WO2020107950A1 - 一种高钙低钠海藻粉及其制备方法和应用 - Google Patents

一种高钙低钠海藻粉及其制备方法和应用 Download PDF

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WO2020107950A1
WO2020107950A1 PCT/CN2019/101026 CN2019101026W WO2020107950A1 WO 2020107950 A1 WO2020107950 A1 WO 2020107950A1 CN 2019101026 W CN2019101026 W CN 2019101026W WO 2020107950 A1 WO2020107950 A1 WO 2020107950A1
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seaweed
sodium
calcium
raw material
algae
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PCT/CN2019/101026
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English (en)
French (fr)
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梁云
王身健
曹晟
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瞿瀚鹏
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L17/00—Food-from-the-sea products; Fish products; Fish meal; Fish-egg substitutes; Preparation or treatment thereof
    • A23L17/60—Edible seaweed
    • 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
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • 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
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
    • 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
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
    • A23L5/23—Removal of unwanted matter, e.g. deodorisation or detoxification by extraction with solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C21/00—Disintegrating plant with or without drying of the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
    • B02C23/14—Separating or sorting of material, associated with crushing or disintegrating with more than one separator
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
    • B02C23/16—Separating or sorting of material, associated with crushing or disintegrating with separator defining termination of crushing or disintegrating zone, e.g. screen denying egress of oversize material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/30—Combinations with other devices, not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
    • B02C23/16—Separating or sorting of material, associated with crushing or disintegrating with separator defining termination of crushing or disintegrating zone, e.g. screen denying egress of oversize material
    • B02C2023/165—Screen denying egress of oversize material

Definitions

  • the invention relates to the technical field of seaweed processing, in particular to a preparation method and application of high calcium low sodium seaweed powder.
  • Calcium is one of the most abundant inorganic elements in the human body. It is located after carbon, hydrogen, oxygen and nitrogen. It is the fifth largest element in the human body. In teeth, only about 1% is distributed in extracellular fluid, that is, the intercellular fluid of blood and soft tissues. Calcium is the main component of human bones and teeth, and plays an important role in maintaining the normal physiological functions of the human circulation, respiration, nerve, endocrine, digestion, blood, muscle, bone, urinary, immune and other systems. In these physiological functions, the most widely recognized is the effect of calcium on the development function of human bones.
  • calcium sources with high calcium content are the first to introduce molecular calcium carbonate of inorganic origin, and such inorganic calcium carbonate has a problem that it is difficult to be digested by stomach acid-the texture is hard and the density is large.
  • the specific surface area of the calcium source needs to be as large as possible in order to increase its contact area with gastric acid, thereby improving the ionization conversion rate, and creating conditions for increasing the absorption rate.
  • seaweed is rich in calcium source and has a honeycomb porous structure.
  • the specific surface area of conventional calcium carbonate is 1.5-1.8m 2 /g, while the ratio of calcium source in seaweed
  • the surface area can reach 8.5-10.1m 2 /g, which is easy to dissolve and ionize in the gastrointestinal tract, improve the body's ability to digest and absorb calcium and have a significant effect of neutralizing stomach acid.
  • seaweed is also rich in magnesium, sodium, potassium and other constant elements required by the human body, which plays an important role in human health.
  • seaweed is generally simply rinsed and directly beaten to form seaweed powder, or dried and crushed to form seaweed powder, which is used as a calcium source.
  • seaweed Due to the particularity of the seaweed growth environment, seaweed It will be rich in sodium and heavy metals in seawater. Excessive sodium intake will break the metabolic balance of the body, hinder the absorption of other nutrients, and pose a threat to kidney organs.
  • cells To maintain normal function, cells must ingest potassium and reject sodium. The potassium content in normal cells is 10 times the sodium content If the cells lose their potassium intake and are damaged, they will immediately start to multiply and divide. The excessive amount of heavy metals will directly cause the safety of seaweed powder as a calcium supplement for the human body, which will affect the application of seaweed as a calcium source.
  • the purpose of the present invention is to overcome the problem of high content of sodium or heavy metals in seaweed in the prior art, and to provide a method for preparing high calcium and low sodium seaweed powder, which effectively reduces the sodium and heavy metal content in seaweed powder, Improve the safety of seaweed powder as a calcium source to meet human needs and food safety requirements.
  • one aspect of the present invention provides a method for preparing high calcium low sodium algae powder, including:
  • the washing in step (1) includes using pure water to perform 2-8 times immersion washing.
  • the mass ratio of the amount of water used to the seaweed raw material is 2-5:1, and the time is 15 -40min.
  • the purified water is reverse osmosis purified water, and the soaking and washing temperature is 70-98°C.
  • the seaweed raw material is Schizophyllum seaweed that has grown for more than two years.
  • the preparation method further includes burning the seaweed raw material, preferably, the burning is performed between the second crushing and step (2), and the burning temperature is 180°C Above, the time is 5-20min.
  • the pulverization includes: crushing the seaweed raw material after the second crushing using a horizontal jet mill, the compressed air used by the horizontal jet mill is clean and dry Air, pressure is 0.7-0.9Mpa.
  • the sieving includes: sieving the ground algae raw material after grinding through a 200-mesh sieve to obtain algae powder with a particle size of 200 mesh, and a powder with a particle size greater than 200 mesh The body is crushed again.
