio of the alkaline protease to the flavourzyme is 2:1, the enzymolysis time is 5h, the enzymolysis temperature is 55 ℃, and the pH value is 7.0. After enzymolysis for 5h, heating to 100 deg.C and boiling for 6min to inactivate enzyme, then filtering the enzymolysis liquid, and collecting the supernatant.
(3) Adding 50% volume of active carbon into the supernatant, performing oscillation adsorption treatment, centrifuging again to obtain a clear solution, adjusting the pH to 7.0, adding 3% of D-glucose and 2% of L-glutamic acid, stirring, and performing Maillard aroma-producing reaction in an oil bath; the reaction time is 20min, the reaction temperature is 120 ℃, and Maillard incense reaction liquid is obtained.
(4) Mixing citric acid powder according to the weight ratio of 70: homogenizing diatomite at a mass ratio of 100, drying to obtain adsorbent cake, mixing the adsorbent cake and Maillard reaction solution at a mass ratio of 1:150, adjusting pH to 9 with food-grade calcium hydroxide at 40 deg.C, shaking for 6 hr, centrifuging, and collecting supernatant.
(5) The obtained reaction liquid is brown, clear, transparent, rich in fish flavor, delicious, free of fishy smell, rich in burnt flavor and free of burnt flavor, and is added with auxiliary materials to prepare the flavor, stirred, cooked, concentrated, subpackaged and sterilized in a high-pressure sterilization kettle to obtain the seafood sauce product.
After enzymolysis according to the step (2), the level of free amino nitrogen in the enzymolysis liquid (supernatant) is at a higher level compared with the level of free amino nitrogen in the same type of fish paste, and the amino acid content in the enzymolysis liquid is shown in the following table 1:
table 1:
comparative examples 8 to 11
Comparative examples 8 to 11 are based on example 2, and the temperatures of enzymolysis were changed from 55 ℃ to 45 ℃, 50 ℃, 60 ℃ and 65 ℃, respectively.
The influence of the enzyme addition amount on the enzymolysis efficiency was compared with the use of amino nitrogen as an evaluation index. The determination of the content of the amino nitrogen is carried out according to the standard GB/T5009.39-2003 by using a free amino acid analyzer.
The amounts of ammonia ground state nitrogen in the enzymatic hydrolysates of example 2 and comparative examples 8 to 11 (the supernatants of step (2)) were measured, and the results are shown in FIG. 2.
As can be seen from FIG. 2, the content of free amino nitrogen in the fish leftover enzymatic hydrolysate increases with temperature, first, reaches the maximum when reaching 55 ℃, and then decreases with temperature. The enzyme activity is sensitive to temperature, and when the temperature is gradually increased to a proper temperature, the activity is gradually increased; the activity then decreases with increasing temperature until irreversible deactivation.
Comparative example 12
Comparative example 12 on the basis of example 2, the procedure (2) was changed to: the mass ratio of the alkaline protease to the flavor protease is 1:1, the enzymolysis time is 5h, the enzymolysis temperature is 55 ℃, and the pH value is 7.0.
Comparative example 13
Comparative example 13 on the basis of example 2, the procedure (2) was changed to: the mass ratio of the alkaline protease to the flavor protease is 3:1, the enzymolysis time is 5.5h, the enzymolysis temperature is 55 ℃, and the pH value is 7.0.
The concentrations of free amino nitrogen in the enzymatic hydrolysates (supernatants) of example 2 and comparative examples 12-13 are shown in table 2 below:
table 2:
group of | Enzyme ratio | Time of enzymolysis | Temperature of | Concentration of free amino nitrogen is mug/ml |
Example 2 | 2:1 | 4.5 |
55℃ | 165.05 |
Comparative example 12 | 1:1 | 5.0 |
55℃ | 132.79 |
Comparative example 13 | 3:1 | 5.5 |
55℃ | 125.78 |
As can be seen from Table 2, the optimum effect was obtained when the mass ratio of alkaline protease to flavourzyme was 2: 1.
