A method for increasing the nutritional and flavor content of soy sauce and soybean paste and reducing fluorine residue

Abstract

The present invention belongs to the technical field of condiment processing, and specifically relates to a method for increasing the content of nutrients and flavor substances in soy sauce and soybean paste and reducing fluorine residue. The method mainly involves frying Antarctic krill powder and crushing it into powder, and then using it as part of the raw materials for the production of soy sauce and soybean paste. The nutrients and trace elements in the Antarctic krill powder increase the amount of protease and glucoamylase secreted by Aspergillus oryzae, and the synergistic dosage control further increases the taste and nutrient content in soy sauce and soybean paste. At the same time, the present invention combines the use of pH conversion and physical processing technology to significantly reduce the fluorine residue in Antarctic krill soy sauce and soybean paste, so that it meets the edible standards. The Antarctic krill soy sauce and soybean paste produced by the method of the present invention have the characteristics of high nutritional components (amino acids, reducing sugars, selenium and calcium) and added value, product safety, green production technology, and environmental protection, and have broad application prospects.

Description

Technical Field

[0001] The invention relates to a method for increasing the content of nutrients and flavor substances in soy sauce and soybean paste and reducing fluorine residue, belonging to the technical field of condiment processing. Background Art

[0002] Soy sauce and soybean paste are condiments made from soybean meal or soybeans, bran or flour, salt, etc., fermented by Aspergillus oryzae, etc., and are indispensable condiments for people. The main production processes of soy sauce and soybean paste include raw material boiling, inoculation, solid state koji making, liquid / semi-solid state (fermentation in 12-22% salt solution) fermentation, oil pouring, blending, sterilization and packaging, etc. At present, the koji making of soy sauce and soybean paste adopts Aspergillus oryzae single strain koji making, and the fermentation stage of sauce mash is multi-strain fermentation (mainly lactic acid bacteria, yeast, etc.). The enzyme that degrades the raw materials of soy sauce and soybean paste mainly comes from the koji making stage, and the enzyme activity determines the content of small molecular weight flavor substances in the product (mainly free amino acids, small molecular weight peptides and reducing sugars, etc.), which is the core indicator of the quality of soy sauce and soybean paste. Soy sauce and soybean paste prepared by single-strain koji making are highly safe. However, since Aspergillus oryzae produces mostly alkaline and neutral proteases and less acidic proteases, and soy sauce and soybean paste fermentation is mainly carried out in an acidic environment (pH 4.5-5.5), the protease activity decreases rapidly during the production process, resulting in low raw material degradation rate (utilization rate) and flavor substance content in the product, bland taste and low quality.

[0003] Antarctic krill is rich in nutrients such as protein, oil, chitin and mineral elements, and is a potential high-quality food raw material. However, studies have shown that Antarctic krill contains a large amount of fluorine. Excessive intake of fluorine can lead to health problems such as dental caries. Therefore, the high fluorine content restricts the application of Antarctic krill. Since Antarctic krill quickly autolyzes (3h) under the action of autolytic enzymes after fishing, the quality drops rapidly and even becomes inedible. Therefore, Antarctic krill must be processed in time after fishing. Due to the limited processing conditions on Antarctic krill fishing ships, Antarctic krill is currently mainly made into shrimp powder by heat drying / cooking, dehydration and steam drying, crushing, etc. after fishing. The fluoride ion concentration of Antarctic krill powder prepared in this way reaches 1200-2100 mg / kg, which is much higher than the 100 mg / kg stipulated by FAO; therefore, Antarctic krill powder needs to be defluorinated before use or during processing to make the fluoride ion content meet the requirements of food laws and regulations. At present, the main method of defluorination is to treat Antarctic krill / meal with acid (hydrochloric acid) and calcium salt (calcium hydroxide / calcium oxide), which will increase the processing steps, labor and equipment investment of Antarctic krill. Therefore, it will be of great significance to expand the application field of Antarctic krill and remove fluoride ions during the use of Antarctic krill. Summary of the invention

[0004] In view of the deficiencies of the prior art, such as the above-mentioned quality defects of soy sauce and bean paste (bland taste) and the limited application of Antarctic krill, the present invention has developed a method for producing soy sauce and bean paste rich in flavor substances and selenium and calcium using Antarctic krill. The invention not only improves the raw material utilization rate and flavor substance content of soy sauce and bean paste, but also significantly increases the selenium and calcium content in soy sauce and bean paste.

[0005] Specifically, the present invention provides a method for producing high-quality soy sauce and soybean paste by fermenting soybean / soybean meal, flour / bran, salt and Antarctic krill meal as main raw materials using Aspergillus oryzae.

[0006] In order to achieve the above purpose, the specific steps of the present invention are as follows:

[0007] (1) Pretreatment of Antarctic krill powder: using an ultrafine grinder to grind the Antarctic krill powder into a particle size of 1-100 μm to obtain ultrafinely ground Antarctic krill powder;

[0008] (2) Preparation of soy sauce or soybean paste based on Antarctic krill powder:

[0009] (a) Preparation of soy sauce: Soybeans or soybean meal are soaked, boiled and cooled to obtain cooled soybeans or soybean meal; flour or crushed fried wheat is mixed with the ultrafinely crushed Antarctic krill meal obtained in step (1), Aspergillus oryzae koji essence is inoculated into the obtained mixture, the inoculated mixture is mixed with the cooled soybeans or soybean meal and then koji is made, and mature koji is obtained after koji making, and the mature koji is mixed with salt water and then fermented in a tank. After the fermentation is completed, oil is poured or squeezed to extract oil, the oil is allowed to stand and filtered according to a conventional method, the pH of the filtered soy sauce is adjusted to 3.0-4.0 using hydrochloric acid, and ultrasound is used to cooperate with steaming and sterilization and removal of fluoride ions under open conditions, and then the pH of the soy sauce is adjusted using sodium hydroxide, and the finished soy sauce is packaged to obtain the finished soy sauce;

[0010] When the raw material is soybean, the soaking time of the soybean is 12 hours; when the raw material is soybean meal, the soaking time of the soybean meal is 30 minutes, wherein the mass ratio of soybean meal to water is 1:1.1; the cooking temperature of the soybean or soybean meal is 135°C and the cooking time is 5 minutes;

[0011] The mass ratio of the soybean or soybean meal, flour or crushed fried wheat and ultrafinely crushed Antarctic krill powder is 50:15:5-40;

[0012] The inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials; the total mass of the raw materials is the sum of the mass of soybeans or soybean meal (dry weight), flour or crushed fried wheat and ultrafinely crushed Antarctic shrimp powder; the koji making temperature is 29° C., the time is 43 hours, and the relative humidity is 95%;

[0013] The mature Daqu is mixed with salt water and then fermented in a tank. When preparing high-salt dilute soy sauce, the mass percentage concentration of the salt water is 21%, and the mass ratio of mature Daqu to salt water is 1:2.5; when preparing low-salt solid soy sauce, the mass percentage concentration of the salt water is 12%, and the mass ratio of mature Daqu to salt water during the fermentation stage is 1:1. After the fermentation is completed, 12% salt water with a mass of 1.5 times the mass of the raw materials is added for leaching; wherein the high-salt dilute soy sauce is fermented at room temperature for 180 days; the low-salt solid soy sauce is fermented at 47°C for 30 days;

[0014] The sterilization conditions are 65-100° C., 10-60 min, and the ultrasonic conditions are: ultrasonic intensity 10-100 W / L, 10-60 min, and frequency 20-60 kHz.

[0015] The molar concentration of sodium hydroxide is 6M / L, and the molar concentration of hydrochloric acid is 6M / L; the pH value of the soy sauce is adjusted to 4.7 again.

[0016] Preferably, the Antarctic krill powder in step (1) is crushed to a particle size of 30-60 μm.

[0017] Preferably, the mass ratio of soybean, flour or crushed fried wheat and ultrafinely crushed Antarctic krill powder in step (2) (a) is 50:1515-35;

[0018] Preferably, the steaming and sterilization conditions are 75-90°C, 30-40min, and the ultrasonic conditions are: ultrasonic intensity 30-70W / L, 30-40min, frequency 35-50kHz.

[0019] (b) Preparation of soybean paste: Soybeans are soaked, steamed and cooled to obtain cooled soybeans; flour is then mixed with the ultrafinely crushed Antarctic krill powder obtained in step (1), the mixture is inoculated with Aspergillus oryzae koji essence, the inoculated mixture is subjected to koji making to obtain mature koji, which is then mixed with salt water and fermented in a tank; after the fermentation is completed, hydrochloric acid is used to adjust the pH to 3.0-4.0; the mixture is steamed and stirred in an open environment to sterilize and remove fluoride ions; the pH is then adjusted using sodium hydroxide; and the finished soybean paste is obtained after packaging.

[0020] The soybean soaking time is 12 hours; the soybean steaming temperature is 135° C. and the time is 5 minutes;

[0021] The mass ratio of soybean, flour and superfine Antarctic krill powder is 50:15:5-40;

[0022] The inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials; the total mass of the raw materials is the sum of the mass of soybeans (dry weight), flour and ultrafinely crushed Antarctic shrimp powder; the koji making temperature is 29° C., the time is 43 hours, and the relative humidity is 95%;

[0023] The mass concentration of the brine is 18%; the ratio of the mature Daqu to the brine is 1:1.5; the fermentation is carried out at room temperature and the fermentation time is 30 days;

[0024] The sterilization conditions are as follows: the sterilization temperature is 65-100° C. and the sterilization time is 10-60 min; and the stirring conditions are as follows: the stirring speed is 10-100 rpm and the stirring time is 10-60 min.

[0025] The molar concentration of sodium hydroxide is 6M / L, and the molar concentration of hydrochloric acid is 6M / L; the pH of the bean paste is adjusted to 4.7 again.

[0026] Preferably, the mass ratio of soybean, flour and ultrafinely crushed Antarctic krill powder in step (2) (b) is 50:15:15-35;

[0027] Preferably, the sterilization conditions in step (2) (b) are as follows: the sterilization temperature is 75-90°C and the sterilization time is 30-40 min; and the stirring conditions are as follows: the stirring speed is 40-70 rpm and the stirring time is 30-40 min.

