WO2021000662A1 - 一种超声-电极-纳米多孔膜耦合制氢灭菌系统 - Google Patents

一种超声-电极-纳米多孔膜耦合制氢灭菌系统 Download PDF

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WO2021000662A1
WO2021000662A1 PCT/CN2020/091171 CN2020091171W WO2021000662A1 WO 2021000662 A1 WO2021000662 A1 WO 2021000662A1 CN 2020091171 W CN2020091171 W CN 2020091171W WO 2021000662 A1 WO2021000662 A1 WO 2021000662A1
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hydrogen
membrane
electrode
cavity
nanobubbles
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PCT/CN2020/091171
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English (en)
French (fr)
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徐恩波
刘东红
周建伟
王浩
丁甜
程焕
叶兴乾
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浙江大学
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Priority to US17/272,654 priority Critical patent/US11985993B2/en
Priority to JP2020556235A priority patent/JP7072928B2/ja
Publication of WO2021000662A1 publication Critical patent/WO2021000662A1/zh

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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
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52—Adding ingredients
    • A23L2/54—Mixing with gases
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C9/00—Milk preparations; Milk powder or milk powder preparations
    • A23C9/152—Milk preparations; Milk powder or milk powder preparations containing additives
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C3/00—Preservation of milk or milk preparations
    • A23C3/07—Preservation of milk or milk preparations by irradiation, e.g. by microwaves ; by sonic or ultrasonic waves
    • A23C3/073—Preservation of milk or milk preparations by irradiation, e.g. by microwaves ; by sonic or ultrasonic waves by sonic or ultrasonic waves
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C3/00—Preservation of milk or milk preparations
    • A23C3/08—Preservation of milk or milk preparations by addition of preservatives
    • A23C3/085—Inorganic compounds, e.g. lactoperoxidase - H2O2 systems
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C9/00—Milk preparations; Milk powder or milk powder preparations
    • A23C9/152—Milk preparations; Milk powder or milk powder preparations containing additives
    • A23C9/1522—Inorganic additives, e.g. minerals, trace elements; Chlorination or fluoridation of milk; Organic salts or complexes of metals other than natrium or kalium; Calcium enrichment of milk
    • 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
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/42—Preservation of non-alcoholic beverages
    • A23L2/44—Preservation of non-alcoholic beverages by adding preservatives
    • 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
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/42—Preservation of non-alcoholic beverages
    • A23L2/50—Preservation of non-alcoholic beverages by irradiation or electric treatment without heating
    • 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
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52—Adding ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/025—Ultrasonics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • the invention relates to a unit combination system for generating hydrogen-rich nanobubbles and a method for preparing antibacterial functional beverages, belonging to the technical field of liquid food processing.
  • Hydrogen is the simplest, smallest molecule, and most widely distributed element in nature. As early as 2007, Japanese scientists discovered the selective antioxidant capacity of hydrogen, which caused many scholars to scramble for research. Hydrogen has the characteristics of strong penetrating power and fast diffusion speed, which can enter any part of the body to exert anti-oxidation, anti-inflammatory, anti-apoptotic and other mechanisms. Compared with other commonly used food-grade antioxidants (such as vitamin C, polyphenols, etc.), hydrogen has a simple structure and reaction products are simple and harmless, easy to be discharged without residue, and selectively free from active/toxic active oxygen Binding to other important active oxygen signal molecules without destroying.
  • the most commonly used method of hydrogen is to prepare hydrogen-rich liquid, especially hydrogen-rich water.
  • the method of dissolving hydrogen is basically based on hydrogen filling and high-pressure solubilization. Especially for beverage systems with ions and dissolved substances, the dissolved hydrogen content is generally higher. Low (0.2 ⁇ 2.2ppm), large volume of dissolved hydrogen (bubbles or micron-sized bubbles visible to the naked eye), hydrogen bubbles rise and break easily, and have poor stability; hydrogen production by pure electrolysis and chemical reaction methods is prone to produce by-products, which can cause damage to liquids.
