WO2021088178A1 - 一种纳米保水剂的制备方法及其在甲壳虾类速冻品中的应用 - Google Patents

一种纳米保水剂的制备方法及其在甲壳虾类速冻品中的应用 Download PDF

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WO2021088178A1
WO2021088178A1 PCT/CN2019/123533 CN2019123533W WO2021088178A1 WO 2021088178 A1 WO2021088178 A1 WO 2021088178A1 CN 2019123533 W CN2019123533 W CN 2019123533W WO 2021088178 A1 WO2021088178 A1 WO 2021088178A1
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water
parts
retaining agent
nano water
frozen
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PCT/CN2019/123533
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English (en)
French (fr)
Inventor
张慜
孙亚男
柏宝松
汪海祥
王向连
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江南大学
扬州冶春食品生产配送股份有限公司
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Priority to US17/425,948 priority Critical patent/US11612169B2/en
Publication of WO2021088178A1 publication Critical patent/WO2021088178A1/zh

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B4/00—General methods for preserving meat, sausages, fish or fish products
    • A23B4/14—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12
    • A23B4/18—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12 in the form of liquids or solids
    • A23B4/20—Organic compounds; Microorganisms; Enzymes
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B4/00—General methods for preserving meat, sausages, fish or fish products
    • A23B4/02—Preserving by means of inorganic salts
    • A23B4/023—Preserving by means of inorganic salts by kitchen salt or mixtures thereof with inorganic or organic compounds
    • A23B4/0235—Preserving by means of inorganic salts by kitchen salt or mixtures thereof with inorganic or organic compounds with organic compounds or biochemical products
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B4/00—General methods for preserving meat, sausages, fish or fish products
    • A23B4/06—Freezing; Subsequent thawing; Cooling
    • A23B4/08—Freezing; Subsequent thawing; Cooling with addition of chemicals or treatment with chemicals before or during cooling, e.g. in the form of an ice coating or frozen block
    • A23B4/09—Freezing; Subsequent thawing; Cooling with addition of chemicals or treatment with chemicals before or during cooling, e.g. in the form of an ice coating or frozen block with direct contact between the food and the chemical, e.g. liquid N2, at cryogenic temperature
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B4/00—General methods for preserving meat, sausages, fish or fish products
    • A23B4/14—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12
    • A23B4/18—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12 in the form of liquids or solids
    • A23B4/24—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L17/00—Food-from-the-sea products; Fish products; Fish meal; Fish-egg substitutes; Preparation or treatment thereof
    • A23L17/40—Shell-fish
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/36—Freezing; Subsequent thawing; Cooling
    • A23L3/37—Freezing; Subsequent thawing; Cooling with addition of or treatment with chemicals
    • A23L3/375—Freezing; Subsequent thawing; Cooling with addition of or treatment with chemicals with direct contact between the food and the chemical, e.g. liquid nitrogen, at cryogenic temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the invention relates to the preparation and application of a nano water retaining agent for crustacean aquatic products, and belongs to the technical field of food processing.
  • Crustacean aquatic products have the characteristics of high protein and high moisture. Under the action of oxidation reaction, microorganisms and endogenous enzymes, they are prone to spoilage and deterioration, resulting in a decline in edible quality and reducing economic value.
  • its sales methods mainly include fresh sales and frozen sales.
  • live sales can maximize the quality of crustacean aquatic products, due to seasonal and regional restrictions, fresh sales are limited to specific regions and seasons.
  • frozen sales are mostly adopted. Frozen preservation can keep the nutritional value of crustacean aquatic products to the utmost extent, but ice crystals produced during the freezing process can easily damage muscle cells, denature protein, increase the loss of juice during thawing, and reduce its flavor and nutritional value.
  • Water retention agent is one of the effective methods to reduce the degree of frozen denaturation of aquatic product protein. It can effectively inhibit the growth of ice crystals in frozen aquatic products, reduce the frozen denaturation of protein, and reduce the impact of frozen storage on muscle quality.
  • Carbohydrates are widely used as water-retaining agents in frozen aquatic products. The mechanism of action is that carbohydrates can change the state of bound water embedded in protein molecules, replace and bind to the bound water on the surface of protein molecules, thereby inhibiting protein The effect of sex change.
  • the hydroxyl groups in the sugar molecules react with certain groups of the protein molecules to avoid aggregation and denaturation between protein molecules.
  • Xylitol is a kind of polyhydroxy sugar alcohol. Its molecule contains multiple hydroxyl groups.
