纳米植物粉体球磨制备技术

5 纳米植物粉体产品研发进展缓慢 如纳米花粉 木耳等天然植物保健食品 人参 灵芝孢子 珍珠 冬虫草等名贵药用植物 以及如马钱子等有毒药用 植物的纳米植物粉体产品尚处在开发阶段 这里既 有科学问题 也有技术问题 科学问题方面 如纳 米植物粉体究竟能解决什么问题 已陆续有应用文 章发表 本文谈的是技术应用问题 由吕庆及曲源等发明的多维摆动式纳米球磨技 术和多层次分级纳米球磨技术 较好地解决了纳米 植物粉体制备的技术应用 前者已获得专利 后者 已进入实审 一 纳米植物球磨制备技术 1 多维摆动式高能纳米球磨技术 多维摆动 式高能纳米球磨机通过罐体快速的多维摆动式运动 使磨介在罐内的不规则运动产生巨大的冲击力 延 长磨介的运动轨迹 提高冲击能 减少撞击盲点 其工作效率是传统球磨机的几十倍 可显著提高罐 内磨介的冲击能量和运动次数 使被粉碎的物质颗 粒达到纳米级 同时大大提高了粉体颗粒的均匀度 粉碎粒径最小为 10nm 属封闭式高能球磨 秦皇 岛市太极环纳米制品有限公司用该设备已成功研制 纳米食品 纳米茶 纳米咖啡 纳米中药 外用 贴膏 并开始推广应用 该设备应用范围广泛 除 植物以外 对金属 非金属 多元合金 机械化合 金 动物 矿物 药材等有机 无机材料均可进行 纳米级粉碎的实验和生产 易燃 易爆物品需加保 护剂如氩气 氮气 二氧化碳等 2 多层次分级纳米球磨技术 多层次分级纳米球磨机采用调酒师手臂动作原 理 双向反复快速运转 加强了磨介轨迹变换的机 率 产生高能冲击 使物料在运动中撞击球磨 微米 级粉体在多机腔 多层次 多直径磨介 由大逐渐 变小 流送中不断地撞击粉碎 产生分级粉碎效果 最后粉碎成 10nm 以上的粉体 该设备为开放式球 The research and development of nano plant fines proceed rather slowly and the health foods of natural plants such as nanopollen and auricula the rare medicinal plants such as ginseng glossy ganoderma pearls and cordyceps sinensis and the toxic medicinal plants such as strychnos nux vomica are all in their development stage owing to the scientific and technical problems In respect of science articles on the application of nano plants and what problem exactly can be solved with the nano plant fines have appeared one and another This article discusses the problem of technical application The multidimensional swinging nano ball milling technology and the multiplayer grading nano ball milling technology invented by Mr Lv Qing and Mr Qu Yuang have solved the problems encountered in the application of nano plant fine preparation technique with the former having obtained a patent and the later being under examination for granting a patent 1 Ball milling technology for the preparation of nano plants 1 Multidimensional swinging and high energy nano ball milling technology Multidimensional swinging and high energy nano ball miller as a closed high energy milling machine and through the quick multidimensional swinging motion of its tank is able to make the irregular motion of milling medium in the tank generate a tremendous impact force with increased impact times prolong the motion trace augment the impact energy and lessen the impact blind spots with its working efficiency increased several dozen times over the traditional ball millers and the particles of broken substance reaching a nano grade Meanwhile the homogeneous degree of particles can also be increased with the minimum diameter of particles standing at 10 nm Using this equipment Qinhuangdao Taiji Ring Nano products Co Ltd has succeeded in preparing nano food nano teas and nano coffee and nano Chinese medicine paste the application of which has been popularized Apart from plants this equipment can be widely used in the experience and production of nano grade fines of organic and inorganic materials such as metals non metals multi alloys mechanization alloys animals mines and medicinal materials for the pulverization of inflammable and explosive materials protective agents such as argon nitrogen and carbon dioxide should be added 2 Multiplayer grading nano ball milling technology Multiplayer grading nano ball miller according to the movement principle of