  • the purpose of the present invention is to solve the shortcomings of the prior art and provide an ultrasonic-electrode-nanoporous membrane coupling hydrogen production sterilization system.
  • the system can easily, intelligently and greenly generate hydrogen-rich nanobubbles with a diameter of 20-1000nm.
  • the dissolved hydrogen (3-6ppm) rises slowly and can exist stably for more than 8-36h in a non-sealed state.
  • the antioxidant and antibacterial functions are remarkable, and the taste is richer and more diverse than the original drink.
  • An ultrasonic-electrode-nanoporous membrane coupling hydrogen production sterilization system includes a container, and several hydrogen production units arranged in the container.
  • the hydrogen production unit includes a cavity, and a broadband ultrasonic generator located in the cavity,
  • the ring-shaped hydrogen-generating electrode, the ring-shaped hydrogen-generating electrode surrounds the broadband ultrasonic generator;
  • the bottom membrane at the bottom of the cavity is an inner hydrophobic and outer hydrophilic membrane;
  • the side membrane is an inner hydrophilic and outer hydrophobic membrane, which is installed vertically or Install at an angle of 0° ⁇ 45°.
  • the top cover is made of airtight material.
  • the bottom membrane is made of non-toxic materials such as nano-scale ( ⁇ 1000 nm pore diameter) ceramics, fibers, metal organic frames, etc.
  • the adjustable range of the broadband ultrasonic generator includes, but is not limited to, 20 KHz to 400 KHz, and is located at the center of the reactor and radiates waves to the surroundings.
  • a hydrogen tester is installed at the water outlet of the system box.
  • the ultrasonic-electrode-nanoporous membrane coupling hydrogen production sterilization system of the present invention can continuously and efficiently promote the self-circulating micro-flow of the liquid system, the dissolution of hydrogen (in the form of nanobubbles), and the interface-bulk bubble transformation, Dispersion, sterilization and other functions
  • the prepared antibacterial functional beverage has high hydrogen content (3-6ppm), among which the diameter of hydrogen-rich nanobubbles can be distributed in 20-1000nm, and the unsealed state can also be retained stably for more than 8 ⁇ 36h.
  • Hydrogen beverages have significant antioxidant and antibacterial functions, and the taste is richer and more diverse than original beverages.
  • the system of the present invention is simple, intelligent, efficient, high-quality, green, and health-care products, avoids a large amount of waste of hydrogen charging and high-pressure energy consumption, prevents the secondary pollution system in processing, and meets food-grade requirements.
  • Fig. 1 is a microcirculation system and its cabinet design for producing hydrogen nanobubbles by coupling ultrasonic-electrode-nanoporous membranes according to the present invention.
  • Figure 2 is an illustration of the nanoporous membrane used in the present invention and its process.
  • FIG. 3 shows the hydrogen generation microsystem array used in the present invention.
  • 1 broadband ultrasonic generator 2 annular hydrogen-producing electrodes, 3 food-grade nanoporous side membrane, 4 food-grade nanoporous bottom membrane, 5 top cover, 6 interface nanobubbles, 7 bulk nanobubbles, 8 containers, 9 Feeding port, 10 discharging port, 11 liquid circulating hydrogen dissolving pipe
  • an ultrasonic-electrode-nanoporous membrane coupling hydrogen production sterilization system includes a container 8 and a plurality of hydrogen production units arranged in the container 8.
  • the hydrogen production unit includes a cavity, And a broadband ultrasonic generator 1 and a ring-shaped hydrogen-producing electrode 2 located in the cavity.
  • the ring-shaped hydrogen-generating electrode 2 surrounds the broadband ultrasonic generator 1;
  • the bottom membrane 4 at the bottom of the cavity is an inner hydrophobic and outer hydrophilic membrane;
  • the membrane 3 is an inner hydrophilic and outer hydrophobic membrane, which is installed vertically or diagonally upward from 0° to 45°. The inclination angle is beneficial to extend the bulk nanobubble generation process and further reduce the bubble diameter.