  • hydroxyl groups can be combined with water molecules in the form of hydrogen bonds.
  • xylitol will absorb some water to enhance the water holding capacity of the product.
  • xylitol will release some water to maintain the moisture retention of the product.
  • carboxymethyl chitosan has a good development prospect in food processing. Its application in the meat industry has caused Received widespread attention. Relevant experiments at home and abroad have found that chitosan can form a film layer on the surface of chilled meat, effectively preventing water loss, reducing juice loss, and improving the water retention of meat.
  • salt helps the dissolution of protein in muscles. After these proteins (mainly myosin) dissolve, an adhesive layer is formed on the surface of the meat to prevent water loss.
  • salt and protein interact to form a powerful three-dimensional network structure, which helps to confine water, thereby achieving the effect of improving the tissue state of meat products.
  • Sodium alginate has good water solubility and has excellent chelating ability to metal ions such as Ca 2+ and Mg 2+ in water. It may chelate with Ca 2+ and Mg 2+ in shrimp meat, thereby preventing muscles. Water loss within the organization.
  • Pullulan is a linear polysaccharide formed by the polymerization of repeating units of maltotriose linked by ⁇ -1,4 glycosidic bonds through ⁇ -1,6 glycosidic bonds, with a molecular weight of 20,000-2 million and a degree of polymerization of 100-5,000.
  • the polysaccharide has two important characteristics: structurally flexible and relatively high solubility.
  • Pullulan has strong film-forming properties, gas barrier properties, plasticity, and viscosity, and has excellent properties such as being easily soluble in water, non-toxic, harmless, colorless and tasteless. It has been widely used in medicine, food, light industry, Chemical and petroleum fields. On May 19, 2006, the Ministry of Health issued the No. 8 Announcement.
  • Pullulan is one of the four new food additives. It can be used in candy, chocolate coating, diaphragm, compound seasoning and fruit and vegetable juice beverages. Used as a coating agent and thickening agent. Studies have shown that pullulan, as a new type of marine product film preservative, can fully and effectively inhibit the accumulation of volatile base nitrogen in marine products, and also has a good protective effect on the evaporation of water in marine products.
  • Inulin is a soluble dietary fiber. It is a linear linear polysaccharide formed by the polymerization of fructose through ⁇ -(2-1) glycosidic bonds. The end of the molecule is connected to a glucose residue, and the degree of polymerization is between 2-60. soluble in water.
  • inulin is used in various foods to improve texture and reduce calories. It can replace fat and sugar, become a low-calorie filler, and can also be used as a water-retaining agent .
  • inulin can be used as a protein protective agent to reduce protein denaturation, and it can stabilize the protein conformation during storage. It may also reduce the formation of ice crystals.
  • inulin can be used as a strain to preserve anti- One of the main components of the cryogel is used to protect cells and proteins.
  • Inulin is different from most sugar antifreezes such as sucrose sugar. It is a non-digestible carbohydrate. Therefore, it has minimal impact on blood sugar and is suitable for diabetics.
  • inulin has the ability to stabilize protein during freeze-drying. Better than trehalose.
  • Xylitol and chitosan in the compound water-retaining agent are a type of polymer that swells when exposed to water. It has a huge polymer "skeleton" and carries a large number of -COOH, -OH, -NH2 and other polar hydrophilic groups. The mass can absorb water hundreds of times or even higher than its own mass. With the same quality of water retaining agent, the smaller the particle size, the larger the specific surface area, the higher the water absorption rate, the shorter the time required for water saturation, and the smaller the particle size, the greater the rate of release of water to the sample when the sample is under water stress. high.
  • Luo Xiaodong et al. disclosed "a practical food water retention agent" (Chinese Patent Application No. CN201510516820.0), the formula includes 7-15 parts of phospholipids, 20-30 parts of sodium bicarbonate, and 2-8 parts of sodium hexametaphosphate. , Trisodium pyrophosphate is 1-4 parts, calcium lactate is 1-3 parts, soybean oil is 20-30 parts.
  • the present invention uses inulin and sugar alcohol to partially replace phosphate, which can not only reduce the added amount of phosphate, but also increase the frozen storage quality of aquatic products.
  • Qi Fugang et al. disclosed "a water-retaining agent for aquatic products" (Chinese Patent Application No. CN201710964216.3), in which 30-50 parts of protease, 10-15 parts of antioxidants, 10-15 parts of tea polyphenols, and 12 parts of lemon peel are added to the raw materials.