  • the magnetic grid adsorption includes: using a magnetic grid adsorption of 6000-12000 Gauss to remove metal components in the seaweed raw material after the screening.
  • the particle size of the particles is 5-10 mm, and after the second crushing, the particle size of the particles is less than 3 mm.
  • a second aspect of the present invention provides a high-calcium low-sodium algae powder prepared by the above method, wherein the calcium content in the algae powder is ⁇ 32%, magnesium content ⁇ 2.5%, sodium content ⁇ 100ppm, and the content ratio of potassium to sodium is not Below 8:1.
  • the high-calcium low-sodium algae powder prepared by the above method in food, wherein the food is preferably a health food or a health food.
  • the sodium components such as sodium chloride and sodium sulfate enriched in seaweed are removed by multiple immersion washings, and the seaweed raw material is effectively removed by magnetic grid adsorption
  • the heavy metal composition ensures that the obtained algae powder and its products meet the needs of the human body and meet the food safety requirements. Further, the organic impurities in the seaweed raw material can be removed by burning, and the purity of the calcium/magnesium compound in the seaweed powder can be improved.
  • the calcium content in the seaweed powder prepared by the method of the present invention ⁇ 32%, magnesium content ⁇ 2.5%, sodium content ⁇ 100ppm, potassium to sodium content ratio is not less than 8:1, magnesium can effectively promote the body's absorption of calcium, the body's absorption rate of calcium in the algae powder obtained by the present invention More than 95%.
  • the particle size of the seaweed powder is ensured to reach 200 meshes, so it is more suitable for application in foods and health care products such as soft capsules, gelatin candies, solid drinks supplemented with calcium and magnesium.
  • the present invention provides a method for preparing high calcium low sodium algae powder, including:
  • the washing in step (1) includes using pure water to perform 2-8 times immersion washing.
  • the mass ratio of the amount of water used to the seaweed raw material is 2-5:1, and the time is 15 -40min.
  • the purified water may be distilled water, deionized water, reverse osmosis purified water, or any other kind of purified water.
  • the purified water is reverse osmosis purified water
  • the temperature of the soaking and washing is 70-98°C, such as 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 98°C or one of the foregoing values Any value between.
  • the reverse osmosis pure water is obtained by a two-stage reverse osmosis pure water mechanism, and its electrical conductivity is less than 10 ⁇ s/cm.
  • the seaweed raw material is a schizophyllum seaweed that has been growing for more than two years.
  • the seaweed raw material is Lithothamnion Corallioides and/or Phymatolithon Calcareum, and the harvested seaweed needs to remove roots as seaweed raw materials to avoid root The impact of accumulated marine pollutants and other ingredients on the product.
  • the preparation method further includes burning the seaweed raw material, preferably, the burning is performed between the second crushing and step (2), and the burning temperature is 180°C Above, the time is 5-20min, more preferably, the burning temperature is 180-350°C, the organic matter such as burnable algae protein in the seaweed raw material is removed, the purity of the seaweed calcium is improved, and a fluffy porous primary is formed product.
  • the pulverization includes: crushing the seaweed raw material after the second crushing using a horizontal jet mill, the compressed air used by the horizontal jet mill is clean and dry Air, the pressure is 0.7-0.9Mpa, the preparation process of the compressed air is: oil-free air compressor provides air with a pressure of 0.7-0.9Mpa, dehumidification through the freeze dryer, the dehumidification condition is dew point temperature ⁇ 10 °C, and then through
  • the medium-efficiency air filter is used for filtering, and more preferably, the high-efficiency filter is used to form clean compressed air.
  • the cleanliness of the compressed air reaches an oil content of ⁇ 0.01mg/m 3 , no bacterial microorganisms are detected, and the air is avoided. Impurities are incorporated into seaweed raw materials.
  • the sieving includes: sieving the ground algae raw material after grinding through a 200-mesh sieve to obtain algae powder with a particle size of 200 mesh, and a powder with a particle size greater than 200 mesh The body is crushed again.
  • the magnetic grid adsorption includes: using a magnetic grid adsorption of 6000-12000 Gauss to remove metal components in the seaweed raw material after the screening.
  • the particle size of the particles is 5-10 mm, and after the second crushing, the particle size of the particles is less than 3 mm.
  • the present invention provides a high-calcium-low-sodium algae powder prepared by the above method, wherein the calcium content in the algae powder is ⁇ 32%, magnesium content ⁇ 2.5%, sodium content ⁇ 100ppm, potassium to sodium content ratio Not less than 8:1.
  • the present invention provides an application of the high-calcium low-sodium algae powder prepared by the above method in food, wherein the food is preferably a health food or a health food.
  • the calcium content is measured by the GB5009.92-2016 method
  • the magnesium content is measured by the GB5009.241-2017 method
  • the sodium content and the potassium content are measured by the GB5009.91-2017 method
  • the heavy metal arsenic content is measured by the GB5009.11-2014 method
  • the heavy metal lead content is measured by GB5009.12-2014 method
  • the heavy metal mercury content is measured by GB5009.17-2014
  • the heavy metal cadmium content is measured by GB5009.15-2014 method
  • human absorption rate adopts human oral test method
  • Human absorption rate (calcium intake-fecal calcium content) / intake
  • seaweed raw material is Lithothamnion Corallioides, Phymatolithon Calcareum from the red algae from the Irish region.
