阅读说明：本技术 一种复合天然抗菌防腐剂及其制备方法和应用 (Composite natural antibacterial preservative and preparation method and application thereof ) 是由 劳敏军 周小敏 于 2021-09-26 设计创作，主要内容包括：本发明公开了一种复合天然抗菌防腐剂及其制备方法和应用,复合天然型抗菌防腐剂由以下成分及其重量份组成：壳聚糖0.5～1.5份、茶多酚0.05～0.15份、乳酸链球菌素0.15～0.25份,所述壳聚糖提取自虾蟹壳。其制备方法包括将虾蟹壳斩碎,进行酸碱循环处理,直至加酸再无气泡产生,再经草酸处理,最后漂洗、干燥,制得甲壳素成品；将所述甲壳素成品移入至反应釜中进行脱乙酰基,过滤,清洗,干燥,粉碎,制得壳聚糖；将壳聚糖0.5～1.5份、茶多酚0.05～0.15份、乳酸链球菌素0.15～0.25份进行混合得到复合天然型抗菌防腐剂。克服了甲壳素生产中环境污染大的问题,进而达到了重复利用节约成本的目的。(The invention discloses a composite natural antibacterial preservative and a preparation method and application thereof, wherein the composite natural antibacterial preservative comprises the following components in parts by weight: 0.5-1.5 parts of chitosan, 0.05-0.15 part of tea polyphenol and 0.15-0.25 part of nisin, wherein the chitosan is extracted from shrimp and crab shells. The preparation method comprises chopping shrimp and crab shell, performing acid-base circulation treatment until no bubbles are generated after adding acid, treating with oxalic acid, rinsing, and drying to obtain chitin product; transferring the chitin finished product into a reaction kettle for deacetylation, filtering, cleaning, drying and crushing to obtain chitosan; 0.5-1.5 parts of chitosan, 0.05-0.15 part of tea polyphenol and 0.15-0.25 part of nisin are mixed to obtain the composite natural antibacterial preservative. Overcomes the problem of great environmental pollution in the production of chitin, and further achieves the purposes of recycling and saving cost.)

1. The compound natural antibacterial preservative is characterized by comprising the following components in parts by weight: 0.5-1.5 parts of chitosan, 0.05-0.15 part of tea polyphenol and 0.15-0.25 part of nisin, wherein the chitosan is extracted from shrimp and crab shells.

2. The composite natural-based antimicrobial preservative according to claim 1, wherein the chitosan is extracted from shrimp and crab shells, and comprises:

chopping shrimp and crab shells, performing acid-base circulation treatment until no bubbles are generated after acid is added, performing oxalic acid treatment, and finally rinsing and drying to obtain a chitin finished product;

and transferring the chitin finished product into a reaction kettle for deacetylation, filtering, cleaning, drying and crushing to obtain the chitosan.

3. The compound natural-type antibacterial preservative according to claim 1, wherein the acid-base cycle treatment comprises:

placing the chopped shrimp and crab shells into 3-6% sodium hydroxide for soaking treatment, taking out the shrimp and crab shells after treatment, and then placing the shrimp and crab shells into 3-6% hydrochloric acid for soaking and deashing treatment, wherein the material-liquid ratio of the shrimp and crab shells to the sodium hydroxide solution is 1: 1-5 (g/mL), wherein the feed-liquid ratio of the shrimp and crab shells to the hydrochloric acid is 1: 1 to 5 (g/mL).

4. The compound natural antimicrobial preservative according to claim 1, wherein the mass concentration of oxalic acid is 0.1-1%.

5. The compound natural antibacterial preservative according to claim 1, wherein the mass ratio of the chitin finished product to the alkali liquor in the reaction kettle is 1: 40-80 percent, wherein the mass concentration of the alkali liquor is 20-50 percent.

6. The compound natural antimicrobial preservative according to claim 1, wherein the reaction temperature in the reaction kettle is 80-100 ℃ and the reaction time is 10-14 hours.

7. A preparation method of a compound natural antibacterial preservative is characterized by comprising the following steps:

chopping shrimp and crab shells, performing acid-base circulation treatment until no bubbles are generated after acid is added, performing oxalic acid treatment, and finally rinsing and drying to obtain a chitin finished product;

transferring the chitin finished product into a reaction kettle for deacetylation, filtering, cleaning, drying and crushing to obtain chitosan;

0.5-1.5 parts of chitosan, 0.05-0.15 part of tea polyphenol and 0.15-0.25 part of nisin are mixed to obtain the composite natural antibacterial preservative.