  • the top cover is made of airtight material.
  • the liquid is introduced from the container 8 until the entire container 8 is filled and covers the hydrogen production unit. As shown in Figure 2, the liquid enters the hydrogen production unit through the bottom membrane 4 of the inner hydrophobic and outer hydrophilic membrane and reacts to generate hydrogen under the action of the ring electrode 2. When a large amount of hydrogen is enriched on the side membrane 3, the ring electrode 2 is closed.
  • the heat generated by the ring electrode 2 should be controlled below 30°C.
  • the adjustable range of the broadband ultrasonic generator 1 includes but is not limited to 20KHz ⁇ 400KHz, and it radiates waves around the center of the reactor. Without additional high pressure, low frequency promotes the growth of nanobubbles, based on the hydrophobic film oscillation on the outer surface of the side surface to protect the interface nanobubble belt diffusion; high frequency promotes the formation of gas explosion cavitation in the liquid and assists the mass generation of bulk nanobubbles.
  • the liquid is introduced from the bottom membrane 4 of the hydrogen production unit, and the electrodes act to generate hydrogen, and then the short-term low-frequency-high-frequency rotating ultrasound (5-20min) cooperates with the porous membrane to form 20-1000nm hydrogen nanobubbles, reducing water molecules Mix and disperse with it.
  • the energy release of ultrasonic cavitation and the bursting of a part of the bubbles and the microjet effect can quickly sterilize the liquid; after filling, the hydrogen-rich nanobubbles (according to the Young-Laplace equation calculates that the internal pressure is 3-30kPa And above)
  • the long-term micro-release during storage further continues to sterilize the beverage.
  • a hydrogen tester can be installed at the water outlet of the system box to detect in real time whether the hydrogen content of the liquid at the outlet meets the standard (3-6ppm), and the material is discharged when the standard is reached.
  • the bottom membrane is made of non-toxic materials such as nano-scale ( ⁇ 1000 nm pore diameter) ceramics, fibers, metal organic frameworks, etc., which is convenient for water penetration and intercepts the entry of foreign matter in the liquid and the dissolution of reaction byproducts.
  • Hydrogen-producing electrodes can be precious metals (such as Pt), non-precious metals (such as Mg), and carbon glass electrodes.
  • the by-products in the reaction process are purified and blocked by membranes. Compared with traditional electrolysis, it avoids contamination of drinks and enhances safety.
  • the food system applicable to the system of the present invention can be pure-phase water, mineral water, diluted fruit juice (with or without fruit particles), milk, alcohol and other liquids. Suitable for most liquid drinks and health functional drinks.
  • the present invention will be described in detail through the following examples. The following examples are for illustrative purposes rather than limiting the scope of the invention.
  • the raw materials used in the following examples are all commercially available products.
  • the production equipment used for processing is a self-designed ultrasonic-electrode-nanoporous membrane coupling microsystem.
  • the amount of dissolved hydrogen and hydrogen nanobubbles are measured by a hydrogen tester or commonly used methods. .
  • the nano-bubbles Compared with the hydrogen-rich water prepared without the side film in the comparative example, in the examples, due to the micro-interfacial tension, surface energy, and nano-effect of the nano-bubbles on the hydrophobic surface, the nano-bubbles have a supersaturated dissolution rate.
  • the hydrogen content of the prepared hydrogen-rich water is significantly increased, and the bubbles can be persistent and stable.
  • the invention adopts a self-designed ultrasonic-electrode-nanoporous membrane coupling to produce hydrogen nanobubbles microcirculation system, which is convenient, intelligent and green to produce hydrogen-rich (3-6ppm) nanobubbles with a diameter of 20-1000nm, and is not sealed It can also exist stably for more than 8 to 36 hours, and the hydrogen-rich beverage prepared therefrom has significant antioxidant and antibacterial functions, diversified varieties, richer taste, diversified layers, and has huge commercial prospects.