Example 3
The embodiment provides a method for preparing seafood sauce by utilizing squid leftovers, which comprises the following steps:
(1) mashing internal organs and skin of the squid according to the mass ratio of 1:1, and adding water according to the volume ratio of 1:1 to obtain slurry.
(2) Adding enzyme into the slurry for enzymolysis, inactivating enzyme, performing solid-liquid separation, and collecting supernatant. The enzymolysis conditions are as follows: the enzyme is a mixed enzyme of alkaline protease and flavourzyme, the addition amount is 0.4 percent (mass fraction), the mass ratio of the alkaline protease to the flavourzyme is 2:1, the enzymolysis time is 5h, the enzymolysis temperature is 55 ℃, and the pH value is 7.0. After enzymolysis for 5h, heating to 100 deg.C and boiling for 6min to inactivate enzyme, then filtering the enzymolysis liquid, and collecting the supernatant.
(3) Adding 50% volume of active carbon into the supernatant, performing oscillation adsorption treatment, centrifuging again to obtain a clear solution, adjusting the pH to 7.0, adding 3% of D-glucose and 2% of L-glutamic acid, stirring, and performing Maillard aroma-producing reaction in an oil bath; the reaction time is 25min, the reaction temperature is 120 ℃, and Maillard incense reaction liquid is obtained.
(4) Mixing citric acid powder according to the weight ratio of 40: homogenizing diatomite at a mass ratio of 100, drying to obtain adsorbent cake, mixing the adsorbent cake and Maillard reaction solution at a mass ratio of 1:150, adjusting pH to 9 with food-grade calcium hydroxide at 45 deg.C, shaking for 6 hr, centrifuging, and collecting supernatant.
(5) Obtaining reaction liquid which is light brown, clear, transparent, rich in fish flavor, delicious, free of fishy smell, rich in burnt flavor and free of burnt flavor, adding auxiliary materials to prepare the flavor, stirring, cooking and concentrating, subpackaging, sterilizing in a high-pressure sterilization kettle, and obtaining the seafood sauce product.
Comparative examples 14 to 17
Comparative examples 14 to 17 were obtained by changing the enzymolysis time in the step (2) to 4.0 hours, 4.5 hours, 5.5 hours and 6.0 hours based on example 3.
The influence of the enzyme addition amount on the enzymolysis efficiency was compared with the use of amino nitrogen as an evaluation index. The content of the amino nitrogen is determined according to the standard GB/T5009.39-2003 and by using a free amino acid analyzer.
The amounts of ammonia ground state nitrogen in the enzymatic hydrolysates of example 3 and comparative examples 14 to 17 (the supernatants of step (2)) were measured, and the results are shown in FIG. 3. The content of free amino nitrogen in the squid leftover enzymatic hydrolysate is in an ascending state and then tends to be stable along with the increase of time. This is due to the limited reaction substrate and over time the enzyme reacts with the substrate and no additional free amino nitrogen is produced. When the enzymolysis time is 5h (example 3), the highest content of free amino nitrogen is achieved and the difference is significant.
Example 4
The embodiment provides a method for preparing seafood sauce by utilizing squid leftovers, which comprises the following steps:
(1) mashing internal organs and skin of the squid according to the mass ratio of 1:1, and adding water according to the volume ratio of 1:1 to obtain slurry.
(2) Adding enzyme into the slurry for enzymolysis, inactivating enzyme, performing solid-liquid separation, and collecting supernatant. The enzymolysis conditions are as follows: the enzyme is a mixed enzyme of alkaline protease and flavourzyme, the addition amount is 0.4 percent (mass fraction), the mass ratio of the alkaline protease to the flavourzyme is 1:1, the enzymolysis time is 5h, the enzymolysis temperature is 55 ℃, and the pH value is 7.0. After enzymolysis for 5h, heating to 100 deg.C and boiling for 6min to inactivate enzyme, then filtering the enzymolysis liquid, and collecting the supernatant.