8. The application of the compound natural antibacterial preservative in the antibacterial preservative treatment of aquatic products, which is characterized by comprising the following components:

unfreezing, cleaning and washing frozen aquatic products;

a step (2) of dissolving the compound natural antimicrobial preservative according to claim 1 into clear water to obtain a natural antimicrobial preservative solution;

and (3) soaking the aquatic product cleaned in the step (1) in the natural antibacterial preservative solution at 1-5 ℃, wherein the ratio of the aquatic product to the natural antibacterial preservative solution is 1: 3 (g/ml);

and (4) draining, placing the dried mixture into a tray, performing heat sealing by using a preservative film, and storing the tray at the temperature of (4 +/-1) DEG C for subsequent processing.

9. The use of claim 8, wherein the aquatic product is one or more of a hairtail, a mackerel, a Peru squid, a North Taiyu squid, a true squid, and a pomfret.

10. The use according to claim 8, wherein the preservative film is a 0.013mm PE preservative film.

Technical Field

The invention relates to a natural aquatic product preservative, and in particular relates to a composite natural antibacterial preservative and a preparation method and application thereof.

Background

At present, China has abundant fishery and fish culture resources, most fishes are not easy to survive after being caught and landed, the water content of the fishes is high, the fishes are rich in nutrition, easy to decay and deteriorate, the preservation time is short, and the fishes are not easy to store and transport for a long distance. It is therefore of great importance to inhibit the proliferation of microorganisms in fresh aquatic products.

In recent years, with the awareness of the necessity of antisepsis and the continuous understanding of the mechanism of antiseptics for inhibiting microorganisms, only sorbic acid and its potassium salt, and chlorine dioxide in a stable state are currently available as preservatives for aquatic products. The use of such chemical preservatives in aquatic products presents various challenges and challenges. Because chemicals added into food have certain toxic and side effects, the dosage is limited, and the addition time needs to be mastered to play the expected role, so that the use of the chemical preservative is limited.

Therefore, the development of a natural preservative for the fresh-keeping of aquatic products is very important.

Disclosure of Invention

The embodiment of the invention aims to provide a composite natural antibacterial preservative and a preparation method and application thereof, so as to overcome the defects of the prior art.

According to the first aspect of the embodiment of the invention, the composite natural antibacterial preservative is provided, and comprises the following components in parts by weight: 0.5-1.5 parts of chitosan, 0.05-0.15 part of tea polyphenol and 0.15-0.25 part of nisin, wherein the chitosan is extracted from shrimp and crab shells.

Further, the chitosan is extracted from shrimp and crab shells and comprises:

chopping shrimp and crab shells, performing acid-base circulation treatment until no bubbles are generated after acid is added, performing oxalic acid treatment, and finally rinsing and drying to obtain a chitin finished product;

and transferring the chitin finished product into a reaction kettle for deacetylation, filtering, cleaning, drying and crushing to obtain the chitosan.

Further, acid-base circulation treatment comprises the following steps:

placing the chopped shrimp and crab shells into 3-6% sodium hydroxide for soaking treatment, taking out the shrimp and crab shells after treatment, and then placing the shrimp and crab shells into 3-6% hydrochloric acid for soaking and deashing treatment, wherein the material-liquid ratio of the shrimp and crab shells to the sodium hydroxide solution is 1: 1-5 (g/mL), wherein the feed-liquid ratio of the shrimp and crab shells to the hydrochloric acid is 1: 1 to 5 (g/mL).

Further, the mass concentration of the oxalic acid is 0.1-1%.

Further, the mass ratio of the chitin finished product to the alkali liquor in the reaction kettle is 1: 40-80 percent, wherein the mass concentration of the alkali liquor is 20-50 percent.

Further, the reaction temperature in the reaction kettle is 80-100 ℃, and the reaction time is 10-14 h.

According to a second aspect of the embodiments of the present invention, there is provided a method for preparing a composite natural-type antibacterial preservative, including:

chopping shrimp and crab shells, performing acid-base circulation treatment until no bubbles are generated after acid is added, performing oxalic acid treatment, and finally rinsing and drying to obtain a chitin finished product;

transferring the chitin finished product into a reaction kettle for deacetylation, filtering, cleaning, drying and crushing to obtain chitosan;

0.5-1.5 parts of chitosan, 0.05-0.15 part of tea polyphenol and 0.15-0.25 part of nisin are mixed to obtain the composite natural antibacterial preservative.