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Abstract

一种超声‑电极‑纳米多孔膜耦合制氢灭菌系统，包括容器，以及设置在容器内的若干个制氢单元，所述制氢单元包括腔体，以及位于腔体内的宽频超声发生器、环形产氢电极，所述环形产氢电极包绕宽频超声发生器；所述腔体的底膜为内疏水外亲水膜；所述腔体的侧膜为内亲水外疏水膜，竖直安装或斜向上呈0°～45°安装。该系统具有连续、高效促进液态体系自循环微流、溶氢(呈纳米气泡)及界面-体相气泡转化、分散、杀菌等功能，所制备抗菌功能饮料的含氢量高(3～6ppm)，其中富氢纳米气泡直径可分布于20～1000nm，未密封状态也可稳定保留8～36h以上。本发明的制备方法简单、智能、高效且产品高质、绿色、保健，避免大量充氢浪费与高压能耗，防止加工二次污染体系，满足食品级需求。

Description

一种超声-电极-纳米多孔膜耦合制氢灭菌系统 技术领域
本发明涉及一种生成富氢纳米气泡的单元组合系统及其制备抗菌功能饮品的方法，属于液体食品加工技术领域。
背景技术
随着氢气科学的日益发展，人们对于氢气与人类健康医疗、饮食的认知与需求也在不断提高。氢是自然界最简单、分子最小、分布最广泛的元素，早在2007年就由日本科学家发现了氢气的选择抗氧化能力，进而引起众多学者争相研究。氢气的穿透力强、扩散速度快的特点，可以进入机体的任何部位发挥抗氧化、抗炎、抗凋亡等机制。相比于其他常用食品级抗氧化剂(如维生素C、多酚类物质等)，氢气自身结构简单且反应产物简单无害、易排出无残留，且选择性地与活性/毒性强的活性氧自由基结合，而不破坏其他重要活性氧信号分子。
氢气最常应用的方法就是制备成富氢液体，尤其是富氢水。然而现有技术中，除富氢液体饮品的品种单一外，其溶氢方式也基本以充入氢气、高压增溶为主，尤其是带离子与内溶物的饮料体系，溶氢含量普遍较低(0.2～2.2ppm)、溶氢体积偏大(肉眼可见气泡或微米级气泡)、氢气泡上浮易破裂、稳定性差；纯电解法、化学反应法制氢则容易产生副产物，对液体造成二次污染，这极大地影响了富氢饮品的抗氧化、抗菌与保健功能，以及优质的多层次口感与多元化品类。最近研究发现，将气体以纳米级尺寸溶解于水中具有宏观原理(亨利定律)无法解释的超饱和溶解率与气泡稳定现象，尤其是在疏水表面，由于纳米气泡的微界面张力、表面能、纳米效应等作用，纳米气泡可以持久而稳定存在。因此，传统及现有的富氢饮品的制备方法亟待科学升级，以满足广大消费者日益增长的对富氢饮品既健康又美味的多向需求。
发明内容
本发明的目的是为了解决现有技术存在的不足，提供一种超声-电极-纳米多孔膜耦合制氢灭菌系统。该系统可便捷、智能、绿色地产生直径分布于20～1000nm的富氢纳米气泡，溶氢(3～6ppm)上浮缓慢且非密闭状态也可稳定存在8～36h以上，所制备富氢饮品的抗氧化与抗菌功能显著，口感较原有饮品更加丰富、多元有层次。
为实现上述目的，本发明具体技术方案如下：
一种超声-电极-纳米多孔膜耦合制氢灭菌系统，包括容器，以及设置在容器内的若干个制氢单元，所述制氢单元包括腔体，以及位于腔体内的宽频超声发生器、环形产氢电极，所述环形产氢电极包绕宽频超声发生器；所述腔体底的底膜为内疏水外亲水膜；所述侧膜为内亲水外疏水膜，竖直安装或斜向上呈0°～45°安装。该膜组装自循环系统形成氢气纳米气泡的同时，防止液体中大颗粒与大分子进入反应环境、促进氢气富集扩散、避免反应副产物二次污染。顶盖由不透气材料构成。