[0028] Beneficial effects of the present invention:

[0029] The present invention uses Antarctic krill powder as a raw material for the production of soy sauce and soybean paste after it is fried and crushed. The nutrients and trace elements in the Antarctic krill powder increase the amount of protease and glucoamylase secreted by Aspergillus oryzae, and the synergistic dosage control further increases the taste and nutrient content in the soy sauce and soybean paste; the soy sauce and soybean paste produced by the method of the present invention have significantly higher total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium, and calcium content than the control, and the quality is significantly improved. At the same time, the present invention combines the use of pH conversion and physical processing technology to significantly reduce the fluorine residue in Antarctic krill soy sauce and soybean paste, and the fluorine ion residue is far lower than the 100 mg / kg specified by FAO, so that it meets the food standard. The method of the present invention is simple to operate, low in investment cost, and significantly improves the added value of new products, and has important economic value and social significance.

[0030] Appendix Description

[0031] As shown in Table 1, the particle size of Antarctic krill powder has a significant effect on the enzyme activity of Daqu prepared with soybean and flour as the main raw materials (p<0.05).

[0032] As the particle size of Antarctic krill powder decreases, the enzyme activity of Daqu (alkaline, acidic and neutral proteases and glucoamylase) shows a trend of first increasing and then decreasing, but the Daqu enzyme activity of superfinely crushed Antarctic krill powder is significantly higher than that of the control (p<0.05). Among them, when the particle size of Antarctic krill powder is 40-50μm, the activity of various enzymes in Daqu is the highest, and the effect is the most prominent. The possible reason for the above phenomenon is that when the particle size of Antarctic krill powder is too large (>40-50μm), it is not conducive to the absorption and utilization of Aspergillus oryzae; when the particle size is too small (<40-50μm), it is easy to block the gaps between the raw materials, which is not conducive to air circulation and heat dissipation. Aspergillus oryzae is an aerobic bacterium and is not heat-resistant (<35℃), which leads to a decrease in the enzyme activity of Aspergillus oryzae. In summary, when Antarctic krill powder is used to make koji, its particle size has an important influence on the quality of Daqu (preparing Daqu with soybeans and flour as the main raw materials).

[0033] Table 1 Effect of particle size of ultrafinely ground Antarctic krill powder on enzyme activity of Daqu (soybean, flour, ultrafinely ground Antarctic krill powder as raw materials)

[0034]

[0035] Note: The control is conventional Antarctic krill powder (particle size 2-3mm) that has not been ultrafinely crushed. Samples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 are Daqu prepared with Antarctic krill powder with particle sizes of 1-10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 80-90 and 90-100 μm as raw materials, respectively. The mass ratio of raw materials for the control and samples is soybean: flour: Antarctic krill powder = 50:15:25, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials.

[0036] As shown in Table 2, the particle size of Antarctic krill meal has a significant effect on the enzyme activity of Daqu prepared with soybean meal and crushed fried wheat flour as the main raw materials (p<0.05).

[0037] As the particle size of Antarctic krill meal decreases, the enzyme activity of Daqu (alkaline, acidic and neutral proteases and glucoamylase) shows a trend of first increasing and then decreasing, but the Daqu enzyme activity of superfinely crushed Antarctic krill meal is significantly higher than that of the control (p<0.05), and the activity of various enzymes in Daqu is the highest when the particle size of Antarctic krill meal is 40-50μm. The reason for the above phenomenon is also that the particle size of Antarctic krill meal is too large (>40-50μm), which is not conducive to the absorption and utilization of Aspergillus oryzae; and when the particle size is too small (<40-50μm), it is easy to block the gaps between the raw materials, which is not conducive to air circulation and heat dissipation. Aspergillus oryzae is an aerobic bacterium and is not heat-resistant (<35℃), which leads to a decrease in the enzyme activity of Aspergillus oryzae. In summary, when Antarctic krill meal is used to make koji, its particle size has an important influence on the quality of Daqu (Daqu prepared with soybean meal and crushed fried wheat flour as the main raw materials).

[0038] Table 2 Effect of particle size of ultrafinely crushed Antarctic krill powder on enzyme activity of Daqu (soybean, crushed fried wheat flour, ultrafinely crushed Antarctic shrimp powder as raw materials)

[0039]

[0040] Note: The control is conventional Antarctic krill powder (particle size 2-3mm) that has not been ultrafinely crushed. Samples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 are Daqu prepared with Antarctic krill powder with particle sizes of 1-10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 80-90 and 90-100 μm as raw materials, respectively. The mass ratio of raw materials for the control and samples is soybean meal: crushed fried wheat flour: Antarctic krill powder = 50:15:25, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials.

[0041] As shown in Table 3, the addition amount of Antarctic krill meal has a significant effect on the enzyme activity of Daqu prepared with soybean and flour as the main raw materials (p<0.05).

[0042] As the amount of Antarctic krill meal added increased, the enzyme activity of Daqu (alkaline, acidic and neutral proteases and glucoamylase) showed a trend of first increasing and then decreasing, but the enzyme activity of Daqu with the addition of ultrafine Antarctic krill meal was significantly higher than that of the control (p<0.05), and a significant effect was achieved when the mass ratio of soybean, flour and ultrafine Antarctic krill meal was 50:15:15-35. When the amount of Antarctic krill meal added was 27.8% (i.e., sample 5, the ratio was 50:15:25), the activity of various enzymes in Daqu was the highest. The possible reason for the above phenomenon is that Antarctic krill meal contains chitin with antibacterial effect. When the amount of Antarctic krill meal added is too high, it will inhibit the growth, reproduction and enzyme production of Aspergillus oryzae, resulting in a decrease in enzyme activity. In summary, the amount of Antarctic krill meal added when making koji has an important influence on the enzyme activity of Daqu (Daqu prepared with soybean and flour as the main raw materials).

[0043] Table 3 Effects of the ratio of soybean, flour and superfinely crushed Antarctic krill powder on the activity of Daqu enzyme

[0044]

[0045]

[0046] Note: The control Daqu is a Daqu prepared with soybean and flour in a mass ratio of 75:25 as raw materials; the Daqu of sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7 and sample 8 are Daqu prepared with soybean, flour and ultrafinely crushed Antarctic krill powder in a mass ratio of 50:15:5, 50:15:10, 50:15:15, 50:15:20, 50:15:25, 50:15:30, 50:15:35 and 50:15:40 as raw materials, respectively, the particle size of Antarctic krill powder is 40-50μm, and the inoculation amount of Aspergillus oryzae koji essence is 0.2% of the total mass of the raw materials.

[0047] As shown in Table 4, the addition amount of Antarctic krill meal had a significant effect on the enzyme activity of Daqu prepared with soybean meal and crushed roasted wheat as the main raw materials (p<0.05).

[0048] As the amount of Antarctic krill meal added increases, the enzyme activity of Daqu (alkaline, acidic and neutral proteases and glucoamylase) shows a trend of first increasing and then decreasing, but the enzyme activity of Daqu with the addition of ultrafine Antarctic krill meal is significantly higher than that of the control (p<0.05). The effect is particularly prominent when the mass ratio of soybean meal, crushed fried wheat and ultrafine Antarctic krill meal is 50:15:20-35. When the amount of Antarctic krill meal added is 27.8% (i.e., sample 5), the activity of various enzymes in Daqu is the highest. The possible reason for the above phenomenon is that Antarctic krill meal contains chitin with antibacterial effect. When the amount of Antarctic krill meal added is too high, it inhibits the growth, reproduction and enzyme production of Aspergillus oryzae, resulting in a decrease in enzyme activity. In summary, the amount of Antarctic krill meal added when making koji has an important influence on the enzyme activity of Daqu (Daqu prepared with soybean meal and crushed fried wheat as the main raw materials).

[0049] Table 4 Effect of the ratio of soybean meal, crushed fried wheat and ultrafinely crushed Antarctic krill meal on the activity of Daqu enzyme

[0050]

[0051] Note: (1) The control Daqu was prepared with soybean and flour in a mass ratio of 75:25 as raw materials; the Daqu of samples 1, 2, 3, 4, 5, 6, 7 and 8 were prepared with soybean meal, crushed fried wheat and superfinely crushed Antarctic krill powder in a mass ratio of 50:15:5, 50:15:10, 50:15:15, 50:15:20, 50:15:25, 50:15:30, 50:15:35 and 50:15:40 as raw materials, respectively. The particle size of Antarctic krill powder was 40-50 μm, and the inoculation amount of Aspergillus oryzae koji was 0.2% of the total mass of the raw materials. (2) The results are mean ± standard deviation (n = 3); if different data in the same column do not contain the same lowercase letters, it means that there is a significant difference between the data (p < 0.05).

[0052] As shown in Table 5, the pH, sterilization temperature, sterilization time, ultrasonic intensity, ultrasonic time and ultrasonic frequency during soy sauce sterilization all have an important influence on the fluorine residue in soy sauce (p<0.05).

[0053] As the pH value increases, the residual fluorine content in soy sauce gradually increases, especially when pH>4.0, the residual fluorine content increases significantly. Although the lower the pH, the lower the residual fluorine content in soy sauce, too low a pH makes the soy sauce lose its original flavor, so after defluorination of the soy sauce, it is necessary to readjust the pH with sodium hydroxide; if the pH during defluorination is too low, a large amount of sodium hydroxide needs to be added later, and sodium hydroxide will be neutralized with hydrochloric acid in the soy sauce to generate NaCl, which will increase the salt content of the soy sauce and bring adverse effects, so the preferred pH is 3.0-4.0. As the sterilization temperature increases and the sterilization time prolongs, the residual fluorine content in the soy sauce gradually decreases, but the rate of decrease of the residual fluorine content decreases rapidly after the temperature is higher than 86°C and the sterilization time is longer than 30 minutes. Considering that excessively high temperatures and long-term sterilization will have an adverse effect on the flavor of the soy sauce and increase energy consumption, the sterilization temperature and time should not be too high or too long, preferably 65-100°C. With the increase and extension of ultrasonic intensity and time, the fluorine residue in soy sauce decreases rapidly, but the rate of decrease of fluorine residue in soy sauce decreases when the ultrasonic intensity and time are higher than 30W / L and longer than 20min. Moreover, if the ultrasonic intensity and time are too high and too long, it may affect the overall flavor of soy sauce. Therefore, the ultrasonic intensity and time should not be too high and too long. With the increase of ultrasonic frequency, the fluorine content in soy sauce shows a trend of first decreasing and then increasing, indicating that the effect of ultrasonic frequency on the removal of fluorine residue in soy sauce is more complicated. On the whole, good results can be achieved when the ultrasonic intensity is 10-100W / L, 10-60min, and the frequency is 20-60kHz. However, when the ultrasonic conditions are: ultrasonic intensity 30-70W / L, 30-60min, and frequency 35-50kHz, the effect is more significant. The above analysis shows that the process of removing fluorine residue in soy sauce produced by Antarctic krill is complicated, and a large number of experiments are required to obtain the optimal production process.