  • the present invention uses ultrasonic waves to process the water-retaining agent into nanoparticles, increase the specific surface area, promote the contact between the sample and the water-retaining agent, and increase the water holding capacity of the product.
  • Yin Lihua et al. disclosed "a composite water retaining agent for meat products" (Chinese Patent Application No. CN201310390049.8), in which 30-50 parts of protease, 10-20 parts of nonionic surfactants, and 20-30 parts of antioxidants are added to the raw materials. Parts, 5-10 parts of carrageenan, 10-20 parts of complex phosphate.
  • the addition of xylitol and chitosan in the present invention can not only keep the meat of aquatic products delicious, but also solve the problem of physical harm to consumers due to excessive phosphate.
  • the present invention adopts a combination of sugar alcohol and nano-treatment, which can also increase the nutrition and water holding capacity of the product.
  • the present invention uses the combination of xylitol, chitosan and sodium alginate, and utilizes the polyhydroxyl water retention of xylitol and the good film-forming properties of chitosan and sodium alginate to improve the safety of the processing process. , Reduce the cost of production.
  • Han Wenbin et al. disclosed "a kind of water retention agent for shrimp" (Chinese Patent Application No. CN201010511883.4), in which 30-50 parts of modified starch, 20-30 parts of antioxidants, and 5-10 parts of food acidity regulators are added to the raw materials. 2-4 parts of mannitol, 1-2 parts of lactitol, 2-4 parts of glycine. In contrast, this patent uses natural fresh-keeping and water-retaining raw materials, which guarantees food safety and improves the economic benefits of aquatic product processing enterprises.
  • Zhang Et al. published "a method for maintaining the delicate texture and flavor of frozen freshwater shrimp and crab shelled aquatic products" (Chinese patent application number CN200610039317.1).
  • the antioxidant solution is cooked and immersed for conditioning, and then combined with quick freezing, vacuum packaging and low-temperature freezing technology.
  • this patent uses ultrasonic technology to process the raw material of the water-retaining agent and process it into a nanometer level, which increases the contact area with the product.
  • the purpose of the present invention is to provide a preparation and application of a nano water-retaining agent for crustacean shrimp, which mainly solves the problem of water loss of crustacean shrimp during the existing frozen storage process, which leads to the decrease of texture and nutritional quality of aquatic products.
  • the method is beneficial to improve the water retention of the product, increase the shelf life of the product, and promote the development of frozen crustacean aquatic products.
  • a preparation method of nano water retaining agent the raw material formula ratio is calculated as follows in parts by weight: 10-15 parts of inulin, 12-20 parts of xylitol, 5-10 parts of carboxymethyl chitosan, pullulan 5- 10 parts, 3-7 parts of sodium tripolyphosphate, 1-3 parts of sodium chloride, 1-3 parts of sodium alginate, 900-1000 parts of water.
  • the raw material formula ratio is as follows in parts by weight: 13 parts of inulin, 16 parts of xylitol, 6 parts of carboxymethyl chitosan, 5 parts of pullulan, 5 parts of sodium tripolyphosphate, 2 parts of sodium chloride Parts, 1 part of sodium alginate, 952 parts of water.
  • the raw materials are fully mixed and then homogenized by a homogenizer 20 Min, colloid mill treatment for 5 min, then ultrasonic cell disruptor 500 W treatment for 30 min, centrifugation, and then the nano water retention agent is obtained.
  • the particle size range of the nano water retaining agent is 50-300 nm.
  • the body length of the crustaceans selected is 10-15 cm.
  • the volume ratio of the crustacean shrimp to the nano water retaining agent in the step (2) is 2-3:8-9.
  • the crustacean shrimp treated in the step (3) is quick-frozen so that the core temperature of the product reaches -10°C within half an hour, and then it is frozen and stored at -18°C.
  • the crustaceans are crayfish, sea prawns or river prawns.
  • the present invention uses inulin, xylitol, and pullulan to partially replace the phosphate in the traditional water-retaining agent to reduce the phosphate content, and at the same time utilizes the polyhydroxy water retention properties of inulin and xylitol and the pullulan Fresh-keeping performance, better maintain the water retention and nutritional quality of frozen aquatic products.
  • the invention adopts the combination of carboxymethyl chitosan and sodium alginate, utilizes the good solubility of carboxymethyl chitosan and the good film-forming properties of sodium alginate, blocks the volatilization of water, and improves the safety of the processing process. , Reduce the cost of production.
  • the water-retaining agent is compounded by ultrasonic treatment, and the water-retaining agent is made into nano particles.