According to a third aspect of the embodiments of the present invention, there is provided an application of the compound natural antimicrobial preservative of the first aspect in antimicrobial preservative treatment of aquatic products, including:

unfreezing, cleaning and washing frozen aquatic products;

a step (2) of dissolving the compound natural antimicrobial preservative according to claim 1 into clear water to obtain a natural antimicrobial preservative solution;

and (3) soaking the aquatic product cleaned in the step (1) in the natural antibacterial preservative solution at 1-5 ℃, wherein the ratio of the aquatic product to the natural antibacterial preservative solution is 1: 3 (g/mL);

and (4) draining, placing the dried mixture into a tray, performing heat sealing by using a preservative film, and storing the tray at the temperature of (4 +/-1) DEG C for subsequent processing.

Further, the aquatic product is one or more of hairtail, mackerel, Peru squid, North Tai squid, true squid and pomfret.

Further, the preservative film is a PE preservative film with the thickness of 0.013 mm.

The technical scheme provided by the embodiment of the invention can have the following beneficial effects:

according to the embodiments, the organic matters in the shell are removed by adopting alkali treatment, so that the acid-alkali circulation treatment effectively reduces the use amount of acid, overcomes the problem of great environmental pollution in chitin production, and further achieves the purposes of recycling and saving cost. Chitosan is extracted and compounded with a natural bacteriostatic agent, so that a novel natural antibacterial preservative is developed and applied to the preservation of aquatic products, and the deterioration of meat quality of the aquatic products in the storage process is effectively slowed down; effectively inhibiting the increase of TMA value and pH value TVB-N content in the refrigeration process of aquatic products, prolonging the refrigeration shelf life of hairtail, mackerel, Peru squid, North Taiyu squid, true squid and pomfret, and playing a better role in keeping fresh.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

Detailed Description

Example 1:

the preparation of chitosan comprises the following steps:

1. peeling Argentina red shrimp shell, spreading for airing, mincing with a mincing machine to obtain a product with length and width of about 5mm, cleaning with clear water, removing impurities, filtering, draining, spreading for airing, and storing in a dry and ventilated environment. It should be noted that the Argentina red shrimp shell can be replaced by other shrimp and crab shells, and preferably, the Argentina red shrimp shell is adopted because the Argentina red shrimp is large in size and easy to separate meat from shell.

2. Taking 100kg of clear water, adding 5kg of sodium hydroxide into the clear water, and uniformly stirring to obtain a 5% sodium hydroxide soak solution; weighing 33kg of crushed shrimp shells, soaking in the prepared soaking solution, controlling the reaction temperature to be 25 +/-2 ℃, controlling the soaking time to be 5h, and stirring once every 0.5 h; filtering, washing with clear water to neutrality, filtering, and draining.

3. Taking 100kg of clear water, adding 5L of hydrochloric acid into the clear water, and uniformly stirring to obtain a hydrochloric acid soak solution with the concentration of 5%; soaking shrimp shells soaked in alkali in the prepared hydrochloric acid soaking solution, controlling the reaction temperature to be 25 +/-2 ℃, controlling the soaking time to be 3h, and stirring once every 0.5 h; filtering, washing with water to neutrality, filtering, and draining.

4. And (3) performing acid-base circulating treatment until no bubbles are generated after acid is added, and finally rinsing and drying to obtain a chitin crude product.

5. Placing the chitin crude product into a water tank, washing with water, filtering, draining water, and placing into a tank filled with 0.5% oxalic acid solution, wherein the material-liquid ratio is 1: 3, fully stirring to completely soak the chitin crude product in the solution, controlling the reaction temperature to be 25 +/-2 ℃ and controlling the soaking time to be 1 h. Washing with water, drying at 65 deg.C to obtain chitin product, and storing in dry and ventilated environment.

6. Cleaning chitin product with water, transferring into a reaction kettle, weighing 10kg chitin product, soaking in 700L solution with 50% alkali (strong base such as sodium hydroxide and potassium hydroxide) concentration, controlling reaction temperature at 90 deg.C for 12 hr, and filtering; cooling to room temperature after the reaction is finished, washing with a large amount of clear water, putting into a basket with a perforated net, draining, drying the basket filled with the chitin crude product in a 65 ℃ oven, and crushing by a crusher to obtain the chitosan which is light yellow powdery solid.

A preparation method of a compound natural antibacterial preservative comprises the following steps:

0.05-0.15 part of tea polyphenol, 0.15-0.25 part of nisin and 0.5-1.5 parts of chitosan prepared by the above steps are mixed to obtain the compound natural type antibacterial preservative.

The application of the composite natural antibacterial preservative in the antibacterial and preservative treatment of aquatic products comprises the following steps:

1) the aquatic product is unfrozen, cleaned and cleaned for later use; taking 100kg of clear water, adding 0.5kg of chitosan, 0.05kg of tea polyphenol and 0.25kg of nisin into the clear water, adding a proper amount of acetic acid to enable the pH value to be 6, and uniformly stirring to prepare the natural antibacterial preservative soak solution.