[0054] Table 5 Effect of production process conditions on fluorine residue in soy sauce produced from Antarctic krill meal (mg / L)

[0055]

[0056]

[0057] Note: (1) Experimental conditions for the effect of pH on the residual fluorine content in soy sauce: the mass ratio of the Daqu raw materials was soybean meal: crushed fried wheat flour: Antarctic krill powder = 50:15:25, the sterilization conditions were temperature 79°C, time 30 min, ultrasonic conditions were ultrasonic intensity 55 W / L, time 30 min, frequency 35 kHz, and the inoculation amount of Aspergillus oryzae koji extract was 0.2% of the total mass of the raw materials.

[0058] (2) Effect of sterilization temperature on fluorine residue in soy sauce Experimental conditions: the mass ratio of Daqu raw materials was soybean meal: crushed fried wheat flour: Antarctic krill powder = 50:15:25, the pH of soy sauce was 3.2, the sterilization condition was time 30 min, the ultrasonic conditions were ultrasonic intensity 55 W / L, time 30 min, frequency 35 kHz, and the inoculum amount of Aspergillus oryzae koji was 0.2% of the total mass of the raw materials.

[0059] (3) Experimental conditions for the effect of sterilization time on the residual fluorine content in soy sauce: the mass ratio of the Daqu raw materials was soybean meal: crushed fried wheat flour: Antarctic krill powder = 50:15:25, the pH of the soy sauce was 3.2, the sterilization conditions were temperature 79°C, the ultrasonic conditions were ultrasonic intensity 55 W / L, time 30 min, frequency 35 kHz, and the inoculum amount of Aspergillus oryzae koji extract was 0.2% of the total mass of the raw materials.

[0060] (4) Effect of ultrasonic intensity on the residual fluorine content in soy sauce Experimental conditions: the mass ratio of the Daqu raw materials was soybean meal: crushed fried wheat flour: Antarctic krill powder = 50:15:25, the pH of the soy sauce was 3.2, the sterilization conditions were temperature 79°C, time 30 min, the ultrasonic conditions were ultrasonic time 30 min, frequency 35 kHz, and the inoculum amount of Aspergillus oryzae koji was 0.2% of the total mass of the raw materials.

[0061] (5) Experimental conditions for the effect of ultrasonic time on the residual fluorine content in soy sauce: the mass ratio of the Daqu raw materials was soybean meal: crushed fried wheat flour: Antarctic krill powder = 50:15:25, the pH of the soy sauce was 3.2, the sterilization conditions were temperature 79°C, time 30 min, ultrasonic conditions were ultrasonic intensity 55 W / L, frequency 35 kHz, and the inoculum amount of Aspergillus oryzae koji was 0.2% of the total mass of the raw materials.

[0062] (6) Experimental conditions for the effect of ultrasonic frequency on the residual fluorine content in soy sauce: the mass ratio of the Daqu raw materials was soybean meal: crushed fried wheat flour: Antarctic krill powder = 50:15:25, the pH of the soy sauce was 3.2, the sterilization conditions were temperature 79°C, time 30 min, the ultrasonic conditions were ultrasonic intensity 55 W / L, time 30 min, and the inoculum amount of Aspergillus oryzae koji was 0.2% of the total mass of the raw materials.

[0063] (7) The results are mean ± SD (n = 3). If different data in the same row do not contain the same lowercase letters, it means that there is a significant difference between the data (p < 0.05).

[0064] It can be seen from Table 6 that the pH, sterilization temperature, sterilization time, stirring speed and stirring time during soybean paste sterilization all have an important influence on the fluorine residue in soybean paste (p<0.05).

[0065] As the pH value increases, the residual fluorine content in soybean paste gradually increases, especially when the pH is > 4.0. Although the lower the pH, the lower the residual fluorine content in soybean paste, but too low a pH will make soybean paste lose its original flavor. Therefore, after defluorination of soybean paste, sodium hydroxide needs to be used to adjust the pH back to near the normal pH of soybean paste. If the pH used during defluorination is too low, a large amount of sodium hydroxide needs to be added. Sodium hydroxide and hydrochloric acid in soybean paste are neutralized to form NaCl, which increases the salt content of soybean paste, which is not good for the health of consumers. As the sterilization temperature increases and the sterilization time prolongs, the residual fluorine content in soybean paste gradually decreases, but the rate of decline of the residual fluorine content decreases rapidly when the temperature is higher than 86°C and the sterilization time is longer than 30 minutes. Considering that excessively high temperature and long-term sterilization will have an adverse effect on the flavor of soybean paste and increase energy consumption, the sterilization temperature and time should not be too high or too long. With the increase and extension of stirring speed and time, the residual fluorine in soybean paste decreases rapidly, but the rate of decrease of residual fluorine in soybean paste decreases when the stirring speed and time are higher than 55rpm and longer than 30min, so the stirring speed and time should not be too high or too long. On the whole, when the sterilization temperature is 65-100℃, the sterilization time is 10-60min; and the stirring conditions are: stirring speed is 10-100rpm, stirring time is 10-60min, good results can be achieved; when the sterilization temperature is 72-100℃, the sterilization time is 30-60min; and the stirring conditions are: stirring speed is 55-100rpm, stirring time is 30-60min, the effect is particularly significant; the above analysis shows that the process of removing residual fluorine in soybean paste produced by Antarctic krill is complicated, and targeted research is needed to obtain the optimal production process.

[0066] Table 6 Effect of production process conditions on fluorine residue in soybean paste produced using Antarctic krill powder (mg / L)

[0067]

[0068] Note: (1) Experimental conditions for the effect of pH on the residual fluorine content in soybean paste: the mass ratio of the Daqu raw materials was soybean: flour: Antarctic krill powder = 50:15:25, the sterilization conditions were temperature 79°C, time 30 min, stirring conditions were stirring speed 55 rpm, time 30 min, and the inoculation amount of Aspergillus oryzae koji extract was 0.2% of the total mass of the raw materials.

[0069] (2) Experimental conditions for the effect of sterilization temperature on the residual fluorine content in soybean paste: the mass ratio of the Daqu raw materials was soybean: flour: Antarctic krill powder = 50:15:25, the pH of the soybean paste was 3.2, the sterilization condition was 30 min, the stirring condition was 55 rpm, the time was 30 min, and the inoculation amount of Aspergillus oryzae koji was 0.2% of the total mass of the raw materials.

[0070] (3) Experimental conditions for the effect of sterilization time on the residual fluorine content in soybean paste: the mass ratio of the Daqu raw materials was soybean: flour: Antarctic krill powder = 50:15:25, the pH of the soybean paste was 3.2, the sterilization conditions were a temperature of 79°C, the stirring conditions were a stirring speed of 55 rpm and a time of 30 min, and the inoculum amount of Aspergillus oryzae koji was 0.2% of the total mass of the raw materials.

[0071] (4) Experimental conditions for the effect of stirring speed on the residual fluorine content in soybean paste: the mass ratio of the Daqu raw materials was soybean: flour: Antarctic krill powder = 50:15:25, the pH of the soybean paste was 3.2, the sterilization conditions were temperature 79°C, time 30 min, stirring time 30 min, and the inoculum amount of Aspergillus oryzae koji was 0.2% of the total mass of the raw materials.

[0072] (5) Experimental conditions for the effect of stirring time on the residual fluorine content in soybean paste: the mass ratio of the Daqu raw materials was soybean: flour: Antarctic krill powder = 50:15:25, the pH of the soybean paste was 3.2, the sterilization conditions were temperature 79°C, time 30 min, ultrasonic speed 55 rpm, and the inoculation amount of Aspergillus oryzae koji was 0.2% of the total mass of the raw materials.

[0073] (6) The results are mean ± SD (n = 3). If different data in the same row do not contain the same lowercase letters, it means that there is a significant difference between the data (p < 0.05). DETAILED DESCRIPTION

[0074] The specific implementation modes of the present invention are further described below in conjunction with examples, but the implementation and protection scope of the present invention are not limited thereto.

[0075] The determination of total selenium, organic selenium, koji enzyme activity, total nitrogen, amino acid nitrogen, reducing sugar and other indicators involved in the present invention refers to the methods in the literature (Gao et al. Effects of sonication during moromi fermentation on antioxidant activities of compounds in raw soy sauce. LWT-Food Science and Technology, 2019, 116: 108605.; Gao et al. A comparative study on physicochemical properties of Chinese-type soy sauces prepared using pure koji and mixed kojis. African Journal of Biotechnology, 2010, 9 (40): 6740–6747.); the determination of calcium and fluoride content refers to the methods in the literature (Quan Qinguo et al. Composition analysis and nutritional evaluation of Antarctic krill meal [J]. Food and Machinery, 2018, 34 (9): 68-76.).

[0076] Example 1: A method for increasing the nutritional and flavor content of soy sauce and reducing the residual fluorine content, the specific method is as follows:

[0077] (1) grinding Antarctic krill powder to a particle size of 1 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0078] (2) Soak soybeans for 12 h, cook at 135 °C for 5 min, and cool;

[0079] (3) mixing flour with ultrafinely crushed Antarctic krill powder, inoculating the obtained mixture with Aspergillus oryzae koji, mixing the inoculated mixture with the cooled soybeans and then making koji, wherein the mass ratio of soybeans, flour and ultrafinely crushed Antarctic krill powder is 50:15:5, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybeans (dry weight), flour and ultrafinely crushed Antarctic krill powder);

[0080] (4) The koji making conditions were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 12% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:1;

[0081] (5) After fermentation for 30 days, add the above-mentioned brine in an amount of 1.5 times the total mass of the raw materials for leaching, then squeeze out the oil, let it stand, and filter;

[0082] (6) The pH of the filtered soy sauce is adjusted to 4.0 using 6M / L hydrochloric acid, and sterilized and fluoride ion removed by ultrasonic assisted cooking under open conditions. The sterilization conditions are 65°C, 60 min, and the ultrasonic conditions are ultrasonic intensity 10W / L, 60 min, and frequency 20 kHz. Then, the pH of the soy sauce is adjusted to 4.7 using 6M / L sodium hydroxide, and the finished soy sauce is obtained after packaging.