进一步地，所述底膜采用纳米级(＜1000nm孔径)的陶瓷、纤维、金属有机框架等无 毒材料制备。
进一步地，所述宽频超声发生器的可调节范围包括但不限于20KHz～400KHz，处于反应器中心位置向四周辐射波。
进一步地，该系统箱体出水口处还安装有一氢气测试仪。
本发明的有益效果是：本发明的超声-电极-纳米多孔膜耦合制氢灭菌系统具有连续、高效促进液态体系自循环微流、溶氢(呈纳米气泡)及界面-体相气泡转化、分散、杀菌等功能，所制备抗菌功能饮料的含氢量高(3～6ppm)，其中富氢纳米气泡直径可分布于20～1000nm，未密封状态也可稳定保留8～36h以上，所制备富氢饮品的抗氧化与抗菌功能显著，口感较原有饮品更加丰富、多元有层次。本发明的系统简单、智能、高效且产品高质、绿色、保健，避免大量充氢浪费与高压能耗，防止加工二次污染体系，满足食品级需求。
附图说明
图1为本发明采用超声-电极-纳米多孔膜耦合制氢气纳米气泡的微循环系统及其箱体设计。
图2为本发明采用纳米多孔膜及过程说明。
图3为本发明采用产氢微系统阵列。
图中，1宽频超声发生器、2环形产氢电极、3食品级纳米多孔侧膜、4食品级纳米多孔底膜、5顶盖、6界面纳米气泡、7体相纳米气泡、8容器、9进料口、10出料口、11液体循环溶氢管
具体实施方式
如图1和3所示，一种超声-电极-纳米多孔膜耦合制氢灭菌系统，包括容器8，以及设置在容器8内的若干个制氢单元，所述制氢单元包括腔体，以及位于腔体内的宽频超声发生器1、环形产氢电极2，所述环形产氢电极2包绕宽频超声发生器1；所述腔体底的底膜4为内疏水外亲水膜；侧膜3为内亲水外疏水膜，竖直安装或斜向上呈0°～45°安装。倾斜角度时有利于延长体相纳米气泡生成过程、进一步减小气泡直径。该膜组装自循环系统形成氢气纳米气泡的同时，防止液体中大颗粒与大分子进入反应环境、促进氢气富集扩散、避免反应副产物二次污染。顶盖由不透气材料构成。
使用时，液体从容器8通入直至充满整个容器8并覆盖制氢单元。如图2所示，液体通过内疏水外亲水膜的底膜4进入制氢单元并在环形电极2作用下反应生成氢气，当大量氢气富集在侧膜3上时，关闭环形电极2，控制宽频超声发生器1对氢气液体混合体系造成线性振荡与空化效应，协同多孔膜作用形成界面氢气纳米气泡并逐步转化为20～1000nm的体相氢气纳米气泡；体相氢气纳米气泡通过制氢单元侧膜3内亲水外疏水膜重新排回容器8中，完成溶氢。而且，由于密度差异，富氢纳米气泡液体在呈微上浮趋势，非富氢纳米气泡液体微下沉，并在水压作用(P＝ρgh；液体饮品ρ越大、底膜距离液面h越深，则促流压力P越高)与膜吸力作用下再次进入制氢单元中，形成微通道内循环溶氢，实现液体的大量、均匀的溶氢。待制氢一定时间后，打开箱体上部出水口导出富氢液体并灌装；
在整个制氢过程中，环形电极2所产热应控制低于30℃，温度越低，水分子间的填充空隙增大、水合作用越强，有利于氢气发生与溶解平衡。宽频超声发生器1的可调节范围 包括但不限于20KHz～400KHz，处于反应器中心位置向四周辐射波。无需额外高压，低频促进纳米气泡生长，基于侧面外表面疏水膜振荡保护界面纳米气泡带扩散；高频促进液体形成气爆空化并辅助体相纳米气泡的大量生成。进一步地，通入液体从制氢单元底膜4，先电极作用生成氢气，后短时低频-高频轮转超声(5～20min)协同多孔膜作用形成20～1000nm氢气纳米气泡，减小水分子团并与其混合分散。