2) 33kg of hairtail is weighed respectively and soaked in the natural antibacterial preservative soak solution for 1h at the temperature of 3 ℃, the hairtail is placed into a plastic tray after being drained, and is thermally sealed by a PE preservative film with the thickness of 0.013mm, and then the hairtail is immediately stored at the temperature of (4 +/-1) ° C.

Example 2:

the preparation of chitosan comprises the following steps:

1. peeling Argentina red shrimp shell, spreading for airing, mincing with a mincing machine to obtain a product with length and width of about 5mm, cleaning with clear water, removing impurities, filtering, draining, spreading for airing, and storing in a dry and ventilated environment. It should be noted that the Argentina red shrimp shell can be replaced by other shrimp and crab shells, and preferably, the Argentina red shrimp shell is adopted because the Argentina red shrimp is large in size and easy to separate meat from shell.

2. Taking 100kg of clear water, adding 3kg of sodium hydroxide into the clear water, and uniformly stirring to prepare a 3% sodium hydroxide soak solution; weighing 20kg of crushed shrimp shells, soaking in the prepared soaking solution, controlling the reaction temperature to be 25 +/-2 ℃, controlling the soaking time to be 5h, and stirring once every 0.5 h; filtering, washing with clear water to neutrality, filtering, and draining.

3. Taking 100kg of clear water, adding 3L of hydrochloric acid into the clear water, and uniformly stirring to obtain a hydrochloric acid soak solution with the concentration of 3%; soaking shrimp shells soaked in alkali in the prepared hydrochloric acid soaking solution, controlling the reaction temperature to be 25 +/-2 ℃, controlling the soaking time to be 3h, and stirring once every 0.5 h; filtering, washing with water to neutrality, filtering, and draining.

4. And (3) performing acid-base circulating treatment until no bubbles are generated after acid is added, and finally rinsing and drying to obtain a chitin crude product.

5. Placing the chitin crude product into a water tank, washing with water, filtering, draining water, and placing into a tank filled with 1% oxalic acid solution, wherein the material-liquid ratio is 1: 3, fully stirring to completely soak the chitin crude product in the solution, controlling the reaction temperature to be 25 +/-2 ℃ and controlling the soaking time to be 1 h. Washing with water, drying at 65 deg.C to obtain chitin product, and storing in dry and ventilated environment.

6. Cleaning chitin product with water, transferring into a reaction kettle, weighing 10kg chitin product, soaking in 800L solution with alkali (strong base such as sodium hydroxide and potassium hydroxide) concentration of 20%, controlling reaction temperature at 100 deg.C for 14 hr, and filtering; cooling to room temperature after the reaction is finished, washing with a large amount of clear water, putting into a basket with a perforated net, draining, drying the basket filled with the chitin crude product in a 65 ℃ oven, and crushing by a crusher to obtain the chitosan which is light yellow powdery solid.

The application of the composite natural antibacterial preservative in the antibacterial and preservative treatment of aquatic products comprises the following steps:

1) the aquatic product is unfrozen, cleaned and cleaned for later use; taking 100kg of clear water, adding 1kg of chitosan, 0.1kg of tea polyphenol and 0.2kg of nisin into the clear water, adding a proper amount of acetic acid to enable the pH value to be 6, and uniformly stirring to prepare the natural antibacterial preservative soak solution.

2) 33kg of hairtail is weighed respectively and soaked in the natural antibacterial preservative soak solution for 1h at the temperature of 3 ℃, the hairtail is placed into a plastic tray after being drained, and is thermally sealed by a PE preservative film with the thickness of 0.013mm, and then the hairtail is immediately stored at the temperature of (4 +/-1) ° C.