(3) Adding 50% volume of active carbon into the supernatant, performing oscillation adsorption treatment, centrifuging again to obtain a clear solution, adjusting the pH to 8.0, adding 3% of D-glucose and 2% of L-glutamic acid, stirring, and performing Maillard aroma-producing reaction in an oil bath; the reaction time is 20min, the reaction temperature is 120 ℃, and Maillard incense reaction liquid is obtained.
(4) Mixing citric acid powder according to the weight ratio of 40: homogenizing diatomite at a mass ratio of 100, drying to obtain adsorbent cake, mixing the adsorbent cake and Maillard reaction solution at a mass ratio of 1:80, adjusting pH to 10 with food-grade calcium hydroxide at 35 deg.C, shaking for 4 hr, centrifuging, and collecting supernatant.
(5) Obtaining reaction liquid which is light brown, clear, transparent, rich in fish flavor, delicious, free of fishy smell, rich in burnt flavor and free of burnt flavor, adding auxiliary materials to prepare the flavor, stirring, cooking and concentrating, subpackaging, sterilizing in a high-pressure sterilization kettle, and obtaining the seafood sauce product.
Comparative examples 18 to 21
Comparative examples 18 to 21 were conducted in the same manner as in example 4 except that the amount of enzyme added was changed to 0.4% (1: 1 by mass) in each case: 0.4% of neutral protease, 0.4% of alkaline protease, 0.4% of flavourzyme and 0.2% of neutral protease and 0.2% of flavourzyme.
The amounts of ammonia ground state nitrogen in the enzymatic hydrolysates of example 4 and comparative examples 18 to 21 (the supernatants of step (2)) were measured, and the results are shown in FIG. 4.
As can be seen from fig. 4, the properties of different hydrolases can affect the quality and flavor of the squid leftover enzymolysis product. The alkaline protease has strong capability of decomposing protein, and has certain superiority in fish protein hydrolysis. The flavor protease is used in a compounding way under the condition of using the alkaline protease, so that the effects of masking bitter taste and reducing fishy smell can be achieved. Therefore, the alkaline protease and the flavourzyme are compounded for enzymolysis, so that the enzymolysis efficiency is better.
Example 5
The embodiment provides a method for preparing seafood sauce by utilizing squid leftovers, which comprises the following steps:
(1) mashing internal organs and skin of the squid according to the mass ratio of 1:1, and adding water according to the volume ratio of 1:1 to obtain slurry.
(2) Adding enzyme into the slurry for enzymolysis, inactivating enzyme, performing solid-liquid separation, and collecting supernatant. The enzymolysis conditions are as follows: the enzyme is a mixed enzyme of alkaline protease and flavourzyme, the addition amount is 0.8 percent (mass fraction), the mass ratio of the alkaline protease to the flavourzyme is 2:1, the enzymolysis time is 5 hours, the enzymolysis temperature is 55 ℃, the pH value is 8.5, after 5 hours of enzymolysis, the mixture is heated to 100 ℃ and boiled for 6min to inactivate the enzyme, then the enzymolysis liquid is filtered, and the supernatant is collected.
(3) Adding 50% volume of active carbon into the supernatant, performing oscillation adsorption treatment, centrifuging again to obtain a clear solution, adjusting the pH to 7.0, adding 3% of D-glucose and 2% of L-glutamic acid, stirring, and performing Maillard aroma-producing reaction in an oil bath; the reaction time is 20min, the reaction temperature is 120 ℃, and Maillard incense reaction liquid is obtained.
(4) Mixing citric acid according to the weight ratio of 50: 100 mass ratio and diatomite homogenate are compounded to obtain the heavy metal adsorbent; mixing heavy metal adsorbent and Maillard reaction solution at a mass ratio of 1:100, oscillating and adsorbing at 50 deg.C and pH of 9 for 4h, and centrifuging.
(5) Obtaining reaction liquid which is light brown, clear, transparent, rich in fish flavor, delicious, free of fishy smell, rich in burnt flavor and free of burnt flavor, adding auxiliary materials to prepare the flavor, stirring, cooking and concentrating, subpackaging, sterilizing in a high-pressure sterilization kettle, and obtaining the seafood sauce product.