而且，制氢过程中，超声空化与一部分气泡破裂的能量释放与微射流效应能对液体的进行快速杀菌；当灌装后富氢纳米气泡(根据Young-Laplace方程推算内部高压在3-30kPa及以上)在储藏过程中长时微释放进一步对饮品持续杀菌。
进一步地，可在该系统箱体出水口处安装一氢气测试仪，实时检测出口处液体含氢量是否达标(3～6ppm)，达标即出料。
进一步地，所述底膜采用纳米级(＜1000nm孔径)的陶瓷、纤维、金属有机框架等无毒材料制备，便于水体渗入，拦截液体中异物进入与反应副产物溶出。产氢电极可为贵金属(如Pt)、非贵金属(如Mg)以及碳玻电极等，反应过程中的副产物由膜净化、阻隔，与传统电解相比避免了污染饮品，增强安全保障。
本发明的系统适用的食品体系可以为纯相的水、矿物质水、稀释果汁(含果粒或不含果粒)、奶类、酒类等液体。适用于大多数液体饮品与保健功能饮料。下面通过实施例对本发明进行具体描述。下列实施例用于说明目的而非用于限制本发明范围。
以下实施例所使用各原料均为市售通用产品，加工所使用生产设备为自设计的超声-电极-纳米多孔膜耦合微系统，溶氢量及氢纳米气泡采用氢气测试仪或现常用方法测定。
实施例1：
将纯水从箱体底部的管道口通入，直至充满整个反应箱体并覆盖制氢单元，液体从制氢单元底部多孔膜进入并在环形电极作用下反应生成氢气，此时控制温度在0℃；氢气大量富集并透过微反应器侧面纳米多孔金属膜时(孔径200nm；θ＝45°)，关闭环形电极，同时宽频超声发生器(20KHz低频5min；400KHz高频15min)对氢气液体混合体系造成线性振荡与空化效应，从而形成界面氢气纳米气泡(～300nm)并逐步转化为体相氢气纳米气泡(～50nm)；超声空化与一部分气泡破裂的能量释放与微射流效应完成对纯水的快速杀菌，打开箱体上部出水口导出富氢水(6ppm；非密封气泡至少稳定约24h)。
实施例2：
将矿物质水从箱体底部的管道口通入，直至充满整个反应箱体并覆盖制氢单元，液体从制氢单元底部多孔膜进入并在电极作用下反应生成氢气，此时控制温度在5℃；氢气大量富集并透过微反应器侧面纳米多孔纤维膜时(孔径100nm；θ＝30°)，关闭电极，同时控制超声发生器(50KHz低频3min；400KHz高频10min)对氢气液体混合体系造成线性振荡与空化效应，从而形成界面氢气纳米气泡(～150nm)并逐步转化为体相氢气纳米气泡(～20nm)；超声空化与一部分气泡破裂的能量释放与微射流效应完成对纯水的快速杀菌，打开箱体上部出水口导出富氢水(4ppm；非密封气泡至少稳定约36h)。
实施例3：
将果汁从箱体底部的管道口通入，直至充满整个反应箱体并覆盖制氢单元，液体从制氢单元底部多孔膜进入并在电极作用下反应生成氢气，此时控制温度在30℃；氢气大 量富集并透过微反应器侧面纳米多孔陶瓷膜时(孔径1000nm；θ＝15°)，关闭电极，同时控制超声发生器(20KHz低频5min；200KHz高频5min)对氢气液体混合体系造成线性振荡与空化效应，从而形成界面氢气纳米气泡(～1000nm)并逐步转化为体相氢气纳米气泡(～800nm)；超声空化与一部分气泡破裂的能量释放与微射流效应完成对纯水的快速杀菌，打开箱体上部出水口导出富氢水(3ppm；非密封气泡至少稳定约8h)。