The sensory score was high during the soaking process relative to the un-soaked hairtail, TMA value: the TMA value of the sample treated by the compound preservative solution is increased to 20.7mg/100g from 5.3mg/100g after 21 days, which is lower than that of the blank control 41.3mg/100 mg. pH value: the pH value of the slightly frozen hairtail shows a slow descending trend in the initial 6 days, the pH values of the compound preservative solution treatment and the control hairtail are respectively reduced to 6.6 and 6.3 on the 6 th day, and then the pH value is rapidly increased. The whole pH change curve is V-shaped. After 9 days of storage, the pH value of the hairtail treated by the compound preservative solution is obviously lower than that of a blank control group. Test results show that the compound preservative solution can effectively delay the autolysis of the hairtail and has an obvious preservation effect. TVB-N: the change trend of the TVB-N values of the compound fresh-keeping liquid treatment and the control group is basically consistent. There was a gradual increase in the TBV-N values, but they began to show differences after 3 d. After the sample is slightly frozen for 3 days, the TVB-N value of the compound preservative solution treatment sample is obviously slower in increasing speed than that of the control sample. The TVB-N value of the control hairtail when stored for 3d in a micro-freezing way already reaches 9.8mg/100 g: the hairtail treated by the compound preservative solution is only 7.9mg/100g on the 3 rd day. After the hairtail is slightly frozen for 21d, the TVB-N values of the control and the hairtail treated by the compound preservative solution reach 79.6mg/100g and 36.9mg/100g respectively. The refrigerating shelf life is prolonged by 1-2 days compared with that of the embodiment 1.

Example 3:

the preparation of chitosan comprises the following steps:

1. peeling Argentina red shrimp shell, spreading for airing, mincing with a mincing machine to obtain a product with length and width of about 5mm, cleaning with clear water, removing impurities, filtering, draining, spreading for airing, and storing in a dry and ventilated environment. It should be noted that the Argentina red shrimp shell can be replaced by other shrimp and crab shells, and preferably, the Argentina red shrimp shell is adopted because the Argentina red shrimp is large in size and easy to separate meat from shell.

2. Taking 100kg of clear water, adding 6kg of sodium hydroxide into the clear water, and uniformly stirring to obtain a 6% sodium hydroxide soak solution; weighing 100kg of crushed shrimp shell, soaking in the prepared soaking solution, controlling the reaction temperature to be 25 +/-2 ℃, controlling the soaking time to be 5h, and stirring once every 0.5 h; filtering, washing with clear water to neutrality, filtering, and draining.

3. Taking 100kg of clear water, adding 6L of hydrochloric acid into the clear water, and uniformly stirring to obtain a hydrochloric acid soak solution with the concentration of 6%; soaking shrimp shells soaked in alkali in the prepared hydrochloric acid soaking solution, controlling the reaction temperature to be 25 +/-2 ℃, controlling the soaking time to be 3h, and stirring once every 0.5 h; filtering, washing with water to neutrality, filtering, and draining.

4. And (3) performing acid-base circulating treatment until no bubbles are generated after acid is added, and finally rinsing and drying to obtain a chitin crude product.

5. Placing the chitin crude product into a water tank, washing with water, filtering, draining water, and placing into a tank filled with 0.1% oxalic acid solution, wherein the material-liquid ratio is 1: 3, fully stirring to completely soak the chitin crude product in the solution, controlling the reaction temperature to be 25 +/-2 ℃ and controlling the soaking time to be 1 h. Washing with water, drying at 65 deg.C to obtain chitin product, and storing in dry and ventilated environment.

6. Cleaning chitin product with water, transferring into a reaction kettle, weighing 10kg chitin product, soaking in 400L solution of 40% alkali (strong base such as sodium hydroxide and potassium hydroxide), controlling reaction temperature at 80 deg.C for 10 hr, and filtering; cooling to room temperature after the reaction is finished, washing with a large amount of clear water, putting into a basket with a perforated net, draining, drying the basket filled with the chitin crude product in a 65 ℃ oven, and crushing by a crusher to obtain the chitosan which is light yellow powdery solid.

The application of the composite natural antibacterial preservative in the antibacterial and preservative treatment of aquatic products comprises the following steps:

1) the aquatic product is unfrozen, cleaned and cleaned for later use; 100kg of clear water is taken, 1.5kg of chitosan, 0.15kg of tea polyphenol and 0.15kg of nisin are added into the clear water, a proper amount of acetic acid is added to ensure that the pH value is 6, and the natural antibacterial preservative soak solution is prepared by uniformly stirring.

2) 33kg of hairtail is weighed respectively and soaked in the natural antibacterial preservative soak solution for 1h at the temperature of 3 ℃, the hairtail is placed into a plastic tray after being drained, and is thermally sealed by a PE preservative film with the thickness of 0.013mm, and then the hairtail is immediately stored at the temperature of (4 +/-1) ° C.

Compared with the unimpregnated Peru squid, the pickled Peru squid has high sensory evaluation value, TMA value, pH value and TVB-N value which slowly rise, and the refrigeration shelf life is prolonged, and is basically unchanged compared with the example 2.

Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.

It will be understood that the application is not limited to the precise arrangements described and illustrated above and that various modifications and changes may be made without departing from the scope thereof. The scope of the application is limited only by the appended claims.