  • seaweed raw materials The harvested Irish sea red algae Lithothamnion Corallioides that have grown for more than two years are sorted to remove roots, and 1 kg is weighed as seaweed raw materials;
  • Burning Burn the seaweed raw material after the second crushing at 180°C for 20min;
  • Screening Use a 200-mesh sieve to screen the algae raw material after grinding, and crush the algae raw material with a particle size greater than 200 meshes again;
  • Magnetic grid adsorption A 6000-gauss magnetic grid adsorption is used to remove metal components in the sieved seaweed raw material to obtain seaweed powder.
  • Screening Use a 200-mesh sieve to screen the algae raw material after grinding, and crush the algae raw material with a particle size greater than 200 meshes again;
  • Magnetic grid adsorption 12000 Gaussian magnetic grid adsorption is used to remove the metal components in the sieved seaweed raw material to obtain seaweed powder.
  • Burning Burn the seaweed raw material after the second crushing at 270°C for 12min;
  • Screening Use a 200-mesh sieve to screen the algae raw material after grinding, and crush the algae raw material with a particle size greater than 200 meshes again;
  • Magnetic grid adsorption 9000 Gauss magnetic grid adsorption is used to remove metal components in the sieved seaweed raw material to obtain seaweed powder.
  • Screening Use a 200-mesh sieve to screen the algae raw material after grinding, and crush the algae raw material with a particle size greater than 200 meshes again;
  • Magnetic grid adsorption 12000 Gaussian magnetic grid adsorption is used to remove the metal components in the sieved seaweed raw material to obtain seaweed powder.
  • seaweed raw materials The harvested Irish sea red algae Lithothamnion Corallioides that have grown for more than two years are sorted to remove roots, and 1 kg is weighed as seaweed raw materials;
  • Screening Use a 200-mesh sieve to screen the algae raw material after grinding, and crush the algae raw material with a particle size greater than 200 meshes again;
  • Magnetic grid adsorption A 6000-gauss magnetic grid adsorption is used to remove metal components in the sieved seaweed raw material to obtain seaweed powder.
  • Screening Use a 200-mesh sieve to screen the algae raw material after grinding, and crush the algae raw material with a particle size greater than 200 meshes again;
  • Magnetic grid adsorption A 14,000 Gauss magnetic grid adsorption is used to remove metal components in the sieved seaweed raw material to obtain seaweed powder.
  • Burning Burn the seaweed raw material after the second crushing at 270°C for 12min;
  • Screening Use a 200-mesh sieve to screen the algae raw material after grinding, and crush the algae raw material with a particle size greater than 200 meshes again;
  • Magnetic grid adsorption 9000 Gauss magnetic grid adsorption is used to remove metal components in the sieved seaweed raw material to obtain seaweed powder.
  • seaweed raw materials The harvested Irish sea red algae Lithothamnion Corallioides that have grown for more than two years are sorted to remove roots, and 1 kg is weighed as seaweed raw materials;
  • Screening Use a 200-mesh sieve to screen the algae raw material after grinding, and crush the algae raw material with a particle size greater than 200 meshes again;
  • the seaweed raw material after the second crushing is beaten by a beating machine, so that the particle size of the obtained seaweed raw material particles is less than 200 mesh;
  • Vacuum freeze-drying is used to vacuum freeze-dry the pulped seaweed raw materials, the degree of vacuum is 0.8MPa, the freezing temperature is -60°C, and the sublimation drying temperature is 110°C to obtain seaweed powder.
  • Seaweed powder was prepared by Examples 1 to 7 and Comparative Examples 1 to 2 respectively, and the calcium, magnesium, sodium, potassium content and human absorption rate of the seaweed powder were measured. The obtained measurement data are shown in Table 1. The content of heavy metals arsenic, lead, cadmium and mercury in seaweed powder was determined, and the obtained measurement data is shown in Table 2.
  • Example 1 32.89 3.56 37.8 372.2 95.8
  • Example 2 33.15 2.87 36.2 360.4 96.7
  • Example 3 34.58 3.49 31.3 349.2 96.9
  • Example 4 32.79 2.84 45.1 381.6 95.2
  • Example 5 32.67 2.83 39.3 386.8 95.3
  • Example 6 32.45 2.81 38.1 379.1 95.7
  • Example 7 31.91 2.76 37.9 382.4 95.6 Comparative Example 1 20.11 2.13 876.9 476.8 81.7 Comparative Example 2 11.65 1.35 1312.4 531.4 71.7
  • Example 1 0.68 0.008 0.56 5.7
  • Example 2 0.59 0.006 0.52 5.5
  • Example 3 0.61 0.007 0.44 4.1
  • Example 4 0.73 0.02 0.57 6.9
  • Example 5 0.69 0.01 0.61 7.1
  • Example 6 0.68 0.008 0.59 5.9
  • Example 7 0.67 0.007 0.57 6.5 Comparative Example 1 0.87 0.019 0.64 10.1 Comparative Example 2 0.99 0.035 0.71 17.2
  • the seaweed powder prepared in Example 1-7 using the method for preparing seaweed powder of the present invention is effective in removing seaweed raw materials by burning compared with the seaweed powder obtained in Comparative Example 1-2.