[0083] Control soy sauce 1: the raw materials are soybean and flour, the mass ratio is 55:15, and the other conditions are the same as the preparation method of Example 1;

[0084] Control soy sauce 2: the raw materials and raw material ratios are the same as those in Example 1; the difference is that the pH of the soy sauce after filtration in step (6) is not adjusted, and the other conditions are the same as those in Example 1;

[0085] Control soy sauce 3: The raw materials and raw material ratios used were the same as those in Example 1; the difference was that ultrasonic treatment was not performed, and other conditions were the same as those in Example 1.

[0086] Control soy sauce 4: The raw materials and raw material ratios used were the same as those in Example 1; the difference was that the pH of the soy sauce after filtration in step (6) was not adjusted and ultrasonic treatment was not performed. Other conditions were the same as in Example 1.

[0087] As shown in Table 7, the total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soy sauce produced according to the method of the present invention and the control 2, control 3 and control 4 soy sauces are significantly higher than those of the control 1 (p<0.05), indicating that the method of the present invention significantly improves the content of nutrients (total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (total nitrogen, amino acid nitrogen, reducing sugar) in soy sauce. As shown in Tables 1-4, the addition of ultrafinely crushed Antarctic krill powder can significantly increase the activity of protease and glucoamylase in Daqu, and protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing substances (total nitrogen) and free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar. In addition, the selenium and calcium contents of Antarctic krill powder are about 3.8 mg / kg and 2.6%. Since soy sauce is an acidic environment, selenium and calcium will gradually blend into soy sauce during the fermentation process. This is the key reason for adding ultrafinely crushed Antarctic krill powder to improve the nutrition and flavor substances of soy sauce. In addition, according to the Shaanxi Province Standard for Selenium-rich Condiments (>75μg / kg, DB61 / T 556-2018), the soy sauce produced by the method of the present invention is a selenium-rich food, and the added value of the soy sauce produced using the technology of the present invention will be significantly improved.

[0088] As shown in Table 7, the fluorine residue in the sample soy sauce produced according to the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard specified by FAO (<100 mg / kg), indicating that the method of the present invention significantly removes the fluorine residue in the soy sauce, and the produced soy sauce is highly safe and has important commercial value.

[0089] Table 7 Nutrition, flavor substances and fluorine content of low-salt solid soy sauce produced by the method of the present invention

[0090]

[0091] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data ( p <0.05).

[0092] Example 2: A method for increasing the nutritional and flavor content of soy sauce and reducing the residual fluorine content, the specific method is as follows:

[0093] (1) grinding Antarctic krill powder to a particle size of 15 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0094] (2) Soak soybeans for 12 h, cook at 135 °C for 5 min, and cool;

[0095] (3) mixing flour with ultrafinely crushed Antarctic krill powder, inoculating the obtained mixture with Aspergillus oryzae koji, mixing the inoculated mixture with the cooled soybeans and then making koji, wherein the mass ratio of soybeans, flour and ultrafinely crushed Antarctic krill powder is 50:15:10, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybeans (dry weight), flour and ultrafinely crushed Antarctic krill powder);

[0096] (4) The koji making conditions were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 12% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:1;

[0097] (5) After fermentation for 30 days, add the above-mentioned brine in an amount of 1.5 times the total mass of the raw materials for leaching, then squeeze out the oil, let it stand, and filter;

[0098] (6) The pH of the filtered soy sauce was adjusted to 3.8 using 6 M / L hydrochloric acid, and sterilized and fluoride ion removed by ultrasonic assisted cooking under open conditions. The sterilization conditions were 70° C. and 53 min, and the ultrasonic conditions were ultrasonic intensity 23 W / L, 53 min, and frequency 25 kHz. Then, the pH of the soy sauce was adjusted to 4.7 using 6 M / L sodium hydroxide, and the finished soy sauce was obtained after packaging.

[0099] Control soy sauce 1: the raw materials are soybean and flour, the mass ratio is 60:15, and other conditions are the same as the above sample preparation method;

[0100] Control soy sauce 2: the raw materials and raw material ratios are the same as those in Example 2; the difference is that the pH of the soy sauce after filtration in step (6) is not adjusted, and the other operations are the same as those in Example 2;

[0101] Control soy sauce 3: The raw materials and raw material ratios used were the same as those in Example 2; the difference was that ultrasonic treatment was not performed, and other operations were the same as in Example 2.

[0102] Control soy sauce 4: The raw materials and raw material ratios used were the same as those in Example 2; the difference was that the pH of the soy sauce after filtration in step (6) was not adjusted and ultrasonic treatment was not performed; other operations were the same as in Example 2.

[0103] As shown in Table 8, the total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soy sauce produced according to the method of the present invention and the control 2, control 3 and control 4 soy sauces are significantly higher than those of the control 1 (p<0.05), indicating that the method of the present invention significantly improves the content of nutrients (total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (total nitrogen, amino acid nitrogen, reducing sugar) in soy sauce. As shown in Tables 1-4, the addition of ultrafinely crushed Antarctic krill powder can significantly improve the enzyme activity of protease and glucoamylase in Daqu, and protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing substances (total nitrogen) and free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar. In addition, the selenium and calcium contents of Antarctic krill powder are about 3.8 mg / kg and 2.6%. Since soy sauce is an acidic environment, selenium and calcium will gradually blend into soy sauce during the fermentation process. This is the key reason for adding ultrafinely crushed Antarctic krill powder to improve the nutrition and flavor substances of soy sauce. In addition, according to the Shaanxi Province Standard for Selenium-rich Condiments (>75μg / kg, DB61 / T 556-2018), the soy sauce produced by the method of the present invention is a selenium-rich food, and the added value of the soy sauce produced using the technology of the present invention will be significantly improved.

[0104] As shown in Table 8, the fluorine residue in the soy sauce samples produced according to the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard specified by FAO (<100 mg / kg), indicating that the method of the present invention significantly removes the fluorine residue in the soy sauce, and the produced soy sauce is highly safe and has important commercial value.

[0105] Table 8 Nutrition, flavor substances and fluorine content of low-salt solid soy sauce produced by the method of the present invention

[0106]

[0107]

[0108] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data (p < 0.05).

[0109] Example 3: A method for increasing the nutritional and flavor content of soy sauce and reducing the residual fluorine content, the specific method is as follows:

[0110] (1) grinding Antarctic krill powder to a particle size of 30 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0111] (2) Soaking soybean meal for 30 min, cooking at 135°C for 5 min, and cooling;

[0112] (3) mixing the crushed roasted wheat with the ultrafinely crushed Antarctic krill meal, inoculating the obtained mixture with Aspergillus oryzae koji, mixing the inoculated mixture with the cooled soybeans and then making koji, wherein the mass ratio of soybeans, flour and ultrafinely crushed Antarctic krill meal is 50:15:15, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybeans (dry weight), flour and ultrafinely crushed Antarctic krill meal);

[0113] (4) The koji making conditions were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 23% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:2.5;

[0114] (5) After 180 days of fermentation, pour oil, let stand, and filter;

[0115] (6) The pH of the filtered soy sauce was adjusted to 3.6 using 6 M / L hydrochloric acid, and sterilized and fluoride ion removed by ultrasonic assisted cooking under open conditions. The sterilization conditions were 75° C. and 46 min, and the ultrasonic conditions were ultrasonic intensity 36 W / L, 46 min, and frequency 30 kHz. Then, the soy sauce was adjusted to pH 4.7 using 6 M / L sodium hydroxide, and the finished soy sauce was obtained after packaging.

[0116] Control soy sauce 1: the raw materials are soybean and flour, the mass ratio is 65:15, and the rest is the same as Example 3;

[0117] Control soy sauce 2: the raw materials and raw material ratios are the same as those in Example 3; the difference is that the pH of the soy sauce after filtration in step (6) is not adjusted, and the other operations are the same as those in Example 3;

[0118] Control soy sauce 3: The raw materials and raw material ratios used were the same as those in Example 3; the difference was that ultrasonic treatment was not performed, and the operation was the same as in Example 3.

[0119] Control soy sauce 4: The raw materials and raw material ratios used were the same as those in Example 3; the difference was that the pH of the soy sauce after filtration in step (6) was not adjusted and ultrasonic treatment was not performed. Other operations were the same as those in Example 3.

[0120] As shown in Table 9, the total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soy sauce produced according to the method of the present invention and the control 2, control 3 and control 4 soy sauces are significantly higher than those of the control 1 (p<0.05), indicating that the method of the present invention significantly improves the content of nutrients (total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (total nitrogen, amino acid nitrogen, reducing sugar) in soy sauce. As shown in Tables 1-4, the addition of ultrafinely crushed Antarctic krill powder can significantly improve the enzyme activity of protease and glucoamylase in Daqu, and protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing substances (total nitrogen) and free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar. In addition, the selenium and calcium contents of Antarctic krill powder are about 3.8 mg / kg and 2.6%. Since soy sauce is an acidic environment, selenium and calcium will gradually blend into soy sauce during the fermentation process. This is the key reason for adding ultrafinely crushed Antarctic krill powder to improve the nutrition and flavor substances of soy sauce. In addition, according to the Shaanxi Province Standard for Selenium-rich Condiments (>75μg / kg, DB61 / T 556-2018), the soy sauce produced by the method of the present invention is a selenium-rich food, and the added value of the soy sauce produced using the technology of the present invention will be significantly improved.

[0121] As shown in Table 9, the fluorine residue in the soy sauce samples produced by the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard (<100 mg / kg) specified by FAO, indicating that the method of the present invention significantly removes the fluorine residue in the soy sauce, and the produced soy sauce is highly safe.

[0122] Table 9 Nutrition, flavor substances and fluorine content of high-salt dilute soy sauce produced by the method of the present invention

[0123]

[0124] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data (p < 0.05).