a rectifier s hand is able to revolve repeatedly and quickly in double directions increase the chance of trace variation of the medium generate a high energy impact and make the materials dash on the miller in motion and the fines continuously pulverized in the multi chambers multi layers and the multi diameter medium changing gradually from large to small during 纳纳米植物粉体球磨制米植物粉体球磨制备备技技术术的的应应用用 曲源 曲莱 曲少忠 Application of Ball Milling Technology for the Preparation of Nano Plant Fines Qu Yuan Qu Lai Qu Shaozhong 6 磨 可连续地进料出料 干磨 湿磨皆可 可广泛 地应用于动 植物 矿物 金属 陶瓷及非易燃易 爆的有机 无机材料 二 纳米植物粉体球磨制备中的若干问题 1 温度问题 由于以上两种球磨技术均属高 能球磨 会迅速升温 易使植物粉体焦化 碳化 为保持植物成份不变 温度是最先需要解决的问题 封闭式球磨法 虽然可以加液氮冷却 但由于液氮 的纯度问题 通常液氮纯度难以控制 植物容易 受到污染 生产成本又高 为此 我们采用罐体夹 套循环水冷却 有效的控制了加工过程的温度 2 湿度问题 通常植物干品含水量在 5 10 左 右 增加了植物的韧性 弹性 为了增加其脆性 需去掉其中的水份 我们采用将微米粉体在 55 干 燥 4 6 小时 干燥后再球磨加工 取得较好效果 如采用实验型设备做小样 可将根 茎 皮 叶 花 果捣碎 或小型粉碎机粗粉 直接干燥后装罐 如采用鲜嫩植物 则先用传统粉碎机打浆 再用高 能球磨机制备纳米植物浆料 然后喷雾干燥 如制 备生绿茶或生凉茶用此法最佳 3 粘韧性问题 植物均含糖 而含糖量过高 产生粘韧性问题 含油过多 含胶质过多也会出现 粘韧性问题 如熟地 枸杞 大枣 乳香 没药等 易在球磨中沾球 沾罐 结球成团 不能达到好的 粉碎效果 这些品种 如采用深冷冻球磨 如加液 氮会污染植物 冰箱冷冻取出加料会产生回温问题 对此 我们采用湿法浆磨 方法是 传统粉碎后加 水搅成浆料 然后用球磨制备成纳米浆料 达到球 磨效果后取出 采用喷雾干燥 较好地解决了此问 题 保留了原植物的特性 4 污染问题 球磨技术 尤其是高能球磨 技术污染问题很突出 如果采用钢球 不做冷却降 温 物料污染很严重 在采用水冷却降温后 将钢 球换成纳米氧化锆球 将罐体也换成氧化锆内衬 使物料的污染降到最低 如果是粉碎植物 半年才 更换一次磨球 可见污染相当低 加之锆元素也是 人体牙齿与骨骼所需求的微量元素 在食品 保健 品中有极微量的锆元素存在 有益无害 5 颗粒团聚的问题 植物粉碎到纳米尺寸 其比 表面积很大 表面能很高 表面电荷很多 加之其 中大多为亲水性物质 极易吸水产生团聚 而保健 品 食品大多倾向做成植物饮料 团聚的纳米植物 粉体用水冲时很难分散 易产生沉淀 影响感观效 果 their being fed in the flow and thus having been finally pulverized to over 10 nm This equipment is an open miller can be operated with or without water with materials fed and discharged continuously It can be widely used to pulverize organic and inorganic materials such as animals plants mines metals ceramics and non inflammable and non explosive materials 2 Some problems in the preparation of nano plant fines with ball milling 1 Temperature Because both the above two ball millers are high energy millers and the plant fines are easy to be coked and carbonized in the quickly increasing temperature in the machines the temperature is the first problem to be solved For the closed miller it can be cooled by adding fluid nitrogen but as the purity of the fluid nitrogen is different to control the plant is apt to be polluted and the production cost is rather high so we have adopted cycling water cooling in a jacket in the tank to effectively control the temperature during the processing 2 Humidity Plants usually have a water content of 5 10 to increase their toughness and elasticity In order to increase their brittleness it is necessary to remove the moisture so we have adopted a method of drying the plants for 4 6 hours under 55 and then processed in the ball miller and gained a better effect If an example is made in a experimental equipment the roots stems barks leaves flowers and fruits of the plants can be pounded to pieces or crushed to rough fines with small miller and then fed into the tank after drying If fresh plants are adopted they can be beaten first with traditional disintegrator then made into size with high energy ball miller and finally dried with spray This method works well in the preparation