  • Organic impurities, the final calcium and magnesium content in the algae powder increased significantly, the calcium content in the algae powder was up to 34.58%, the use of multiple immersion washing greatly reduced the sodium content in the algae powder, so that the sodium content in the prepared algae powder is not Above 100ppm, the content ratio of potassium to sodium is not less than 8:1.
  • the seaweed powder prepared in Examples 1-7 has a calcium content of not less than 32% and a magnesium content of not less than 2.5%, and the human body's absorption rate of the calcium source is more than 95%, up to 96.7%.

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Abstract

一种高钙低钠海藻粉的制备方法，包括：(1)将海藻原料依次进行初碎、洗涤和第二次破碎；(2)将步骤(1)所得的海藻原料进行磨粉、筛分和磁栅吸附，得到海藻粉；其中，步骤(1)中所述洗涤包括采用纯净水进行2-8次浸泡洗涤，每次所述浸泡洗涤中，用水量与所述海藻原料的质量比为2-5∶1、时间为15-40min。所述制得的海藻粉中钙含量≥32％、镁含量≥2.5％，且钠含量≤100ppm、钾与钠的含量比不低于8∶1，可应用于软胶囊、凝胶糖果、固体饮料等多种食品中。

Description

一种高钙低钠海藻粉及其制备方法和应用 技术领域
本发明涉及海藻加工技术领域，具体涉及一种高钙低钠海藻粉的制备方法及应用。
背景技术
钙是人体中含量最多的无机元素之一，位于碳、氢、氧、氮之后，为人体第五大元素，人体中钙的含量占总体重的1.5-2％，其中99％贮存在骨骼和牙齿中，仅1％左右分布在细胞外液，即血液和软组织的细胞间液中。钙是构成人体骨骼和牙齿的主要成分，且在维持人体循环、呼吸、神经、内分泌、消化、血液、肌肉、骨骼、泌尿、免疫等各系统正常生理功能中起重要调节作用。在这些生理功能上，大众认知最为广泛的是钙对人体骨骼发育功能的影响方面，这一功能在人体的婴儿期、青少年期这两个骨骼生长高峰期时期的影响也最为显著：婴儿期是1岁以前，婴儿缺钙将导致发育迟缓、发育不良，诸如出牙晚、学步晚；青少年期是12-14岁，如果钙摄入不足，容易身材矮小，产生生长痛。20岁以后骨质依然在增加，35-40岁骨密度达到峰值，40岁以后骨钙逐渐流失，老年人的骨钙流失将加快，导致身材变短、骨质疏松和骨质增生。基于这些认知，补钙也就成为大众的共识，因为人体自身无法形成钙，需要从外界摄取补充。
目前高钙含量的钙源，首推无机来源的分子型碳酸钙，而这类无机来源的碳酸钙都存在一个难以被胃酸消化的问题---质地坚硬、密度大。在钙源的离子化转换过程中，需要钙源的比表面积尽量大，以便增加其与胃酸的接触面积，从而提高离子化转换率，为提高吸收率创造条件。经过长期的研究发现，海藻中含有丰富的钙源，并呈蜂窝型多孔状结构，同样颗粒 大小情况下，常规碳酸钙的比表面积为1.5-1.8m 2/g，而海藻中钙源的比表面积可达8.5-10.1m 2/g，容易在肠胃中进行溶解和离子化，提高人体消化吸收钙的能力而且中和胃酸的效果显著。此外海藻中还蕴含丰富的镁、钠、钾等人体所需的常量元素，对人体健康起着重要的作用。
然而现有技术中对于海藻的处理，一般是将海藻进行简单漂洗后，直接打浆形成海藻粉，或干燥后进行粉碎形成海藻粉，以作为钙源使用，由于海藻生长环境的特殊性，海藻中会富集大量海水中的钠和重金属。钠摄入过量会打破人体体内的代谢平衡，阻碍其他营养素的吸收，对肾器官构成威胁，细胞如要维持正常功能，必须摄取钾，排斥钠，正常细胞内的钾含量是钠含量的10倍左右，如果细胞失去钾摄入而受损，就会立刻开始繁殖分裂；重金属的残留量过高会直接导致海藻粉作为人体补充钙源的安全性存在隐患，从而影响海藻作为钙源的应用。
发明内容
本发明的目的是为了克服现有技术存在的海藻中存在高含量钠或重金属的问题，提供一种高钙低钠海藻粉的制备方法，该方法有效降低海藻粉中的钠及重金属的含量，提高海藻粉作为钙源的安全性，满足人体需求和食品安全要求。