[0125] Example 4: A method for increasing the nutritional and flavor content of soy sauce and reducing the residual fluorine content, the specific method is as follows:

[0126] (1) grinding Antarctic krill powder to a particle size of 45 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0127] (2) soybean meal was mixed with 1.1 times the mass ratio of water, moistened for 30 min, then steamed at 135°C for 5 min, and cooled;

[0128] (3) mixing the crushed fried wheat with the ultrafinely crushed Antarctic krill meal, inoculating the obtained mixture with Aspergillus oryzae koji, and mixing the inoculated mixture with the cooled soybean meal to make koji, wherein the mass ratio of soybean meal, crushed fried wheat and ultrafinely crushed Antarctic krill meal is 50:15:20, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybean meal (dry weight), crushed fried wheat and ultrafinely crushed Antarctic krill meal);

[0129] (4) The koji making conditions were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 21% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:2.5;

[0130] (5) After 180 days of fermentation, pour oil, let stand, and filter;

[0131] (6) The pH of the filtered soy sauce was adjusted to 3.4 using 6 M / L hydrochloric acid, and sterilized and fluoride ion removed by ultrasonic assisted cooking under open conditions. The sterilization conditions were 80° C. and 39 min, and the ultrasonic conditions were ultrasonic intensity 50 W / L, 39 min, and frequency 36 kHz. Then, the soy sauce was adjusted to pH 4.7 using 6 M / L sodium hydroxide, and the finished soy sauce was obtained after packaging.

[0132] Control soy sauce 1: the raw materials are soybean meal and crushed fried wheat, the mass ratio is 65:15, and other conditions are the same as the above sample preparation method;

[0133] Control soy sauce 2: the raw materials and raw material ratios used were the same as those in Example 4; the difference was that the pH of the soy sauce after filtration in step (6) was not adjusted, and the other conditions were the same as those in Example 4;

[0134] Control soy sauce 3: The raw materials and raw material ratios used were the same as those in Example 4; the difference was that no ultrasonic treatment was performed, but the pH was adjusted to 3.4, and the other conditions were the same as those in Example 4.

[0135] Control soy sauce 4: The raw materials and raw material ratios used were the same as those in Example 4; the difference was that the pH of the soy sauce after filtration in step (6) was not adjusted and ultrasonic treatment was not performed, and other conditions were the same as those in Example 4.

[0136] As shown in Table 10, the total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soy sauce produced according to the method of the present invention and the control 2, control 3 and control 4 soy sauces are significantly higher than those of the control 1 (p<0.05), indicating that the method of the present invention significantly improves the content of nutrients (total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (total nitrogen, amino acid nitrogen, reducing sugar) in soy sauce. As shown in Tables 1-4, the addition of ultrafinely crushed Antarctic krill powder can significantly improve the activity of protease and glucoamylase in Daqu, and protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing substances (total nitrogen) and free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar. In addition, the selenium and calcium contents of Antarctic krill powder are about 3.8 mg / kg and 2.6%. Since soy sauce is an acidic environment, selenium and calcium will gradually blend into soy sauce during the fermentation process. This is the key reason for adding ultrafinely crushed Antarctic krill powder to improve the nutrition and flavor substances of soy sauce. In addition, according to the Shaanxi Province Standard for Selenium-rich Condiments (>75μg / kg, DB61 / T 556-2018), the soy sauce produced by the method of the present invention is a selenium-rich food, and the added value of the soy sauce produced using the technology of the present invention will be significantly improved.

[0137] As shown in Table 10, the fluorine residue in the soy sauce samples produced according to the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard specified by FAO (<100 mg / kg), indicating that the method of the present invention significantly removes the fluorine residue in the soy sauce, and the produced soy sauce is highly safe and has important commercial value.

[0138] Table 10 Nutrition, flavor substances and fluorine content of high-salt dilute soy sauce produced by the method of the present invention

[0139]

[0140] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data (p < 0.05).

[0141] Example 5: A method for increasing the nutritional and flavor content of soy sauce and reducing the residual fluorine content, the specific method is as follows:

[0142] (1) grinding Antarctic krill powder with an ultrafine grinder to a particle size of 60 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0143] (2) Soak soybeans for 12 h, cook at 135 °C for 5 min, and cool;

[0144] (3) mixing the crushed fried wheat with the ultrafinely crushed Antarctic krill powder, inoculating the obtained mixture with Aspergillus oryzae koji, and mixing the inoculated mixture with the cooled soybeans to make koji, wherein the mass ratio of soybeans, crushed fried wheat and ultrafinely crushed Antarctic krill powder is 50:15:25, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybeans (dry weight), crushed fried wheat and ultrafinely crushed Antarctic krill powder);

[0145] (4) The koji making conditions were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 21% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:2.5;

[0146] (5) After 180 days of fermentation, pour oil, let stand, and filter;

[0147] (6) The pH of the filtered soy sauce was adjusted to 3.4 using 6 M / L hydrochloric acid, and sterilized and fluoride ion removed by ultrasonic assisted cooking under open conditions. The sterilization conditions were 85° C. and 32 min, and the ultrasonic conditions were ultrasonic intensity 65 W / L, 32 min, and frequency 42 kHz. Then, the soy sauce was adjusted to pH 4.7 using 6 M / L sodium hydroxide, and the finished soy sauce was obtained after packaging.

[0148] Control soy sauce 1: the raw materials are soybean and crushed fried wheat, the mass ratio is 90:15, and other conditions are the same as the above sample preparation method;

[0149] Control soy sauce 2: the raw materials and raw material ratios are the same as those in Example 5; the difference is that the pH of the soy sauce after filtration in step (6) is not adjusted, and the other operations are the same as those in Example 5;

[0150] Control soy sauce 3: The raw materials and raw material ratios used were the same as those in Example 5; the difference was that no ultrasonic treatment was performed, but the pH was adjusted to 3.4, and other operations were the same as those in Example 5;.

[0151] Control soy sauce 4: The raw materials and raw material ratios used were the same as those in Example 5; the difference was that the pH of the soy sauce after filtration in step (6) was not adjusted and ultrasonic treatment was not performed, and other operations were the same as those in Example 5.

[0152] As shown in Table 11, the total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soy sauce produced according to the method of the present invention and the control 2, control 3 and control 4 soy sauces are significantly higher than those of the control 1 (p<0.05), indicating that the method of the present invention significantly improves the content of nutrients (total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (total nitrogen, amino acid nitrogen, reducing sugar) in soy sauce. As shown in Tables 1-4, the addition of ultrafinely crushed Antarctic krill powder can significantly improve the enzyme activity of protease and glucoamylase in Daqu, and protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing substances (total nitrogen) and free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar. In addition, the selenium and calcium contents of Antarctic krill powder are about 3.8 mg / kg and 2.6%. Since soy sauce is an acidic environment, selenium and calcium will gradually blend into soy sauce during the fermentation process. This is the key reason for adding ultrafinely crushed Antarctic krill powder to improve the nutrition and flavor substances of soy sauce. In addition, according to the Shaanxi Province Standard for Selenium-rich Condiments (>75μg / kg, DB61 / T 556-2018), the soy sauce produced by the method of the present invention is a selenium-rich food, and the added value of the soy sauce produced using the technology of the present invention will be significantly improved.

[0153] As can be seen from Table 11, the fluorine residue in the soy sauce samples produced according to the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard specified by FAO (<100 mg / kg), indicating that the method of the present invention significantly removes the fluorine residue in the soy sauce, and the produced soy sauce is highly safe and has important commercial value.

[0154] Table 11 Nutrition, flavor substances and fluorine content of high-salt dilute soy sauce produced by the method of the present invention

[0155]

[0156] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data (p < 0.05).

[0157] Example 6: A method for increasing the nutritional and flavor content of soy sauce and reducing the residual fluorine content, the specific method is as follows:

[0158] (1) grinding Antarctic krill powder to a particle size of 75 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0159] (2) Soak soybeans for 12 h, cook at 135 °C for 5 min, and cool;

[0160] (3) mixing flour with ultrafine Antarctic krill powder, inoculating the obtained mixture with Aspergillus oryzae koji, mixing the inoculated mixture with the cooled soybeans and then making koji, wherein the mass ratio of soybeans, flour and ultrafine Antarctic krill powder is 50:15:30, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybeans (dry weight), flour and ultrafine Antarctic krill powder);

[0161] (4) The koji making conditions were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 21% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:2.5;

[0162] (5) After 180 days of fermentation, pour oil, let stand, and filter;

[0163] (6) The pH of the filtered soy sauce is adjusted to 3.2 using 6 M / L hydrochloric acid, and sterilized and fluoride ion removed by ultrasonic assisted cooking under open conditions. The sterilization conditions are 90° C. and 25 min, and the ultrasonic conditions are ultrasonic intensity 78 W / L, 25 min, and frequency 48 kHz. Then, the soy sauce is adjusted to pH 4.7 using 6 M / L sodium hydroxide, and the finished soy sauce is obtained after packaging.

[0164] Control soy sauce 1: The raw materials are soybean and flour, and the mass ratio is 95:15. Other conditions are the same as the above sample preparation method;

[0165] Control soy sauce 2: the raw materials and raw material ratios are the same as those in Example 6; the difference is that the pH of the soy sauce after filtration in step (6) is not adjusted, and the other operations are the same as those in Example 6;

[0166] Control soy sauce 3: the raw materials and raw material ratios were the same as those in Example 6; the difference was that no ultrasonic treatment was performed, but the pH was adjusted to 3.4, and other operations were the same as those in Example 6;

[0167] Control soy sauce 4: The raw materials and raw material ratios used were the same as those in Example 6; the difference was that the pH of the soy sauce after filtration in step (6) was not adjusted and ultrasonic treatment was not performed. Other operations were the same as those in Example 6.

[0168] As shown in Table 12, the total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soy sauce produced according to the method of the present invention and the soy sauces of control 2, control 3 and control 4 are significantly higher than those of control 1 (p<0.05), indicating that the method of the present invention significantly improves the content of nutrients (total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (total nitrogen, amino acid nitrogen, reducing sugar) in soy sauce. As shown in Tables 1-4, when too much ultrafinely crushed Antarctic krill powder is added, the production of Aspergillus oryzae in Daqu begins to be inhibited, and the activity of protease and glucoamylase begins to decrease, while protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing substances (total nitrogen) and free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar, so relative to Example 5, the content of nutrients and flavor substances in the soy sauce begins to decrease slightly, but the content of each nutrient and flavor substance is still significantly higher than that of control 1. In addition, the selenium and calcium content of Antarctic krill powder is about 3.8 mg / kg and 2.6%. Since soy sauce is an acidic environment, selenium and calcium will gradually blend into the soy sauce during the fermentation process. This is the key reason why the addition of ultrafinely crushed Antarctic krill powder improves the nutrition and flavor of soy sauce. In addition, according to the Shaanxi Province Selenium-rich Condiment Standard (>75μg / kg, DB61 / T 556-2018), the soy sauce produced by the method of the present invention is a selenium-rich food, and the added value of the soy sauce produced using the technology of the present invention will be significantly improved.