  • the carboxymethyl chitosan-xylitol nano water-retaining agent is composed of the following raw materials in parts by weight: 10 parts of inulin, 16 parts of xylitol, and carboxymethyl 6 parts of base chitosan, 5 parts of pullulan, 5 parts of sodium tripolyphosphate, 2 parts of sodium chloride, 2 parts of sodium alginate, and 954 parts of water. Proceed as follows:
  • the nano water retention agent prepared by this method has better water retention of crayfish and shrimp during the freezing storage process, and the water loss rate after 6 months of freezing storage is below 10%.
  • Sodium alginate-xylitol nano water-retaining agent is composed of the following raw materials in parts by weight: 12 parts of inulin, 20 parts of xylitol, carboxymethyl chitosan 5 parts of sugar, 5 parts of pullulan, 6 parts of sodium tripolyphosphate, 2 parts of sodium chloride, 2 parts of sodium alginate, and 948 parts of water. Proceed as follows:
  • the nano-water-retaining agent prepared by this method has better water retention in the process of frozen storage, and the water loss rate after 6 months of frozen storage is less than 10%.
  • the carboxymethyl chitosan-xylitol nano water retention agent is composed of the following raw materials: 13 parts of inulin, 16 parts of xylitol, carboxymethyl 6 parts of base chitosan, 5 parts of pullulan, 5 parts of sodium tripolyphosphate, 2 parts of sodium chloride, 2 parts of sodium alginate, and 951 parts of water. Proceed as follows:
  • the nano-water-retaining agent prepared by this method has better water retention in the process of frozen storage, and the water loss rate after 6 months of frozen storage is less than 10%.

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Abstract