为了实现上述目的，本发明一方面提供一种高钙低钠海藻粉的制备方法，包括：
(1)将海藻原料依次进行初碎、洗涤和第二次破碎；
(2)将步骤(1)所得的海藻原料进行磨粉、筛分和磁栅吸附，得到海藻粉；
其中，步骤(1)中所述洗涤包括采用纯净水进行2-8次浸泡洗涤，每次所述浸泡洗涤中，用水量与所述海藻原料的质量比为2-5:1、时间为15-40min。
优选地，所述纯净水为反渗透纯净水，所述浸泡洗涤的温度为70-98℃。
优选地，所述海藻原料为生长两年以上的石枝藻属海藻。
优选地，该制备方法还包括，对所述海藻原料进行灼烧，优选地，所述灼烧在所述第二次破碎和步骤(2)之间进行，所述灼烧的温度为180℃以上、时间为5-20min。
优选地，步骤(2)中，所述磨粉包括：采用卧式气流粉碎机对经所述第二次破碎后的海藻原料进行粉碎，所述卧式气流粉碎机使用的压缩空气为洁净干燥空气，压力为0.7-0.9Mpa。
优选地，步骤(2)中，所述筛分包括：采用200目的筛网对经所述磨粉后的海藻原料进行筛分，得到粒径为200目的海藻粉，将粒径大于200目的粉体进行再次粉碎。
优选地，步骤(2)中，所述磁栅吸附包括：采用6000-12000高斯的磁栅吸附去除经所述筛分后的海藻原料中的金属成分。
优选地，所述海藻原料经所述初碎后，颗粒的粒径为5-10mm，经所述第二次破碎后，颗粒的粒径小于3mm。
本发明的第二方面，提供由上述方法制备的高钙低钠海藻粉，其中所述海藻粉中钙含量≥32％、镁含量≥2.5％、钠含量≤100ppm、钾与钠的含量比不低于8:1。
本发明的第三方面，提供由上述方法制备的高钙低钠海藻粉在食品中的应用，其中所述食品优选为健康食品或保健食品。
通过上述技术方案，可以达到以下优点：本发明的制备方法中利用多次浸泡洗涤将海藻内富集的氯化钠、硫酸钠等钠成分去除，通过磁栅吸附的方式有效去除海藻原料中的重金属成分，保证得到的海藻粉及其产品满足人体需求，达到食品安全要求。进一步地，通过灼烧可去除海藻原料中的有机杂质，提高海藻粉中钙/镁化合物的纯度，经选用生长两年以上的红藻作为海藻原料，本发明方法制得的海藻粉中钙含量≥32％、镁含量≥2.5％、 钠含量≤100ppm、钾与钠的含量比不低于8:1，镁可以有效促进人体对钙的吸收，人体对本发明所得的海藻粉中钙的吸收率为95％以上。本发明中确保海藻粉的粒径达到200目，从而更适于应用到补充钙、镁的软胶囊、凝胶糖果、固体饮料等食品与保健品中。
为使本发明的上述目的、特征和优点能更明显易懂，下文特举较佳实施例，作详细说明。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
第一方面，本发明提供了一种高钙低钠海藻粉的制备方法，包括：
(1)将海藻原料依次进行初碎、洗涤和第二次破碎；
(2)将步骤(1)所得的海藻原料进行磨粉、筛分和磁栅吸附，得到海藻粉；
其中，步骤(1)中所述洗涤包括采用纯净水进行2-8次浸泡洗涤，每次所述浸泡洗涤中，用水量与所述海藻原料的质量比为2-5:1、时间为15-40min。所述纯净水可以是蒸馏水、去离子水、反渗透纯净水或其他任意一种纯净水。
优选地，所述纯净水为反渗透纯净水，所述浸泡洗涤的温度为70-98℃，如70℃、75℃、80℃、85℃、90℃、95℃、98℃或前述数值之间的任意值。本发明中，所述反渗透纯净水采用二级反渗透纯水机制得，其电导率小于10μs/cm。
优选地，所述海藻原料为生长两年以上的石枝藻属海藻，优选地，所 述海藻原料选用Lithothamnion Corallioides和/或Phymatolithon Calcareum，且经采收的海藻需去除根部作为海藻原料，避免根部所积累的海洋污染物等成分对产品的影响。
优选地，该制备方法还包括，对所述海藻原料进行灼烧，优选地，所述灼烧在所述第二次破碎和步骤(2)之间进行，所述灼烧的温度为180℃以上、时间为5-20min，更优选地，所述灼烧的温度为180-350℃，将海藻原料中可灼烧的藻体蛋白质等有机物去除，提高海藻钙的纯度，形成蓬松多孔的初级产品。
优选地，步骤(2)中，所述磨粉包括：采用卧式气流粉碎机对经所述第二次破碎后的海藻原料进行粉碎，所述卧式气流粉碎机使用的压缩空气为洁净干燥空气，压力为0.7-0.9Mpa，所述压缩空气的制备过程为：无油空压机提供压力为0.7-0.9Mpa的空气，经过冻干机除湿，除湿条件为露点温度≤10℃，再通过中效空气过滤器进行过滤，更优选地，采用高效过滤器进行过滤，形成洁净的压缩空气，压缩空气的洁净度达到含油量≤0.01mg/m 3、没有细菌微生物的检出，避免空气中的杂质被掺入海藻原料中。
优选地，步骤(2)中，所述筛分包括：采用200目的筛网对经所述磨粉后的海藻原料进行筛分，得到粒径为200目的海藻粉，将粒径大于200目的粉体进行再次粉碎。