And (3) taking the enzymolysis liquid obtained after the enzymolysis in the step (2) and the reaction liquid obtained after the Maillard reaction in the step (3) (before adding auxiliary materials), and analyzing flavor substances to obtain results shown in tables 3 and 4.
TABLE 3 comparison of the major volatile odor components of squid enzymolysis liquid and Maillard liquid
Comparative Components | Enzymolysis liquid | Maillard liquid | Variations in |
Amines as herbicides | 33.41% | 7.27% | -26.14% |
Alcohols | 17.17% | 16.64% | -0.53% |
Aldehydes | 8.73% | 18.36% | +9.63% |
Ketones | 5.78% | 10.21% | +4.43% |
Furans | 0.32% | 2.40% | +2.08% |
Pyrazines and their use as anti-inflammatory agents | 1.29% | 9.48% | +8.19% |
Sulfur-containing compounds | 1.55% | 4.11% | +2.56% |
TABLE 4 comparison of characteristic flavor component contents of enzymatic hydrolysate and Maillard liquid
As can be seen from table 3, the maillard reaction of the enzymatic hydrolysate obtained by the complex enzyme hydrolysis under specific conditions can significantly reduce the content of amines, which are the main source of fishy smell, as verified by the large reduction of the DMA and TMA contents in table 4. The flavor threshold of the alcohol substances is higher, and the influence on the flavor is smaller; while the contents of aldehydes, ketones, furans, pyrazines and some sulfur-containing compounds which have a positive influence on the flavor are increased to a certain extent after the Maillard reaction. Wherein, the baking fragrance brought by the alkyl pyrazine is increased to the highest extent, and the crab fragrance in the total flavor is also improved obviously. The Maillard reaction solution obtained according to the conditions is black, bright and clear in color, rich in burnt flavor and fresh and fragrant in taste, and has market prospect of being developed into seafood sauce.
Comparative examples 22 to 23
Comparative examples 22 to 23 are based on example 5, wherein "pH adjustment to 7.0" in the reaction conditions of step (3) was changed to "pH adjustment to 8.0" and "pH adjustment to 9.0", respectively.
Comparative examples 24 to 25
Comparative examples 24 to 25 were prepared by changing the reaction conditions of step (3) from "the reaction temperature was 120 ℃ to" the reaction temperature was 110 ℃ and "the reaction temperature was 100 ℃", respectively, based on example 5.
Comparative examples 26 to 27
Comparative examples 26 to 27 were prepared by changing the reaction conditions of step (3) to "L-glutamic acid 2%" to "L-glutamic acid 1%" and "L-glutamic acid 3%" respectively, based on example 5.
Sensory evaluation scoring was performed according to the sensory evaluation table shown in table 5 with the sensory evaluation score of the maillard aroma-producing reaction solution as the evaluation standard and the ultraviolet spectral absorbance at 420nm as the reference, and the results are shown in table 6 below.
Table 5: maillard reaction product sensory evaluation table
Table 6: sensory evaluation scoring of Maillard reaction solutions under different reaction conditions
Example 6
The maillard aroma-producing reaction liquid obtained in the step (3) of example 5 was subjected to Cd content measurement, and the initial concentration was 2450003 ppb (1ppm to 100 ppb).
Dividing the Maillard fragrance-generating reaction liquid into 8 parts, respectively carrying out heavy metal removal treatment according to the following conditions, and counting the Cd content (ppb) and the removal rate after treatment, wherein the results are shown in the following table 7:
TABLE 7
Acid/soil ratio | Liquid-solid ratio | pH | Adsorption temperature C | Duration h | ppb | Removal rate | |
A | 10:100 | 20:1 | 7 | 30 | 0.5 | 1686.9 | 93.11% |
B | 10:100 | 200:1 | 9 | 40 | 4 | 71.84 | 99.71% |
C | 30:100 | 20:1 | 8 | 50 | 6 | 2540.9 | 89.63% |
D | 30:100 | 80:1 | 7 | 60 | 4 | 3485.89 | 85.77% |
E | 30:100 | 200:1 | 9 | 40 | 0.5 | 206.08 | 99.16% |
F | 50:100 | 20:1 | 9 | 60 | 2 | 1551.8 | 93.67% |
G | 50:100 | 150:1 | 7 | 40 | 6 | 4321.9 | 82.36% |
H | 70:100 | 200:1 | 7 | 50 | 2 | 5409.6 | 77.92% |
According to the experiment in the group E, when the mass ratio of the citric acid to the diatomite is 30:100, the liquid-solid ratio is 200:1, the pH value is 9, and the adsorption temperature is 40 ℃, the adsorption treatment is carried out for 0.5 hour, and the removal rate of Cd in the Maillard reaction liquid reaches 99.16%. Under the same conditions, the citric acid is changed into the same amount of acetic acid and phytic acid, and the removal rate of Cd is less than 80% and 90%.