一种纳米保水剂的制备方法及其在甲壳虾类速冻品中的应用，属于食品加工技术领域。本发明配方包括菊粉、木糖醇、羧甲基壳聚糖、普鲁兰多糖、三聚磷酸钠、氯化钠、海藻酸钠，将粉类原料与水混合均匀后经均质机、胶体磨、超声波处理，然后得到纳米保水剂。本发明方法同时还涉及该抗冻保水剂在冷冻甲壳类水产品中的应用，与现有技术相比，本发明中的纳米保水剂能有效避免冷冻保藏过程甲壳类水产品的蛋白变性和氧化，较大程度保持甲壳类水产品的持水性及其营养价值，6个月速冻期间水分流失率在10%以下，从而使其获得良好的经济价值。

Description

一种纳米保水剂的制备方法及其在甲壳虾类速冻品中的应用 技术领域
本发明涉及一种甲壳类水产品的纳米保水剂的制备及应用，属于食品加工技术领域。
 背景技术
甲壳类水产品具有高蛋白、高水分的特点，在氧化反应、微生物及内源酶的作用下极易发生腐败变质，导致食用品质下降，降低了经济价值。目前其销售形式主要有鲜销和冻销两种方式，活体销售虽然能最大限度保持甲壳类水产品的品质，但由于受季节性、地域性等条件限制，鲜销仅限于特定的地区和季节，对于生产淡季或出口到国外的产品多采用冻销的方式。冷冻保藏可最大限度地保持甲壳类水产品的营养价值，但冻藏过程中产生的冰晶，易使肌肉细胞受损、蛋白质变性，增加解冻时的汁液损失，导致其风味和营养价值下降。
保水剂是降低水产品蛋白质冷冻变性程度有效的方法之一，其可有效抑制冷冻水产品中冰晶的生长，减少蛋白质的冷冻变性，降低冻藏对肌肉品质造成的影响。糖类物质作为保水剂被广泛应用于冷冻水产品中，其作用机理是糖类可改变包埋在蛋白质分子中结合水的状态，取代蛋白质分子表面的结合水并与之结合，从而达到抑制蛋白质变性的效果。此外，糖分子中的羟基与蛋白质分子的某些基团发生反应，从而避免蛋白质分子间的聚集变性。木糖醇是一种多羟基糖醇，其分子中含有多个羟基，这些羟基能以氢键形式与水分子结合，在潮湿的环境中，木糖醇会吸收一些水分，增强产品的持水性，同时降低产品的水分活度，当环境中的湿度降低时，木糖醇则会释放出一些水分维持产品的保湿性。羧甲基壳聚糖作为一种天然、无毒、高效的食品防腐剂、成膜剂，在食品加工中具有很好的开发前景，其在肉品工业中的应用，近十多年来引起了广泛关注。国内外有关实验发现，壳聚糖能在冷却肉表面形成薄膜层，有效地防止水分散失，能够减少汁液流失，提高肉的保水性。食盐的添加有助于肌肉中蛋白质的溶出，这些蛋白质(主要是肌球蛋白)溶出后，在肉表面形成一粘着层,可防止水分流失。另外，水产品在蒸煮过程中，食盐和蛋白质相互作用，可形成一个强大的三维立体网状结构，有助于束缚水分，从而达到改善肉制品组织状态的功效。海藻酸钠具有水溶性好、对水中的Ca 2+、Mg 2+等金属离子具有优良的螯合能力，可能与虾肉中的Ca 2+、Mg 2+发生螯合作用，从而阻止了肌肉组织内部水分流失。
普鲁兰多糖是由α-1，4糖苷键连接的麦芽三糖重复单位经α-1，6糖苷键聚合而成的直链状多糖，分子量2万～200万，聚合度100～5000。该多糖有两个重要的特性：结构上富有弹性，溶解度比较大。普鲁兰多糖的成膜性、阻气性、可塑性、粘性均较强，并且具有易溶于水、无毒无害、无色无味等优良特性，已广泛应用于医药、食品、轻工、化工和石油等领域。2006年5月19日，国家卫生部发布了第8号公告，普鲁兰多糖为新增四种食品添加剂产品之一，可在糖果、巧克力包衣、膜片、复合调味科和果蔬汁饮料中用作被膜剂和增稠剂。研究表明，普鲁兰多糖作为一种新型海产品被膜保鲜剂，能充分有效地抑制海产品体内挥发性盐基氮的大量积累，对海产品体内水分蒸发也有良好地保护作用。
菊粉是一种可溶性的膳食纤维，它是果糖通过β-（2-1）糖苷键聚合而成的线性直链多糖，其分子末端连接一个葡萄糖残基，聚合度在2-60 之间，易溶于水。菊粉作为食品和营养的增补剂，被用于各种食品中，具有改善质构、减少热量等作用，它可以代替脂肪和糖类，成为低卡路里的填充剂，也可以作为一种保水剂。除此之外，菊粉可作为蛋白保护剂，减少蛋白质的变性，而且在储藏过程中起到稳定蛋白质构象的作用，还可能起到减少冰晶生成的作用，如菊粉可作为菌种保藏抗冻剂的主要成分之一，用于对细胞和蛋白的保护。菊粉与蔗糖果糖等大多数糖类抗冻剂不同，它是不易消化的碳水化合物，因此，对血糖的影响极小，适合糖尿病者使用；另外，菊粉在冷冻干燥过程中稳定蛋白质的能力比海藻糖更好。