优选地，步骤(2)中，所述磁栅吸附包括：采用6000-12000高斯的磁栅吸附去除经所述筛分后的海藻原料中的金属成分。
优选地，所述海藻原料经所述初碎后，颗粒的粒径为5-10mm，经所述第二次破碎后，颗粒的粒径小于3mm。
第二方面，本发明提供一种由上述方法制备的高钙低钠海藻粉，其中所述海藻粉中钙含量≥32％、镁含量≥2.5％、钠含量≤100ppm、钾与钠的含量比不低于8:1。
第三方面，本发明的提供一种由上述方法制备的高钙低钠海藻粉在食 品中的应用，其中所述食品优选为健康食品或保健食品。
以下将通过实施例对本发明进行详细描述。
钙含量通过GB5009.92-2016方法测得，镁含量通过GB5009.241-2017方法测得，钠含量、钾含量通过GB5009.91-2017方法测得，重金属砷含量通过GB5009.11-2014方法测得、重金属铅含量通过GB5009.12-2014方法测得、重金属汞含量通过GB5009.17-2014测得、重金属镉含量通过GB5009.15-2014方法测得；人体吸收率采用人体口服的测试方法，人体吸收率＝(钙摄入量-粪便钙含量)/摄入量；海藻原料为来自爱尔兰区域的石枝属红藻Lithothamnion Corallioides、Phymatolithon Calcareum。
实施例1
(1)海藻原料的制备：将采收的生长两年以上的爱尔兰海域红藻Lithothamnion Corallioides进行分拣去根，称取1kg作为海藻原料；
(2)初碎：用破碎机将海藻原料破碎成粒径大小为5-10mm的颗粒；
(3)洗涤：将经初碎后的海藻原料放入反渗透纯净水中，在温度为70℃的条件下进行2次浸泡洗涤，每次浸泡洗涤的用水量为5kg、时间为40min；
(4)第二次破碎：采用破碎机将洗涤后的海藻原料进行第二次破碎，形成粒径小于3mm的颗粒；
(5)灼烧：将第二次破碎后的海藻原料在180℃条件下灼烧20min；
(6)磨粉：采用卧式气流粉碎机，在0.7MPa的压缩空气条件下，将灼烧后的海藻原料进行粉碎；
(7)筛分：采用200目的筛网对磨粉后海藻原料进行筛分，将粒径大于200目的海藻原料进行再次粉碎；
(8)磁栅吸附：采用6000高斯的磁栅吸附去除筛分后的海藻原料中的金属成分，得到海藻粉。
实施例2
(1)海藻原料的制备：将采收的生长两年以上的爱尔兰海域红藻Phymatolithon Calcareum进行分拣去根，称取1kg作为海藻原料；
(2)初碎：用破碎机将海藻原料破碎成粒径大小为5-10mm的颗粒；
(3)洗涤：将经初碎后的海藻原料放入反渗透纯净水中，在温度为98℃的条件下进行8次浸泡洗涤，每次浸泡洗涤的用水量为2kg、时间为15min；
(4)第二次破碎：采用破碎机将洗涤后的海藻原料进行第二次破碎，形成粒径小于3mm的颗粒；
(5)灼烧：将第二次破碎后的海藻原料在350℃条件下灼烧5min；
(6)磨粉：采用卧式气流粉碎机，在0.9MPa的压缩空气条件下，将灼烧后的海藻原料进行粉碎；
(7)筛分：采用200目的筛网对磨粉后海藻原料进行筛分，将粒径大于200目的海藻原料进行再次粉碎；
(8)磁栅吸附：采用12000高斯的磁栅吸附去除筛分后的海藻原料中的金属成分，得到海藻粉。
实施例3
(1)海藻原料的制备：将采收的生长两年以上的爱尔兰海域红藻Phymatolithon Calcareum进行分拣去根，称取1kg作为海藻原料；
(2)初碎：用破碎机将海藻原料破碎成粒径大小为5-10mm的颗粒；
(3)洗涤：将经初碎后的海藻原料放入反渗透纯净水中，在温度为80℃的条件下进行5次浸泡洗涤，每次浸泡洗涤的用水量为4kg、时间为30min；
(4)第二次破碎：采用破碎机将洗涤后的海藻原料进行第二次破碎，形成粒径小于3mm的颗粒；
(5)灼烧：将第二次破碎后的海藻原料在270℃条件下灼烧12min；
(6)磨粉：采用卧式气流粉碎机，在0.8MPa的压缩空气条件下，将 灼烧后的海藻原料进行粉碎；
(7)筛分：采用200目的筛网对磨粉后海藻原料进行筛分，将粒径大于200目的海藻原料进行再次粉碎；
(8)磁栅吸附：采用9000高斯的磁栅吸附去除筛分后的海藻原料中的金属成分，得到海藻粉。
实施例4
(1)海藻原料的制备：将采收的生长两年以上的爱尔兰海域红藻Phymatolithon Calcareum进行分拣去根，称取1kg作为海藻原料；
(2)初碎：用破碎机将海藻原料破碎成粒径大小为5-10mm的颗粒；
(3)洗涤：将经初碎后的海藻原料放入反渗透纯净水中，在温度为40℃的条件下进行6次浸泡洗涤，每次浸泡洗涤的用水量为2kg、时间为15min；
(4)第二次破碎：采用破碎机将洗涤后的海藻原料进行第二次破碎，形成粒径小于3mm的颗粒；
(5)灼烧：将第二次破碎后的海藻原料在300℃条件下灼烧5min；