of fresh green tea and cold tea 3 Stickiness Some plants such as prepared rhizome of rehmannia medlar Chinese dates frankincense and myrrh contain too much sugar or oil or colloid which might stick onto the balls the tank or palletized in the ball miller and reduce the milling effect For these kind of plants if a method of deep cooling and milling is adopted the temperature of the materials will increased after taking out from the refrigerator and if fluid nitrogen is added the plants will be polluted For these reasons we have adopted humid milling In this method the plants are crashed and water is added to form a kind of size and then made with ball miller into nano size and finally dried with spay after having reached milling effect This method have solved the problem of stickiness and also preserved the characteristics of these plants 4 Pollution The ball milling technology especially the high energy milling is faced with a problem of plant pollution and the problem will be more serious if steel balls are adopted and the plants are not cooled and temperature not reduced We therefore have replaced the steel balls with zirconium balls and have the tank lined with zirconium oxide to minimize the pollution to the materials The zirconium balls are usually replaced once half a year if milling plants showing the pollution is rather low Besides the trace element zirconium exits in many health foods benefits health and is needed by human body to grow teeth and skeleton 5 Agglomeration When the plants are milled into nano size the particles will have a large specific surface area with high energy and much electric load and their 7 hydrophily are apt to obsorb water and pelletized 口感也涩涩地 克服此缺点的方法就成了各国各公 司的商业秘密 一种是磨前将微米级物料中加入食 品级分散剂 在球磨过程中进行表面改性 清除表 面能 消除表面静电 提高其分散性 分散剂还 能提高球磨效果 另一种是在球磨前在微米级物料 中加入食品级表面改性剂 通过球磨过程的研磨分 散 对纳米植物颗粒表面进行改性处理 提高其分 散性 无论用冷 热水冲饮 绿茶立即碧绿 红茶 立刻红亮 长时间不出现沉淀 6 粒度及均匀度问题 粒度即颗粒的粒径 一般都用平均粒径表示 也就是粉末的统计性平均 粒径值 纳米植物粉体究竟多大粒径为好 我们多 年研究认为 平均粒径不应小于 100 纳米 在 120 180 之间最好 此区间植物不但破壁 其内的细胞 也已经打碎 其物理细化过程已经完成 可达到营 养及药物成分的充分吸收作用 用于研究病毒植物 除外 如果完全追求 100 纳米以下 则增加其不 稳定因素 改性 变性及产生毒副作用的风险 纳 米植物加工目的是为了提高其高吸收度 而以其生 产新的改性材料 则言之尚早 均匀度即颗粒的分布范围 分布愈集中 则表 示颗粒愈均匀 球磨制备纳米粉体的均匀度不佳 所以用来制备金属等严格地纳米改性材料很不理想 但用来制备纳米植物粉体则很适用 因纳米植物物 理加工是为了 保性 而不是改性 所以我们努力 将颗粒控制大部分在 60 180 纳米 控制要点为 就 是最大程度的降低球磨时间 所以我们采用 纳米 茶制备三步法 先经传统粉碎 再经气流粉碎 气流粉碎是物料之间的撞击 并不增加铁的污染 然后将微米级物料进行高能球磨制备成纳米粉体 大大的缩短了球磨时间 减少了污染 经过前二步的控制 如粉碎 过筛 气流粉碎 再过筛 使球磨颗粒不均匀的问题很大程度上得到 解决 达到预期均匀度 三 纳米植物粉体球磨技术发展与展望 植物中含有大量的蛋白质 氨基酸 维生素 纤维素 微量元素等有机物 以及数十种人体必需 的无机矿物元素及药物成分 对人体有着重要的保 健治疗作用 研究证明 如果不将其破壁 营养或 药用成分就不会充分吸收 而在物理粉碎技术中 球磨技术以其高效率 低成本而受人青睐 但在纳米粉体制备中 尤其是 纳米植物粉体制备方面遇到了新的挑战 如颗粒不 Meanwhile most health foods are made to be plant drinks Pelletized nano plant fines are difficult to disperse when watered apt to settle and this will affect its appearance and taste The methods to over come this shortage have become a commercial secret for many companies the world over one of them is to add food grade dispersing agent in the micro grade materials before ball milling to modify their surface characteristics remove their surface energy and static electricity and improve their dispersion The dispersing agent can also diameter should