复配保水剂中的木糖醇、壳聚糖是一类遇水膨胀的聚合物，具有一个庞大的聚合物“骨架”并携带大量的-COOH，-OH，-NH2等极性亲水基团，可吸附自身质量数百倍甚至更高的水分。相同质量的保水剂，粒径越小，比表面积越大，吸水速率越高，吸水饱和所需的时间越短，且粒径越小，当样品水分处于胁迫时向样品释放水分的速率也越高。
罗小东等人公开了“一种实用食品保水剂”（中国专利申请号CN201510516820.0），配方包括磷脂为7-15份、碳酸氢钠为20-30份、六偏磷酸钠为2-8份、焦磷酸一氢三钠为1-4份、乳酸钙为1-3份、大豆油为20-30份。与其相比，本发明采用菊粉、糖醇部分替代磷酸盐，不仅可降低磷酸盐添加量，还可以增加水产品的冻藏品质。
齐富刚等人公开了“一种水产品保水剂”（中国专利申请号CN201710964216.3），原料中添加蛋白酶30～50份、抗氧化剂10～15份、茶多酚10～15份、柠檬皮12～18份、海藻酸钠0～15份、海藻糖0～6份、鱼腥草5～10份、低聚木糖6～8份、氨基乙酸3～5份、壳聚糖4～5份、甘露醇2～4份、食品酸度调节剂1～3份、软化剂0.5～3份、乳糖醇1～3份、红曲红0～1份、琼脂粉0.1～0.5份、碱性磷酸盐0.1～0.3份。与其相比，本发明采用超声波将保水剂处理成纳米颗粒，增大比表面积，促进样品与保水剂接触，增加产品的持水性。
尹立华等人公开了“一种复合型肉制品保水剂”（中国专利申请号CN201310390049.8），原料中添加了蛋白酶30-50份、非离子表面活性剂10-20份、抗氧化剂20-30份、卡拉胶5-10份、复合磷酸盐10-20份。与其相比，本发明添加木糖醇、壳聚糖，不仅可保持水产品肉质鲜美，还解决了因磷酸盐超标给消费者带来身体伤害等问题。
励建荣等人公开了“一种用于虾仁的无磷保水剂及其使用方法”（中国专利申请号CN201010523259.6），配方包括褐藻胶低聚糖0.5~3%；变性淀粉1~10%；氯化钙0.3~3%；山梨糖醇0.5~10%；乳酸0.5~5%；余量为纯净水。与其相比，本发明采用糖醇与纳米处理相结合的方式，还可以增加产品的营养性和持水性。
张小利等人研究不同糖醇对南美对虾的影响表明，木糖醇、异麦芽糖醇及甘露糖醇可作为抗冻保水剂加以使用, 可为低糖、安全的无磷保水剂生产应用提供基础。与其相比，本发明采用木糖醇、壳聚糖与海藻酸钠相结合，利用木糖醇的多羟基保水性与壳聚糖、海藻酸钠的良好成膜性，提高了加工过程安全性，降低了生产的成本。
林佑任等人公开了“一种提升加工肉品组织口感及多汁性的无磷保水剂”（中国专利申请号CN201410464374.9），原料中添加了碳酸氢钠20-40份、碳酸钾10-20份、柠檬酸钠10-20份、环糊精10-20份、海藻酸钠8-15份、卡拉胶5-15份、黄原胶3-10份。与其相比，本发明采用糖醇体系与食盐相结合处理，可明显改善冷冻虾仁质构，避免虾仁在烹饪过程中变硬、易碎、肉质变粗糙和缓解汁液流失。
韩文彬等人公开了“一种虾保水剂”（中国专利申请号CN201010511883.4），原料中添加了变性淀粉30-50份、抗氧化剂20-30份、食品酸度调节剂5-10份、甘露醇2-4份、乳糖醇1-2份、氨基乙酸2-4份。与其相比，本专利均是采用天然保鲜、保水原料，食品安全性得到保障，提高了水产品加工企业的经济效益。
张
Figure 615c
等人公开了“保持调理冷冻淡水虾蟹带壳水产品细嫩质构和风味的方法”（中国专利申请号CN200610039317.1），将鲜活的水产品进行清洗后，对其采用添加保水剂和抗氧化剂的溶液进行蒸煮和浸泡调理，再联合使用速冻、真空包装和低温冻藏技术。与其相比，本专利采用超声技术处理保水剂原料将其加工成纳米级别，增大与产品的接触面积。
邹国勇等人公开了“甲壳类水产品的微冻保鲜工艺”（中国专利申请号CN201810989188.5），将捕捞时间不超过8个小时的甲壳类水产，先进行预冷处理、在加工车间进行消毒处理、在甲壳类水产的冰点区间零下27.5～30.1℃进行15～30分钟的微冻处理，之后在零下28～30℃区间的冷库进行保存。与其相比，本专利开发新型保水剂，经其处理后迅速降温至-10 ℃，然后即可于冷库中贮藏，工艺简单，节约成本。
 技术问题
本发明的目的是提供一种甲壳虾类的纳米保水剂的制备及应用，主要解决现有的冷冻贮藏过程中甲壳虾类水分流失，导致水产品质构、营养品质下降的问题。该方法有利于改善产品持水性，提高产品的保质期，促进甲壳类冷冻水产品的发展。