(6)磨粉：采用卧式气流粉碎机，在0.9MPa的压缩空气条件下，将灼烧后的海藻原料进行粉碎；
(7)筛分：采用200目的筛网对磨粉后海藻原料进行筛分，将粒径大于200目的海藻原料进行再次粉碎；
(8)磁栅吸附：采用12000高斯的磁栅吸附去除筛分后的海藻原料中的金属成分，得到海藻粉。
实施例5
(1)海藻原料的制备：将采收的生长两年以上的爱尔兰海域红藻Lithothamnion Corallioides进行分拣去根，称取1kg作为海藻原料；
(2)初碎：用破碎机将海藻原料破碎成粒径大小为20-30mm的颗粒；
(3)洗涤：将经初碎后的海藻原料放入去离子水中，在温度为70℃的条件下进行2次浸泡洗涤，每次浸泡洗涤的用水量为5kg、时间为40min；
(4)第二次破碎：采用破碎机将洗涤后的海藻原料进行第二次破碎，形成粒径5-10mm的颗粒；
(5)灼烧：将第二次破碎后的海藻原料在500℃条件下灼烧20min；
(6)磨粉：采用卧式气流粉碎机，在0.7MPa的压缩空气条件下，将灼烧后的海藻原料进行粉碎；
(7)筛分：采用200目的筛网对磨粉后海藻原料进行筛分，将粒径大于200目的海藻原料进行再次粉碎；
(8)磁栅吸附：采用6000高斯的磁栅吸附去除筛分后的海藻原料中的金属成分，得到海藻粉。
实施例6
(1)海藻原料的制备：将采收的生长一年的爱尔兰海域红藻Lithothamnion Corallioides进行分拣去根，称取1kg作为海藻原料；
(2)初碎：用破碎机将海藻原料破碎成粒径大小为5-10mm的颗粒；
(3)洗涤：将经初碎后的海藻原料放入蒸馏水中，在温度为70℃的条件下进行6次浸泡洗涤，每次浸泡洗涤的用水量为3kg、时间为35min；
(4)第二次破碎：采用破碎机将洗涤后的海藻原料进行第二次破碎，形成粒径小于3mm的颗粒；
(5)灼烧：将第二次破碎后的海藻原料在300℃条件下灼烧10min；
(6)磨粉：采用卧式气流粉碎机，在0.5MPa的压缩空气条件下，将灼烧后的海藻原料进行粉碎；
(7)筛分：采用200目的筛网对磨粉后海藻原料进行筛分，将粒径大于200目的海藻原料进行再次粉碎；
(8)磁栅吸附：采用14000高斯的磁栅吸附去除筛分后的海藻原料中 的金属成分，得到海藻粉。
实施例7
(1)海藻原料的制备：将采收的生长两年以上的爱尔兰海域红藻Phymatolithon Calcareum进行分拣去根，称取1kg作为海藻原料；
(2)初碎：用破碎机将海藻原料破碎成粒径大小为5-10mm的颗粒；
(3)洗涤：将经初碎后的海藻原料放入去离子水中，在温度为90℃的条件下进行6次浸泡洗涤，每次浸泡洗涤的用水量为2.5kg、时间为25min；
(4)第二次破碎：采用破碎机将洗涤后的海藻原料进行第二次破碎，形成粒径小于3mm的颗粒；
(5)灼烧：将第二次破碎后的海藻原料在270℃条件下灼烧12min；
(6)磨粉：采用卧式气流粉碎机，在0.8MPa的压缩空气条件下，将灼烧后的海藻原料进行粉碎；
(7)筛分：采用200目的筛网对磨粉后海藻原料进行筛分，将粒径大于200目的海藻原料进行再次粉碎；
(8)磁栅吸附：采用9000高斯的磁栅吸附去除筛分后的海藻原料中的金属成分，得到海藻粉。
对比例1
(1)海藻原料的制备：将采收的生长两年以上的爱尔兰海域红藻Lithothamnion Corallioides进行分拣去根，称取1kg作为海藻原料；
(2)初碎：用破碎机将海藻原料破碎成粒径大小为5-10mm的颗粒；
(3)洗涤：将经初碎后的海藻原料放入反渗透纯净水中，在温度为70℃的条件下进行浸泡洗涤40min、用水量为2kg；
(4)第二次破碎：采用破碎机将洗涤后的海藻原料进行第二次破碎，形成粒径小于3mm的颗粒；
(5)磨粉：采用辊式粉碎机，在0.7MPa的压缩空气条件下，将灼烧后的海藻原料进行粉碎；
(6)筛分：采用200目的筛网对磨粉后海藻原料进行筛分，将粒径大于200目的海藻原料进行再次粉碎；
(7)干燥：将经筛分后的海藻原料采用热风干燥箱进行干燥，干燥温度为120℃。
对比例2
(1)将采收的生长两年以上的爱尔兰海域红藻Lithothamnion Corallioides进行分拣去根，称取1kg作为海藻原料；
(2)初碎：用破碎机将海藻原料破碎成粒径大小为5-10mm的颗粒；
(3)洗涤：将经初碎后的海藻原料放入温度为50℃的反渗透纯净水中，浸泡洗涤30min；
(4)第二次破碎：采用破碎机将洗涤后的海藻原料进行第二次破碎，形成粒径小于3mm的颗粒；
(5)将第二次破碎后的海藻原料采用打浆机打浆，使得到的海藻原料颗粒粒度小于200目；
(6)采用真空冷冻干燥机对打浆后的海藻原料进行真空冷冻干燥，真空度为0.8MPa、冷冻温度为-60℃、升华干燥温度为110℃，得到海藻粉。
实验结果