According to the B group experiment, when the mass ratio of the citric acid to the diatomite is 10:100, the liquid-solid ratio is 200:1, the pH value is 9, and the adsorption temperature is 40 ℃, the adsorption treatment is carried out for 4 hours, the removal rate of Cd in the Maillard reaction liquid reaches 99.71%, the content of Cd in the reaction liquid is 71.84ppb, and the content is lower than the 100ppb concentration specified by the GB2762-2017 standard. According to the H group experiment, the proportion of citric acid is simply improved, and Cd is not easy to remove.
According to the invention, squid viscera and squid skin are used as raw materials, the protein rich in the raw materials is hydrolyzed into amino acid by a biological enzymolysis method, then Maillard aroma enhancement reaction is carried out, and then auxiliary materials are added for stewing, so that the seafood flavor seasoning with unique flavor and rich nutrition is developed, and a new technical approach is provided for reducing the environmental pollution of squid processing by-products, promoting the comprehensive utilization of squid leftovers and improving the technical level of deep processing of squids. The seafood sauce is prepared by compounding the flavor of the squid skin and the internal organs, so that the fishy smell of the internal organs can be reduced to a certain extent, the flavor is blended, the factors of high concentrations of heavy metal and biogenic amine and the like caused by single use of squid internal organs are avoided, and meanwhile, the squid skin is utilized to supplement vitamins, so that the nutrition of the product is coordinated, the waste of squid resources can be greatly reduced, and the utilization efficiency and the economic value of the squid can be improved. The enzymolysis liquid is subjected to Maillard flavor-producing reaction, so that fishy smell and bitter taste after enzymolysis are removed, and meat flavor is added.
Wherein, when squid leftovers are subjected to enzymolysis, the alkali protease and the flavourzyme are compounded for use, so that the effects of masking bitter taste and reducing fishy smell can be achieved
Through analysis of free amino acids in the enzymolysis liquid, when the addition amount of the enzyme is 0.8 percent of the total amount of the slurry, the mass ratio of the alkaline protease to the flavourzyme is 2:1, the enzymolysis time is 5 hours, and when the enzymolysis temperature is 55 ℃, the protein in the substrate of the slurry can be almost completely decomposed into the free amino acids, and the content of free amino nitrogen reaches the highest value. Under the optimized condition, the free amino nitrogen is obtained at 1.085mg/100ml, the yield of amino acid is high, and the enzymolysis efficiency is greatly improved.
In the Maillard flavor-generating reaction, the addition amount of reducing sugar is 3%, the reaction pH is 7.0, the reaction time is 100-120min (more preferably 100min), the reaction temperature is 120 ℃, and when the addition amount of L-glutamic acid is 2%, compared with the enzymolysis solution obtained in the previous step, after the Maillard flavor-generating reaction, the amine content is remarkably reduced (reduced by more than 26%), TMA (fishy syndrome trimethylamine) and DMA (dimethylamine) which generate fishy smell become trace amounts, aldehydes (increased by more than 9.6%), ketones (increased by more than 4.4%), furans (increased by more than 2.0%), pyrazines (increased by more than 8.1%) and some sulfur-containing compounds which have positive influence on the flavor are all increased to a certain extent after the Maillard reaction, wherein the increase range of the "alkylpyrazine" which generates the roasted smell is the highest, and the crab smell is remarkably improved in the overall flavor.