[0169] As can be seen from Table 12, the fluorine residue in the soy sauce samples produced according to the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard specified by FAO (<100 mg / kg), indicating that the method of the present invention significantly removes the fluorine residue in the soy sauce, and the produced soy sauce is highly safe and has important commercial value.

[0170] Table 12 Nutrition, flavor substances and fluorine content of high-salt dilute soy sauce produced by the method of the present invention

[0171]

[0172] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data ( p <0.05).

[0173] Example 7: A method for increasing the nutritional and flavor content of soy sauce and reducing the residual fluorine content, the specific method is as follows:

[0174] (1) grinding Antarctic krill powder to a particle size of 90 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0175] (2) Soak soybeans for 12 h, cook at 135 °C for 5 min, and cool;

[0176] (3) mixing flour with ultrafinely crushed Antarctic krill powder, inoculating the obtained mixture with Aspergillus oryzae koji, mixing the inoculated mixture with the cooled soybeans and then making koji, wherein the mass ratio of soybeans, flour and ultrafinely crushed Antarctic krill powder is 50:15:35, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybeans (dry weight), flour and ultrafinely crushed Antarctic krill powder);

[0177] (4) The koji making conditions were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 21% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:2.5;

[0178] (5) After 180 days of fermentation, pour oil, let stand, and filter;

[0179] (6) The filtered soy sauce is adjusted to a pH of 3.1 using 6 M / L hydrochloric acid, and sterilized and fluoride ion removed by ultrasonic assisted cooking under open conditions. The sterilization conditions are 95° C. for 18 min, and the ultrasonic conditions are an ultrasonic intensity of 90 W / L for 18 min and a frequency of 54 kHz. The soy sauce is then adjusted to a pH of 4.7 using 6 M / L sodium hydroxide, and the finished soy sauce is obtained after packaging.

[0180] Control soy sauce 1: the raw materials are soybean and flour, the mass ratio is 100:15, and other conditions are the same as the above sample preparation method;

[0181] Control soy sauce 2: the raw materials and raw material ratios used were the same as those in Example 7; the difference was that the pH of the soy sauce after filtration in step (6) was not adjusted, and the other operations were the same as those in Example 7;

[0182] Control soy sauce 3: the raw materials and raw material ratios were the same as those in Example 7; the difference was that no ultrasonic treatment was performed, but the pH was adjusted to 3.4, and other operations were the same as those in Example 7;

[0183] Control soy sauce 4: The raw materials and raw material ratios used were the same as those in Example 7; the difference was that the pH of the soy sauce after filtration in step (6) was not adjusted and ultrasonic treatment was not performed, and other operations were the same as those in Example 7.

[0184] As shown in Table 13, the total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soy sauce produced according to the method of the present invention and the soy sauces of control 2, control 3 and control 4 are significantly higher than those of control 1 (p<0.05), indicating that the method of the present invention significantly improves the content of nutrients (total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (total nitrogen, amino acid nitrogen, reducing sugar) in soy sauce. As shown in Tables 1-4, when too much ultrafinely crushed Antarctic krill powder is added, the production of Aspergillus oryzae in Daqu begins to be inhibited, and the activity of protease and glucoamylase begins to decrease, while protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing substances (total nitrogen) and free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar, so relative to Example 5, the content of nutrients and flavor substances in the soy sauce begins to decrease slightly, but the content of each nutrient and flavor substance is still significantly higher than that of control 1. In addition, the selenium and calcium content of Antarctic krill powder is about 3.8 mg / kg and 2.6%. Since soy sauce is an acidic environment, selenium and calcium will gradually blend into the soy sauce during the fermentation process. This is the key reason why the addition of ultrafinely crushed Antarctic krill powder improves the nutrition and flavor of soy sauce. In addition, according to the Shaanxi Province Selenium-rich Condiment Standard (>75μg / kg, DB61 / T 556-2018), the soy sauce produced by the method of the present invention is a selenium-rich food, and the added value of the soy sauce produced using the technology of the present invention will be significantly improved.

[0185] As shown in Table 13, the fluorine residue in the soy sauce samples produced according to the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard specified by FAO (<100 mg / kg), indicating that the method of the present invention significantly removes the fluorine residue in the soy sauce, and the produced soy sauce is highly safe and has important commercial value.

[0186] Table 13 Nutrition, flavor substances and fluorine content of high-salt dilute soy sauce produced by the method of the present invention

[0187]

[0188] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data ( p <0.05).

[0189] Example 8: A method for increasing the nutritional and flavor content of soy sauce and reducing the residual fluorine content, the specific method is as follows:

[0190] (1) grinding Antarctic krill powder to a particle size of 100 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0191] (2) soybean meal was mixed with 1.1 times the mass ratio of water, moistened for 30 min, then steamed at 135°C for 5 min, and cooled;

[0192] (3) mixing flour with ultrafinely crushed Antarctic krill meal, inoculating the obtained mixture with Aspergillus oryzae koji, and mixing the inoculated mixture with the cooled soybean meal to make koji, wherein the mass ratio of soybean meal, flour and ultrafinely crushed Antarctic krill meal is 50:15:40, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybean meal (dry weight), flour and ultrafinely crushed Antarctic krill meal);

[0193] (4) The koji making conditions were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 21% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:2.5;

[0194] (5) After 180 days of fermentation, pour oil, let stand, and filter;

[0195] (6) The pH of the filtered soy sauce is adjusted to 3.0 using 6 M / L hydrochloric acid, and sterilized and fluoride ion removed by ultrasonic assisted cooking under open conditions. The sterilization conditions are 100° C. for 10 min, and the ultrasonic conditions are ultrasonic intensity 100 W / L, 10 min, and frequency 60 kHz. Then, the soy sauce is adjusted to pH 4.7 using 6 M / L sodium hydroxide, and the finished soy sauce is obtained after packaging.

[0196] Control soy sauce 1: the raw materials are soybean meal and flour, the mass ratio is 105:15, and other conditions are the same as the above sample preparation method;

[0197] Control soy sauce 2: the raw materials and raw material ratios used were the same as those in Example 8; the difference was that the pH of the soy sauce after filtration in step (6) was not adjusted, and the other operations were the same as those in Example 8;

[0198] Control soy sauce 3: the raw materials and raw material ratios were the same as those in Example 8, except that no ultrasonic treatment was performed, but the pH was adjusted to 3.4, and other operations were the same as those in Example 8;

[0199] Control soy sauce 4: the raw materials and raw material ratios are the same as those in Example 8; the difference is that the pH of the soy sauce after filtration in step (6) is not adjusted and ultrasonic treatment is not performed, and other operations are the same as those in Example 8;

[0200] As shown in Table 14, the total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soy sauce produced according to the method of the present invention and the soy sauces of control 2, control 3 and control 4 are significantly higher than those of control 1 (p<0.05), indicating that the method of the present invention significantly improves the content of nutrients (total nitrogen, amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (total nitrogen, amino acid nitrogen, reducing sugar) in soy sauce. As shown in Tables 1-4, when too much ultrafinely crushed Antarctic krill powder is added, the production of Aspergillus oryzae in Daqu begins to be inhibited, and the activity of protease and glucoamylase begins to decrease, while protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing substances (total nitrogen) and free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar, so relative to Example 5, the content of nutrients and flavor substances in the soy sauce begins to decrease slightly, but the content of each nutrient and flavor substance is still significantly higher than that of control 1. In addition, the selenium and calcium content of Antarctic krill powder is about 3.8 mg / kg and 2.6%. Since soy sauce is an acidic environment, selenium and calcium will gradually blend into the soy sauce during the fermentation process. This is the key reason why the addition of ultrafinely crushed Antarctic krill powder improves the nutrition and flavor of soy sauce. In addition, according to the Shaanxi Province Selenium-rich Condiment Standard (>75μg / kg, DB61 / T 556-2018), the soy sauce produced by the method of the present invention is a selenium-rich food, and the added value of the soy sauce produced using the technology of the present invention will be significantly improved.

[0201] As can be seen from Table 14, the fluorine residue in the soy sauce samples produced according to the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard specified by FAO (<100 mg / kg), indicating that the method of the present invention significantly removes the fluorine residue in the soy sauce, and the produced soy sauce is highly safe and has important commercial value.

[0202] Table 14 Nutrition, flavor substances and fluorine content of high-salt dilute soy sauce produced by the method of the present invention

[0203]

[0204] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data (p < 0.05).

[0205] Embodiment 9:

[0206] A method for increasing the nutritional and flavor content of soybean paste and reducing the residual fluorine content, the specific method is as follows:

[0207] (1) grinding Antarctic krill powder to a particle size of 1 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0208] (2) Soak soybeans for 12 h, cook at 135 °C for 5 min, and cool;

[0209] (3) mixing flour with ultrafinely crushed Antarctic krill powder, inoculating the obtained mixture with Aspergillus oryzae koji, mixing the inoculated mixture with the cooled soybeans and then making koji, wherein the mass ratio of soybeans, flour and ultrafinely crushed Antarctic krill powder is 50:15:5, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybeans (dry weight), flour and ultrafinely crushed Antarctic krill powder);

[0210] (4) The conditions for making koji were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 18% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:1.5;

[0211] (5) After fermentation for 30 days, the pH of the soybean paste was adjusted to 4.0 using 6 M / L hydrochloric acid, and sterilized and fluoride ions were removed by steaming while stirring under open conditions. The sterilization conditions were 65°C for 60 min and the stirring conditions were 10 rpm for 60 min. Then, the pH of the soybean paste was adjusted to 4.7 using 6 M / L sodium hydroxide, and the finished soybean paste was obtained after packaging.