通过实施例1-实施例7和对照例1-对照例2分别制得海藻粉，对海藻粉中钙、镁、钠、钾含量和人体吸收率进行测定，得到的测定数据见表1，对海藻粉中重金属砷、铅、镉、汞含量进行测定，得到的测定数据见表2。
表1
编号 钙(g/100g) 镁(g/100g) 钠(mg/kg) 钾(mg/kg) 人体吸收率(％)
实施例1 32.89 3.56 37.8 372.2 95.8
实施例2 33.15 2.87 36.2 360.4 96.7
实施例3 34.58 3.49 31.3 349.2 96.9
实施例4 32.79 2.84 45.1 381.6 95.2
实施例5 32.67 2.83 39.3 386.8 95.3
实施例6 32.45 2.81 38.1 379.1 95.7
实施例7 31.91 2.76 37.9 382.4 95.6
对比例1 20.11 2.13 876.9 476.8 81.7
对比例2 11.65 1.35 1312.4 531.4 71.7
表2
编号 砷(mg/kg) 铅(mg/kg) 镉(mg/kg) 汞(μg/kg)
实施例1 0.68 0.008 0.56 5.7
实施例2 0.59 0.006 0.52 5.5
实施例3 0.61 0.007 0.44 4.1
实施例4 0.73 0.02 0.57 6.9
实施例5 0.69 0.01 0.61 7.1
实施例6 0.68 0.008 0.59 5.9
实施例7 0.67 0.007 0.57 6.5
对比例1 0.87 0.019 0.64 10.1
对比例2 0.99 0.035 0.71 17.2
通过表1的结果可以看出，采用本发明海藻粉的制备方法的实施例1-7制得的海藻粉与对比例1-2得到的海藻粉相比，通过灼烧有效去除海藻原料 中的有机杂质，最终海藻粉中钙、镁含量明显增加，海藻粉中钙含量最高达34.58％，利用多次浸泡洗涤大大降低了海藻粉中的钠含量，使制得的海藻粉中，钠含量不高于100ppm、钾与钠的含量比不低于8:1。从表2的结果可以看出，通过磁栅吸附的方式有效降低了海藻原料中的重金属含量，重金属砷、铅、镉、汞的含量明显降低，保证得到的海藻粉及其产品的食用安全性。实施例1-7制得的海藻粉中钙含量不低于32％、镁含量不低于2.5％，人体对钙源的吸收率为95％以上，最高达96.7％。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (10)

  1. 一种高钙低钠海藻粉的制备方法，其特征在于，包括：
    (1)将海藻原料依次进行初碎、洗涤和第二次破碎；
    (2)将步骤(1)所得的海藻原料进行磨粉、筛分和磁栅吸附，得到海藻粉；
    其中，步骤(1)中所述洗涤包括采用纯净水进行2-8次浸泡洗涤，每次所述浸泡洗涤中，用水量与所述海藻原料的质量比为2-5:1、时间为15-40min。
  2. 根据权利要求1所述的高钙低钠海藻粉的制备方法，其特征在于，所述纯净水为反渗透纯净水，所述浸泡洗涤的温度为70-98℃。
  3. 根据权利要求1所述的高钙低钠海藻粉的制备方法，其特征在于，所述海藻原料为生长两年以上的石枝藻属海藻。
  4. 根据权利要求1所述的高钙低钠海藻粉的制备方法，其特征在于，该制备方法还包括，对所述海藻原料进行灼烧，优选地，所述灼烧在所述第二次破碎和步骤(2)之间进行，所述灼烧的温度为180℃以上、时间为5-20min。
  5. 根据权利要求1所述的高钙低钠海藻粉的制备方法，其特征在于，步骤(2)中，所述磨粉包括：采用卧式气流粉碎机对经所述第二次破碎后的海藻原料进行粉碎，所述卧式气流粉碎机使用的压缩空气为洁净干燥空气，压力为0.7-0.9Mpa。
  6. 根据权利要求1所述的高钙低钠海藻粉的制备方法，其特征在于， 步骤(2)中，所述筛分包括：采用200目的筛网对经所述磨粉后的海藻原料进行筛分，得到粒径为200目的海藻粉，将粒径大于200目的粉体进行再次粉碎。
  7. 根据权利要求1所述的高钙低钠海藻粉的制备方法，其特征在于，步骤(2)中，所述磁栅吸附包括：采用6000-12000高斯的磁栅吸附去除经所述筛分后的海藻原料中的金属成分。
  8. 根据权利要求1所述的高钙低钠海藻粉的制备方法，其特征在于，所述海藻原料经所述初碎后，颗粒的粒径为5-10mm，经所述第二次破碎后，颗粒的粒径小于3mm。
  9. 由权利要求1-8中任一项所述的方法制备的高钙低钠海藻粉，其中所述海藻粉中钙含量≥32％、镁含量≥2.5％、钠含量≤100ppm、钾与钠的含量比不低于8:1。
  10. 权利要求9所述的高钙低钠海藻粉在食品中的应用，其中所述食品优选为健康食品或保健食品。
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