实施例4：
将牛奶从箱体底部的管道口通入，直至充满整个反应箱体并覆盖制氢单元，液体从制氢单元底部多孔膜进入并在电极作用下反应生成氢气，此时控制温度在0℃；氢气大量富集并透过微反应器侧面纳米多孔金属膜时(孔径500nm；θ＝0)，关闭电极，同时控制超声发生器(30KHz低频2min；300KHz高频8min)对氢气液体混合体系造成线性振荡与空化效应，从而形成界面氢气纳米气泡(～550nm)并逐步转化为体相氢气纳米气泡(～300nm)；超声空化与一部分气泡破裂的能量释放与微射流效应完成对纯水的快速杀菌，打开箱体上部出水口导出富氢水(3.5ppm；非密封气泡至少稳定约12h)。
对比例1：
将纯水从箱体底部的管道口通入，直至充满整个反应箱体并覆盖制氢单元，液体从制氢单元底部多孔膜进入并在环形电极作用下反应生成氢气，此时控制温度在0℃；氢气大量富集(无侧膜)，关闭环形电极，同时宽频超声发生器(20KHz低频5min；400KHz高频15min)对氢气液体混合体系造成线性振荡与空化效应，从而形成一定的溶解氢；超声空化与一部分气泡破裂的能量释放与微射流效应完成对纯水的快速杀菌，打开箱体上部出水口导出富氢水(0.6ppm；非密封气泡稳定小于20min)。
与对比例中无侧膜制备的富氢水相比，实施例中，在疏水表面由于纳米气泡的微界面张力、表面能、纳米效应等作用，使得纳米气泡具有超饱和溶解率，因而实施例制备的富氢水氢含量显著增加，并且气泡可以持久而稳定存在。本发明采用自设计的超声-电极-纳米多孔膜耦合制氢气纳米气泡的微循环系统，不仅便捷、智能、绿色地产生直径分布于20～1000nm的富氢(3～6ppm)纳米气泡，非密封也可稳定存在8～36h以上，并且由此所制备富氢饮品的抗氧化与抗菌功能显著，品种多样化，口感更加丰富、多元有层次，具有巨大的商业前景。
综上，上述一般性文字说明及具体实施例已对本发明作了详尽描述，但在本发明的制氢单元与饮品制备方面可作一些改进或提高，这对本领域技术人员而言是显而易见的，因此也均属于本发明要求保护的范围。

Claims (4)

  1. 一种超声-电极-纳米多孔膜稠合制氢灭菌系统，其特征在于，包括容器，以及设置在容器内的若干个制氢单元，所述制氢单元包括腔体，以及位于腔体内的宽频超声发生器、环形产氢电极，所述环形产氢电极包绕宽频超声发生器：所述腔体底的底膜为内疏水外亲水膜。所述侧膜为内亲水外疏水膜，坚直安装或斜向上呈0°～45°安装。顶盖由不透气材料构成。
  2. 根据权利要求1所述的系统，其特征在于，所述底膜采用纳米级(＜1000nm孔径)的陶瓷、纤维、金属有机框架等无毒材料制备。
  3. 根据权利要求1所述的系统，其特征在于，所述宽频超声发生器的可调节范围包括但不限于20KHz～400KHz，处于反应器中心位置向四周辐射波。
  4. 根据权利要求1所述的系统，其特征在于，该系统箱体出水口处还安装有一氢气测试仪。
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