not less than 100 nm and 120 180 nm is the best In this range of diameter not only the walls of plants are broken the cells in them are broken as well and the process of physical fining have been completed with the nutrition and medical component of the fines able to be sufficiently absorbed except the plants to be used for the research of viruses If pursuing completely for less than 100 nm it would be dangerous to increase unstable factors change the characteristics of the plants and generate side effects The nano plant processing is aimed at improving the absorption and it is too early to expect it to produce new modified materials food grade modifier in the micro grade materials before ball milling modify the surface of nano plant particles and increase their dispersion in the course of ball milling After thus processed whether watered with cold or hot water the green tea will become immediately dark green the black tea glow and will not deposit 6 Granularity and evenness Granularity the diameter of the particles is usually expressed by the average diameter namely the statistical average diameter value How much is the best diameter of the particles of nano plant fines Through several years research we think that the average Evenness means the distribution range of the particles The more concentrated of the distribution the more even the particles would be The evenness of the fine particles prepared by ball milling is not well and therefore not ideal for producing strictly nano modified materials such as metals However it is best suitable to prepare nano plant fines because the nano plant processing is not aimed at modification but at preservation Therefore we are striving to control the particles at a range of 60 180 nm The key point of the control is to shorten the milling time to the greatest degree For this purpose we have adopted a procedure named three steps of nano tea preparation first crushed with traditional method second crushed with air flow impact between materials not polluted by iron finally the micro grade materials are prepared into nano fines with high energy ball milling thus greatly shortened the milling time and decreased the pollution Controlled in the first two steps crush screen crush with air flow and screen again the evenness can be achieved as expected 3 Development and forecast of nano plant ball milling technology Plants contain a lot of such organic substances as protein and medical components are difficult to be absorbed Among the physical crush technologies the ball milling technology is welcomed by many people However the nano fines preparation especially in the field of nano plant fine preparation was confronted with challenges from 8 many problems such as unevenness of particles serious pollution 均匀 污染严重 加工时间过长等一度受到轻视 经过几年的徘徊 新的球磨技术也在发展 回头来 看仍不失为纳米植物粉体制备的低成本 高效率的 可行方法 多维摆动式及多层次分级式新球磨技术制备的 纳米植物粉体是纯物理方法加工出来的 植物本身 无破坏 也不引入其它成份 相对的保证了植物成 份的天然性与完整性 应用领域特别广泛 我们的 实践已说明并将继续证明 日本虽抢先一步 将超 细技术引进植物中药领域 我们则是最先研发并将 高能纳米球磨技术引入植物及中药领域 这种全新 的粉碎技术及其制备的纳米级植物粉末 必将给植 物加工相关行业带来新的活力 成为食品 保健品 化妆品 中药行业新的生长点 以其高溶解度 高 溶出度 高吸收度 高吸附力度 高生物利用度生 产出速效 高效 长效产品 为人类的健康服务 纳米青茶粒径图 and long time processing which were once neglected Ho