[0212] Control bean paste 1: the raw materials are soybean and flour, the mass ratio is 55:15, and other conditions are the same as the above sample preparation method;

[0213] Control bean paste 2: the raw materials and raw material ratios used were the same as those in Example 9; the pH of the fermented bean paste in step (5) was not adjusted; other operations were the same as those in Example 9;

[0214] Control bean paste 3: the raw materials and raw material ratios were the same as those in Example 9; the difference was that stirring was not performed, but the pH was adjusted to 4.0, and other operations were the same as those in Example 9;

[0215] Control bean paste 4: the raw materials and the raw material ratios used were the same as those in Example 9; the pH of the fermented bean paste in step (5) was not adjusted and stirring was not performed, and other operations were the same as those in Example 9.

[0216] As shown in Table 15, the amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soybean paste produced according to the method of the present invention and the soybean pastes of control 2, control 3 and control 4 are significantly higher than those of control 1 (p<0.05), indicating that the method of the present invention significantly improves the content of nutrients (amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (amino acid nitrogen, reducing sugar) in soybean paste. As shown in Tables 1-4, the addition of part of the ultrafinely ground Antarctic krill powder can significantly improve the activity of protease and glucoamylase in Daqu, and protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing substances free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar. In addition, the selenium and calcium contents of Antarctic krill powder are about 3.8 mg / kg and 2.6%. Since soybean paste is an acidic environment, selenium and calcium will gradually blend into soybean paste during the fermentation process. This is the key reason for adding ultrafinely ground Antarctic krill powder to improve the nutrition and flavor substances of soybean paste. In addition, according to the Shaanxi Province Selenium-rich Condiment Standard (>75μg / kg, DB61 / T 556-2018), the bean paste produced by the method of the present invention is a selenium-rich food, so the added value of the bean paste produced using the technology of the present invention will be significantly improved.

[0217] As can be seen from Table 15, the fluorine residue in the sample bean paste produced according to the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard specified by FAO (<100 mg / kg), indicating that the method of the present invention significantly removes the fluorine residue in the bean paste, and the produced bean paste is highly safe and has important commercial value.

[0218] Table 15 Nutrition, flavor substances and fluorine content of soybean paste produced by the method of the present invention

[0219]

[0220] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data ( p <0.05).

[0221] Embodiment 10:

[0222] A method for increasing the nutritional and flavor content of soybean paste and reducing the residual fluorine content, the specific method is as follows:

[0223] (1) grinding Antarctic krill powder to a particle size of 25 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0224] (2) Soak soybeans for 12 h, cook at 135 °C for 5 min, and cool;

[0225] (3) mixing flour with ultrafinely crushed Antarctic krill powder, inoculating the obtained mixture with Aspergillus oryzae koji, mixing the inoculated mixture with the cooled soybeans and then making koji, wherein the mass ratio of soybeans, flour and ultrafinely crushed Antarctic krill powder is 50:15:25, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybeans (dry weight), flour and ultrafinely crushed Antarctic krill powder);

[0226] (4) The conditions for making koji were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 18% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:1.5;

[0227] (5) After fermentation for 30 days, the pH of the soybean paste was adjusted to 3.6 using 6 M / L hydrochloric acid, and sterilized and fluoride ions were removed by steaming while stirring under open conditions. The sterilization conditions were 75 ° C and 40 min, and the stirring conditions were 40 rpm and 40 min. Then, the pH of the soybean paste was adjusted to 4.7 using 6 M / L sodium hydroxide, and the finished soybean paste was obtained after packaging.

[0228] Control bean paste 1: the raw materials are soybean and flour, the mass ratio is 90:15, and other conditions are the same as the above sample preparation method;

[0229] Control bean paste 2: the raw materials and raw material ratios used were the same as those in Example 10; the difference was that the pH of the fermented bean paste in step (5) was not adjusted, and the other conditions were the same as those in Example 10;

[0230] Control bean paste 3: The raw materials and raw material ratios used were the same as those in Example 10; the difference was that stirring was not performed, but the pH was adjusted to 3.6, and the other conditions were the same as those in Example 10.

[0231] Control bean paste 4: the raw materials and the raw material ratios used were the same as those in Example 10; the pH of the fermented bean paste in step (5) was not adjusted and stirring was not performed, and other conditions were the same as those in Example 10.

[0232] As shown in Table 16, the amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soybean paste produced according to the method of the present invention and the soybean pastes of control 2, control 3 and control 4 are significantly higher than those of control 1 (p<0.05), indicating that the method of the present invention significantly improves the content of nutrients (amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (amino acid nitrogen, reducing sugar) in soybean paste. As shown in Tables 1-4, the addition of ultrafinely crushed Antarctic krill powder can significantly increase the activity of protease and glucoamylase in Daqu, and protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar. In addition, the selenium and calcium contents of Antarctic krill powder are about 3.8 mg / kg and 2.6%. Since soybean paste is an acidic environment, selenium and calcium will gradually blend into soybean paste during the fermentation process. This is the key reason for adding ultrafinely crushed Antarctic krill powder to improve the nutrition and flavor substances of soybean paste. In addition, according to the Shaanxi Province Selenium-rich Condiment Standard (>75μg / kg, DB61 / T 556-2018), the bean paste produced by the method of the present invention is a selenium-rich food, so the added value of the bean paste produced using the technology of the present invention will be significantly improved.

[0233] As can be seen from Table 16, the fluorine residue in the sample bean paste produced according to the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard specified by FAO (<100 mg / kg), indicating that the method of the present invention significantly removes the fluorine residue in the bean paste, and the produced bean paste is highly safe and has important commercial value.

[0234] Table 16 Nutrition, flavor substances and fluorine content of soybean paste produced by the method of the present invention

[0235]

[0236]

[0237] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data ( p <0.05).

[0238] Example 11: A method for increasing the nutritional and flavor content of soybean paste and reducing the residual fluorine content, the specific method is as follows:

[0239] (1) grinding Antarctic krill powder to a particle size of 75 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0240] (2) Soak soybeans for 12 h, cook at 135 °C for 5 min, and cool;

[0241] (3) mixing flour with ultrafine Antarctic krill powder, inoculating the obtained mixture with Aspergillus oryzae koji, mixing the inoculated mixture with the cooled soybeans and then making koji, wherein the mass ratio of soybeans, flour and ultrafine Antarctic krill powder is 50:15:30, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybeans (dry weight), flour and ultrafine Antarctic krill powder);

[0242] (4) The conditions for making koji were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 18% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:1.5;

[0243] (5) After fermentation for 30 days, the pH of the soybean paste was adjusted to 3.3 using 6 M / L hydrochloric acid, and sterilized and fluoride ions were removed by steaming while stirring under open conditions. The sterilization conditions were 90 ° C, 20 min, and the stirring conditions were 70 rpm, 20 min. Then, the pH of the soybean paste was adjusted to 4.7 using 6 M / L sodium hydroxide, and the finished soybean paste was obtained after packaging.

[0244] Control bean paste 1: the raw materials are soybean and flour, the mass ratio is 95:15, and other conditions are the same as the above sample preparation method;

[0245] Control bean paste 2: the raw materials and raw material ratios used were the same as those in Example 11; the pH of the fermented bean paste in step (5) was not adjusted, and other conditions were the same as those in Example 11;

[0246] Control bean paste 3: The raw materials and raw material ratios used were the same as those in Example 11; the difference was that stirring was not performed, and other conditions were the same as those in Example 11.

[0247] Control bean paste 4: The raw materials and raw material ratios used were the same as those in Example 11; the difference was that the pH of the fermented bean paste in step (5) was not adjusted and stirring was not performed, and other conditions were the same as those in Example 11.

[0248] As shown in Table 17, the amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soybean paste produced according to the method of the present invention and the soybean pastes of control 2, control 3 and control 4 are significantly higher than those of control 1 (p<0.05), indicating that the method of the present invention significantly increases the content of nutrients (amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (amino acid nitrogen, reducing sugar) in soybean paste. As shown in Tables 1-4, when too much ultrafinely crushed Antarctic krill powder is added, the production of Aspergillus oryzae in Daqu begins to be inhibited, and the activities of protease and glucoamylase begin to decrease. Protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing substances (total nitrogen) and free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar. Therefore, relative to Example 10, the amino acid nitrogen and reducing sugar contents in soybean paste begin to decrease slightly, but the contents of various nutrients and flavor substances are still significantly higher than those of control 1. In addition, the selenium and calcium content of Antarctic krill powder is about 3.8 mg / kg and 2.6%. Since soybean paste is an acidic environment, selenium and calcium will gradually be integrated into the soybean paste during the fermentation process. This is the key reason why the addition of ultra-finely ground Antarctic krill powder improves the nutrition and flavor of soybean paste. In addition, according to the Shaanxi Province Selenium-rich Condiment Standard (>75μg / kg, DB61 / T556-2018), the soybean paste produced by the method of the present invention is a selenium-rich food, so the added value of the soybean paste produced using the technology of the present invention will be significantly improved.

[0249] As can be seen from Table 17, the fluorine residue in the sample bean paste produced according to the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard specified by FAO (<100 mg / kg), indicating that the method of the present invention significantly removes the fluorine residue in the bean paste, and the produced bean paste is highly safe and has important commercial value.

[0250] Table 17 Nutrition, flavor substances and fluorine content of soybean paste produced by the method of the present invention

[0251]

[0252] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data (p < 0.05).

[0253] Embodiment 12:

[0254] A method for increasing the nutritional and flavor content of soybean paste and reducing the residual fluorine content, the specific method is as follows:

[0255] (1) grinding Antarctic krill powder to a particle size of 100 μm to obtain ultrafinely ground Antarctic krill powder for later use;

[0256] (2) Soak soybeans for 12 h, cook at 135 °C for 5 min, and cool;

[0257] (3) mixing flour with ultrafinely crushed Antarctic krill powder, inoculating the obtained mixture with Aspergillus oryzae koji, mixing the inoculated mixture with the cooled soybeans and then making koji, wherein the mass ratio of soybeans, flour and ultrafinely crushed Antarctic krill powder is 50:15:40, and the inoculation amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials (soybeans (dry weight), flour and ultrafinely crushed Antarctic krill powder);

[0258] (4) The conditions for making koji were as follows: temperature 29°C, relative humidity 95%, time 43 h, mature daqu was mixed with brine with a mass concentration of 18% and then fermented in a tank, and the mass ratio of mature daqu to brine was 1:1.5;

[0259] (5) After fermentation for 30 days, the pH of the soybean paste was adjusted to 3.0 using 6 M / L hydrochloric acid, and sterilized and fluoride ions were removed by steaming while stirring under open conditions. The sterilization conditions were 10°C for 10 min and the stirring conditions were 100 rpm for 10 min. Then, the pH of the soybean paste was adjusted to 4.7 using 6 M / L sodium hydroxide. The finished soybean paste was obtained after packaging.