Further, removing heavy metals from the Maillard aroma-producing reaction liquid by using a citric acid-diatomite adsorption combination method, specifically, adding a citric acid solid powder according to the weight ratio of 10-70: compounding 100 mass ratio with diatomite, homogenizing and drying to obtain adsorbent cakes, mixing the adsorbent cakes and Maillard reaction liquid according to the mass ratio of 1:200, oscillating and adsorbing for 4 hours at 40 ℃ and pH 9, reducing the concentration of Cd in the obtained reaction liquid from 24500ppb to 71.84ppb, meeting the GB2762 + 2017 standard, and then centrifuging to further remove heavy metal Cd, thereby meeting the requirement of the national standard on the heavy metal content of fish food flavoring agents.
The reaction liquid treated by the steps is black, bright and clear in color, rich in burnt flavor and fresh and fragrant in taste, and a high-quality seafood sauce product is obtained after the reaction liquid is prepared by auxiliary materials.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A method for preparing seafood sauce by utilizing squid leftovers is characterized in that the squid viscera and squid skin are used as raw materials to prepare the seafood sauce, and the preparation process comprises the following steps:
s1: pulping:
smashing and homogenizing squid viscera and squid skin according to the mass ratio of 3-1: 1;
s2: enzymolysis:
adding enzyme into the slurry containing squid viscera and squid skin for enzymolysis, inactivating enzyme, performing solid-liquid separation, and collecting supernatant; the enzymolysis conditions are as follows: the enzyme is a mixed enzyme composed of alkaline protease and flavourzyme in a mass ratio of 1-2: 1, the addition amount is 0.8-1.0% by mass, the enzymolysis time is 4.5-5h, and the enzymolysis temperature is 50-55 ℃; s3: maillard aroma generation reaction:
subjecting the supernatant obtained in the step S2 to active carbon oscillation adsorption treatment, centrifuging again to obtain a clear solution, adjusting pH, adding D-xylose or/and D-glucose and L-glutamic acid, stirring, and performing Maillard aroma-producing reaction in an oil bath to obtain Maillard aroma-producing reaction liquid;
wherein the addition amount of D-xylose or D-glucose is 1-3%, the addition amount of L-glutamic acid is 1-3%, the reaction pH is 7.0-9.0, the reaction time is 15-25min, and the reaction temperature is 100-120 ℃;
s4: removing heavy metals from the Maillard aroma-producing reaction liquid by using an organic acid-diatomite combination method; the specific method comprises the following steps: uniformly mixing citric acid solid powder and diatomite according to a mass ratio of 10:100, adding water, mixing to obtain slurry, drying to prepare an adsorbent cake, mixing Maillard reaction liquid according to a liquid-solid mass ratio of 200:1, performing oscillation adsorption for 4-6h at the temperature of 40 ℃ and under the condition of pH =9, centrifuging, and collecting clear liquid;
s5: adding adjuvants, blending, stirring, steaming, and concentrating;
s6: subpackaging and sterilizing to obtain the seafood sauce product.
2. The method of claim 1, wherein in step S1, after mixing squid viscera and squid skin and mashing, water is added according to a volume ratio of 1:0.8-1.2 to obtain the slurry used in step S2.
3. The method according to claim 1, wherein the mass ratio of the alkaline protease to the flavourzyme in step S2 is 2: 1.
4. The method according to claim 1, wherein in step S2, the enzymolysis temperature is 55 ℃ and the enzymolysis time is 5 h; the enzymolysis pH = 7-8.5.
5. The method of claim 4, wherein in step S2, the enzymatic pH = 8.5.
6. The method according to claim 1, wherein in step S3, the D-xylose and D-glucose are added in an amount of 3%, the reaction pH is 7.0, the reaction time is 15min, the reaction temperature is 120 ℃, and the L-glutamic acid is added in an amount of 2%.
7. The method according to claim 1, wherein in step S5, the sterilization is membrane filtration or ultra-high pressure sterilization.
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