 技术解决方案
一种纳米保水剂的制备方法，原料配方比例按重量份计如下：菊粉10-15份、木糖醇12-20份、羧甲基壳聚糖5-10份、普鲁兰多糖5-10份、三聚磷酸钠3-7份、氯化钠1-3份、海藻酸钠1-3份、水900-1000份。
进一步的，原料配方比例按重量份计如下：菊粉13份、木糖醇16份、羧甲基壳聚糖6份、普鲁兰多糖5份、三聚磷酸钠5份、氯化钠2份、海藻酸钠1份、水952份。
具体过程：将原料充分混匀后经均质机均质15-25 min，胶体磨处理4-6 min，然后超声波细胞破碎仪400-600 W处理25-35 min，离心，即得到纳米保水剂。
进一步的，具体过程：将原料充分混匀后经均质机均质20 min，胶体磨处理5 min，然后超声波细胞破碎仪500 W处理30min，离心，即得到纳米保水剂。
所述纳米保水剂的粒度范围为50-300nm。
一种纳米保水剂在甲壳虾类速冻品中的应用，步骤如下：
（1）将鲜活的甲壳虾类快速致死，清洗，沥干水分，备用；
（2）将处理后的甲壳虾类打孔，浸泡于制备的纳米保水剂中，浸泡温度2-6 ℃，浸泡时间2-4h；
（3）将浸泡后的产品从纳米保水剂中取出，用纱布擦干水分；
（4）将上述水产品分装，于-16~-20 ℃下冻藏。
所述步骤（1）选取甲壳虾类的体长均为10~15 cm。
所述步骤（2）的甲壳虾类与纳米保水剂的体积比2-3：8-9。
所述步骤（4），将步骤（3）处理后的甲壳虾类进行速冻，使产品的中心温度在半小时内达到-10 ℃，然后于-18 ℃冻藏。
所述甲壳虾类为小龙虾、海虾或河虾等。
 有益效果
本发明通过用菊粉、木糖醇、普鲁兰多糖部分替代传统法保水剂中的磷酸盐，降低磷酸盐含量，同时利用菊粉、木糖醇的多羟基保水性能及普鲁兰多糖的保鲜性能，较好的维持冻藏水产品的保水性及营养品质。本发明采用羧甲基壳聚糖与海藻酸钠相结合，利用羧甲基壳聚糖较好的溶解性、海藻酸钠的良好成膜性，阻断水分的挥发，提高了加工过程安全性，降低了生产的成本。本发明利用超声波处理复配保水剂，将其制成纳米粒子，相同质量的保水剂，粒径越小，比表面积越大，吸水速率越高，可较好的维持产品的保水性。
 本发明的实施方式
实施例1
纳米保水剂制备及在小龙虾速冻品中的保水应用，羧甲基壳聚糖-木糖醇纳米保水剂按照以下原料的重量份数组成：菊粉10份、木糖醇16份、羧甲基壳聚糖6份、普鲁兰多糖5份、三聚磷酸钠5份、氯化钠2份、海藻酸钠2份、水954份。步骤如下：
（1）原料混合：将原料按以上比例称量后混合均匀，备用；
（2）超声波处理：将步骤（1）中混合均匀后的原料加入定量的水，搅拌后，将原料充分混匀后经均质机均质20 min，胶体磨处理5 min，将容器放置于超声波细胞破碎仪内，将直径为2 cm的探头伸入原料中，使用低温水浴保持样品温度处于室温，密封，在500 W超声波处理30 min，超声周期为工作4 s，间歇2 s；
（3）保水剂的应用：将步骤（2）中超声波处理后的纳米保水剂在冷冻水产品中的应用。
A、将鲜活的小龙虾(体长10~15 cm)快速致死，清洗，沥干水分，备用；
B、将处理后的小龙虾浸泡于制备的纳米保水剂中(小龙虾与纳米保水剂的体积比2：8)，浸泡温度4 ℃，浸泡时间2h；
C、将浸泡后的产品从保水剂中取出，用纱布擦干水分；
D、将上述水产品分装，于-18 ℃下冻藏。
与普通保水剂相比该方法制备的纳米保水剂在冻藏过程中小龙虾虾仁水分保持性较好，冻藏6个月后水分流失率在10%以下。
实施例2
纳米保水剂制备及在海虾速冻品中的保水应用，海藻酸钠-木糖醇纳米保水剂按照以下原料的重量份数组成：菊粉12份、木糖醇20份、羧甲基壳聚糖5份、普鲁兰多糖5份、三聚磷酸钠6份、氯化钠2份、海藻酸钠2份、水948份。步骤如下：
（1）原料混合：将原料按以上比例称量后混合均匀，备用；
（2）超声波处理：将步骤（1）中混合均匀后的原料加入定量的水，搅拌后，将原料充分混匀后经均质机均质20 min，胶体磨处理5 min，将容器放置于超声波细胞破碎仪内，将直径为2 cm的探头伸入原料中，使用低温水浴保持样品温度处于室温，密封，在500 W超声波处理30 min，超声周期为工作4 s，间歇2 s；
（3）保水剂的应用：将步骤（2）中超声波处理后的纳米保水剂在冷冻水产品中的应用。