[0260] Control bean paste 1: the raw materials are soybean and flour, the mass ratio is 105:15, and other conditions are the same as the above sample preparation method;

[0261] Control bean paste 2: the raw materials and raw material ratios used were the same as those in Example 12; the difference was that the pH of the fermented bean paste in step (5) was not adjusted, and the other conditions were the same as those in Example 12;

[0262] Control bean paste 3: The raw materials and raw material ratios used were the same as those in Example 12; the difference was that stirring was not performed, and other conditions were the same as those in Example 12.

[0263] Control bean paste 4: the raw materials and the raw material ratios used were the same as those in Example 12; the pH of the fermented bean paste in step (5) was not adjusted and stirring was not performed, and other conditions were the same as those in Example 12.

[0264] As shown in Table 18, the amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium contents of the sample soybean paste produced according to the method of the present invention and the soybean pastes of control 2, control 3 and control 4 are significantly higher than those of control 1 (p<0.05), indicating that the method of the present invention significantly increases the content of nutrients (amino acid nitrogen, reducing sugar, total selenium, organic selenium and calcium) and flavor substances (amino acid nitrogen, reducing sugar) in soybean paste. As shown in Tables 1-4, when too much ultrafinely crushed Antarctic krill powder is added, the production of Aspergillus oryzae in Daqu begins to be inhibited, and the activity of protease and glucoamylase begins to decrease. Protease can catalyze the degradation of protein in the raw material into soluble nitrogen-containing substances (total nitrogen) and free amino acids (amino nitrogen), and glucoamylase can catalyze the degradation of starch in the raw material into reducing sugar. Therefore, relative to Example 10, the content of nutrients (except total nitrogen) and flavor substances (except total nitrogen) in soybean paste begins to decrease slightly, but the content of each nutrient and flavor substance is still significantly higher than that of control 1. In addition, the selenium and calcium content of Antarctic krill powder is about 3.8 mg / kg and 2.6%. Since soybean paste is an acidic environment, selenium and calcium will gradually be integrated into soybean paste during the fermentation process. This is the key reason why the addition of ultrafine Antarctic krill powder improves the nutrition and flavor of soybean paste. In addition, according to the Shaanxi Province Selenium-rich Condiment Standard (>75μg / kg, DB61 / T 556-2018), the soybean paste produced by the method of the present invention is a selenium-rich food, so the added value of the soybean paste produced using the technology of the present invention will be significantly improved.

[0265] As can be seen from Table 18, the fluorine residue in the sample bean paste produced according to the method of the present invention is significantly lower than that in the control 2-4 (p<0.05), and lower than the limit standard specified by FAO (<100 mg / kg), indicating that the method of the present invention significantly removes the fluorine residue in the bean paste, and the produced bean paste is highly safe and has important commercial value.

[0266] Table 18 Nutrition, flavor substances and fluorine content of soybean paste produced by the method of the present invention

[0267]

[0268] Note: The results are mean ± standard deviation (n = 3); values ​​in the same column without the same lowercase letters indicate significant differences between the data (p < 0.05).

[0269] Although the present invention has been disclosed as above in the form of a preferred embodiment, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the scope defined in the claims.

Claims

1. A method for increasing the nutritional and flavor content of soy sauce and soybean paste and reducing fluorine residue, characterized in that: The following steps are involved: (1) Pretreatment of Antarctic krill powder: grinding the Antarctic krill powder to a particle size of 1-100 µm to obtain ultrafinely ground Antarctic krill powder; (2) Preparation of soy sauce or soybean paste based on Antarctic krill powder: (a) Preparation of soy sauce: Soybeans or soybean meal are soaked, steamed and cooled to obtain cooled soybeans or soybean meal; flour or crushed fried wheat is mixed with the ultrafinely crushed Antarctic krill powder obtained in step (1) to obtain a mixture; Inoculate the obtained mixture with Aspergillus oryzae koji essence, mix the inoculated mixture with the cooled soybean or soybean meal and then make koji, obtain mature koji after making koji, mix the mature koji with salt water and then ferment in a tank, wherein the mass ratio of soybean or soybean meal, flour or crushed fried wheat and ultrafinely crushed Antarctic krill powder is 50:15:5-40; after the fermentation is completed, pour oil or squeeze oil, stand and filter according to a conventional method, adjust the pH of the filtered soy sauce to 3.0-4.0 with hydrochloric acid, and use ultrasound to cooperate with steaming and sterilizing and remove fluoride ions in an open condition, wherein the steaming and sterilizing temperature is 65-100 ° C, the time is 10-60 min, and the ultrasound conditions are: ultrasound intensity 10-100 W / L, 10-60 min, frequency 20-60 kHz; finally, adjust the pH of the soy sauce again with sodium hydroxide, and obtain the finished soy sauce after packaging; (b) Preparation of soybean paste: Soybeans are soaked, steamed and cooled to obtain cooled soybeans; flour is then mixed with the ultrafinely crushed Antarctic krill powder obtained in step (1) to obtain a mixture, Aspergillus oryzae koji is inoculated into the obtained mixture, the inoculated mixture is mixed with the cooled soybeans to make koji, and the mature koji is obtained, which is then mixed with salt water and fermented in a tank, wherein the mass ratio of soybeans, flour and ultrafine Antarctic krill powder is 50:15:5-40; after the fermentation is completed, hydrochloric acid is used to adjust the pH to 3.0-4.0, and the mixture is steamed and sterilized and fluoride ions are removed under open conditions while stirring, wherein the sterilization temperature is 65-100°C and the sterilization time is 10-60 min; the stirring conditions are: the stirring speed is 10-100 rpm and the stirring time is 10-60 min; finally, the pH of the soybean paste is adjusted again using sodium hydroxide, and the finished soybean paste is obtained after packaging.

2. The method for increasing the nutritional and flavor content of soy sauce and soybean paste and reducing fluorine residue according to claim 1, characterized in that: The particle size of the ultrafinely ground Antarctic krill powder in step (1) is 30-60 µm.

3. The method for increasing the nutritional and flavor content of soy sauce and soybean paste and reducing fluorine residue according to claim 1, characterized in that: In step (2) (a), when the raw material is soybeans, the soybeans are soaked for 12 h; when the raw material is soybean meal, the soybean meal is soaked in water for 30 min, wherein the mass ratio of soybean meal to water is 1:1.1; the soybean or soybean meal is cooked at a temperature of 135 °C for 5-10 min.

4. The method for increasing the nutritional and flavor content of soy sauce and soybean paste and reducing fluorine residue according to claim 1, characterized in that: The mass ratio of soybean or soybean meal, flour or crushed fried wheat and ultrafinely crushed Antarctic krill powder in step (2) (a) is 50:15:15-35; the inoculum amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials; the total mass of the raw materials is the sum of the masses of soybean or soybean meal, flour or crushed fried wheat and ultrafinely crushed Antarctic shrimp powder, and the mass of the soybean or soybean meal is based on dry weight; the koji making temperature is 29~30°C, the time is 40~43 h, and the relative humidity is 95%.

5. The method for increasing the nutritional and flavor content of soy sauce and soybean paste and reducing fluorine residue according to claim 1, characterized in that: In step (2) (a), the mature Daqu is mixed with salt water and then fermented in a tank. When preparing high-salt dilute soy sauce, the mass percentage concentration of the salt water is 21%, and the mass ratio of mature Daqu to salt water is 1:2.5; when preparing low-salt solid soy sauce, the mass percentage concentration of the salt water is 12%, and the mass ratio of mature Daqu to salt water during the fermentation stage is 1:

1. After the fermentation is completed, salt water with a mass percentage concentration of 12% and a weight percentage concentration of 1.5 times that of the raw materials is added for extraction; the high-salt dilute soy sauce is fermented at room temperature for 180 days; the low-salt solid soy sauce is fermented at 47°C for 30 days.

6. The method for increasing the nutritional and flavor content of soy sauce and soybean paste and reducing fluorine residue according to claim 1, characterized in that: The sterilization conditions in step (2) (a) are 75-90 °C, 30-40 min, and the ultrasonic conditions are: ultrasonic intensity 30-70 W / L, 30-40 min, frequency 35-50 kHz; the concentration of hydrochloric acid is 6 M / L; the concentration of sodium hydroxide is 6 M / L, and the pH of the soy sauce is adjusted to 4.7 again.

7. The method for increasing the nutritional and flavor content of soy sauce and soybean paste and reducing fluorine residue according to claim 1, characterized in that: In step (2) (b), the soybeans are soaked for 12 h; and the soybeans are steamed at 135 °C for 5-10 min.

8. The method for increasing the nutritional and flavor content of soy sauce and soybean paste and reducing fluorine residue according to claim 1, characterized in that: In step (2) (b), the mass ratio of the soybeans, flour and ultrafine Antarctic krill meal is 50:15:20-35; the inoculum amount of Aspergillus oryzae koji is 0.2% of the total mass of the raw materials; the total mass of the raw materials is the sum of the masses of the soybeans, flour and ultrafine Antarctic krill meal, and the mass of the soybeans or soybean meal is based on dry weight; the koji making temperature is 29-30°C, the time is 42-43 h, and the relative humidity is 95%.

9. The method for increasing the nutritional and flavor content of soy sauce and soybean paste and reducing fluorine residue according to claim 1, characterized in that: In step (2) (b), the mass concentration of the brine is 18%; the ratio of the mature Daqu to the brine is 1: 1.5; the fermentation is carried out at room temperature and the fermentation time is 30 days; the sterilization conditions are as follows: the sterilization temperature is 72-100 ° C and the sterilization time is 30-60 min; the stirring conditions are as follows: the stirring speed is 55-100 rpm and the stirring time is 30-60 min; the concentration of hydrochloric acid is 6 M / L; the concentration of sodium hydroxide is 6 M / L, and the pH of the bean paste is adjusted to 4.7 again.

10. Soy sauce or soybean paste prepared according to the method according to any one of claims 1 to 9.

Images