A、将鲜活的海虾快速致死，清洗，沥干水分，备用；
B、将处理后的海虾浸泡于制备的纳米保水剂中(海虾与纳米保水剂的体积比2：8)，浸泡温度4 ℃，浸泡时间2 h；
C、将浸泡后的产品从保水剂中取出，用纱布擦干水分；
D、将上述水产品分装，于-18℃下冻藏。
与普通保水剂相比该方法制备的纳米保水剂在冻藏过程中海虾虾仁水分保持性较好，冻藏6个月后水分流失率在10%以下。
实施例3
纳米保水剂制备及在河虾速冻品中的保水应用，羧甲基壳聚糖-木糖醇纳米保水剂按照以下原料的重量份数组成：菊粉13份、木糖醇16份、羧甲基壳聚糖6份、普鲁兰多糖5份、三聚磷酸钠5份、氯化钠2份、海藻酸钠2份、水951份。步骤如下：
（1）原料混合：将原料按上述比例称量后混合均匀，备用；
（2）超声波处理：将步骤（1）中混合均匀后的原料加入定量的水，搅拌后，将原料充分混匀后经均质机均质20 min，胶体磨处理5 min，将容器放置于超声波细胞破碎仪内，将直径为2 cm的探头伸入原料中，使用低温水浴保持样品温度处于室温，密封，在500 W超声波处理30 min，超声周期为工作4 s，间歇2 s；
（3）保水剂的应用：将步骤（2）中超声波处理后的纳米保水剂在冷冻水产品中的应用。
A、将鲜活的河虾(体长10~15 cm)快速致死，清洗，沥干水分，备用;
B、将处理后的河虾浸泡于制备的纳米保水剂中(河虾与纳米保水剂的体积比2：8)，浸泡温度4 ℃，浸泡时间2h；
C、将浸泡后的产品从保水剂中取出，用纱布擦干水分；
D、将上述水产品分装，于-18 ℃下冻藏。
与普通保水剂相比该方法制备的纳米保水剂在冻藏过程中河虾虾仁水分保持性较好，冻藏6个月后水分流失率在10%以下。

Claims (10)

  1. 一种纳米保水剂的制备方法，其特征在于，原料配方比例按重量份计如下：菊粉10-15份、木糖醇12-20份、羧甲基壳聚糖5-10份、普鲁兰多糖5-10份、三聚磷酸钠3-7份、氯化钠1-3份、海藻酸钠1-3份、水900-1000份；具体过程：将原料充分混匀后经均质机均质15-25 min，胶体磨处理4-6 min，然后超声波细胞破碎仪400-600 W处理25-35 min，离心，即得到纳米保水剂。
  2. 根据权利要求1所述的一种纳米保水剂的制备方法，其特征在于，原料配方比例按重量份计如下：菊粉13份、木糖醇16份、羧甲基壳聚糖6份、普鲁兰多糖5份、三聚磷酸钠5份、氯化钠2份、海藻酸钠1份、水952份。
  3. 根据权利要求1或2所述的一种纳米保水剂的制备方法，其特征在于，具体过程：将原料充分混匀后经均质机均质20 min，胶体磨处理5 min，然后超声波细胞破碎仪500 W处理30min，离心，即得到纳米保水剂。
  4. 根据权利要求1或2所述的一种纳米保水剂的制备方法，其特征在于，所述纳米保水剂的粒度范围为50-300nm。
  5. 根据权利要求3所述的一种纳米保水剂的制备方法，其特征在于，所述纳米保水剂的粒度范围为50-300nm。
  6. 采用权利要求1-5任一所述的方法制备的纳米保水剂在甲壳虾类速冻品中的应用，其特征在于，步骤如下：
    （1）将鲜活的甲壳虾类快速致死，清洗，沥干水分，备用；
    （2）将处理后的甲壳虾类打孔，浸泡于制备的纳米保水剂中，浸泡温度2-6 ℃，浸泡时间2-4h；
    （3）将浸泡后的产品从纳米保水剂中取出，用纱布擦干水分；
    （4）将上述水产品分装，于-16~-20 ℃下冻藏。
  7. 根据权利要求6所述的应用，其特征在于，所述步骤（2）的甲壳虾类与纳米保水剂的体积比为2-3：8-9。
  8. 根据权利要求6或7所述的应用，其特征在于，所述步骤（4），将甲壳虾类进行速冻，使产品的中心温度在半小时内达到-10 ℃，然后于-18 ℃冻藏。
  9. 根据权利要求6或7所述的应用，其特征在于，所述步骤（1）中，选取甲壳虾类的体长均为10~15 cm；所述甲壳虾类为小龙虾、海虾或河虾等。
  10. 根据权利要求8所述的应用，其特征在于，所述步骤（1）中，选取甲壳虾类的体长均为10~15 cm；所述甲壳虾类为小龙虾、海虾或河虾等。
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