WO2015154703A1 - 果蔬清洗机 - Google Patents

果蔬清洗机 Download PDF

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Publication number
WO2015154703A1
WO2015154703A1 PCT/CN2015/076236 CN2015076236W WO2015154703A1 WO 2015154703 A1 WO2015154703 A1 WO 2015154703A1 CN 2015076236 W CN2015076236 W CN 2015076236W WO 2015154703 A1 WO2015154703 A1 WO 2015154703A1
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WO
WIPO (PCT)
Prior art keywords
water
permeable membrane
fruit
washing machine
vegetable washing
Prior art date
Application number
PCT/CN2015/076236
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English (en)
French (fr)
Inventor
肖志邦
Original Assignee
大连双迪创新科技研究院有限公司
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Publication of WO2015154703A1 publication Critical patent/WO2015154703A1/zh

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23N—MACHINES OR APPARATUS FOR TREATING HARVESTED FRUIT, VEGETABLES OR FLOWER BULBS IN BULK, NOT OTHERWISE PROVIDED FOR; PEELING VEGETABLES OR FRUIT IN BULK; APPARATUS FOR PREPARING ANIMAL FEEDING- STUFFS
    • A23N12/00—Machines for cleaning, blanching, drying or roasting fruits or vegetables, e.g. coffee, cocoa, nuts
    • A23N12/02—Machines for cleaning, blanching, drying or roasting fruits or vegetables, e.g. coffee, cocoa, nuts for washing or blanching
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4616—Power supply
    • C02F2201/4617—DC only

Definitions

  • the invention relates to a fruit and vegetable washing machine, belonging to the technical field of electrolysis equipment.
  • the market has launched a cleaning machine for vegetables and fruits that can degrade pesticides.
  • Mechanical fruit and vegetable washing machine removes pesticides attached to the surface of vegetables and fruits by means of water circulation or ultrasonic vibration.
  • the disadvantage is that the removal of pesticides is inefficient.
  • Ozone-type fruit and vegetable washing machine By generating ozone and utilizing the strong oxidation of ozone, the efficiency of degrading pesticides is better than that of mechanical fruit and vegetable washing machines. However, the fatal problem of ozone oxidation is accompanied by pungent odor, especially the formation of a strong carcinogen, bromate. In addition, ozone has a poor removal effect on residual heavy metals in fruits and vegetables.
  • the technical problem solved by the invention is to propose a fruit and vegetable washing machine which can effectively and reliably degrade pesticides and insecticides in foods such as fruits and vegetables, thereby being beneficial to health.
  • a fruit and vegetable washing machine comprising a water container and an electrolytic power source, wherein the water container is provided with at least one electrolytic unit, and the electrolytic unit includes at least one pair of An electrode and an anode electrode, wherein the electrolysis power source is used to supply power to the cathode electrode and the anode electrode; and a pair of a porous membrane and a positive electrode are provided with a water-permeable membrane, and the water-permeable membrane has a water permeability diameter of 2 mm or less and Greater than or equal to 1 nanometer.
  • the water permeable membrane described in the above technical solution is also referred to as a water permeable membrane, and refers to a water permeable membrane having a water permeability pore diameter ranging from millimeters to nanometers (the present invention defines a water permeable pore size ranging from 2 mm to 1 nm), including various kinds of daily water treatment.
  • Filter membranes such as ultrafiltration membrane (UF), nanofiltration membrane (NF) and microfiltration membrane (MF), and the like.
  • the water permeable membrane in the apparatus of the present invention is not a conventionally used ion membrane, but is a separator which has never been used in the field of water electrolysis.
  • the inventors have innovatively introduced a water permeable membrane into an electrolytic cell as a cathode and an anode electrode. Inter-membrane. Therefore, we believe that the reaction process of the electrolysis unit of the present invention in addition to the conventional electrolysis reaction process In addition, a new important reaction process has emerged, namely a low-pressure cold plasma discharge reaction process in a water body.
  • the specific analysis is as follows:
  • the plasma generated in the water is often required to give an initial high voltage of excitation, and one of the main factors affecting the initial voltage is the parameter of the discharge electrode.
  • the electrode material, the discharge pitch, and the electrode diameter have an effect on the initial excitation voltage.
  • the initial excitation voltage decreases. From another point of view, the smaller the electrode diameter, the better the enhancement of the radical generation in the ion channel under the same voltage.
  • the separator has a plurality of pores having a small diameter of water permeability (millimeter or even nanometer), which can be regarded as macroscopically decomposing the discharge reaction in a large range of electrodes. Discharges the tip of an electrode with a myriad of extremely small radius of curvature. This in turn greatly reduces the initial voltage that excites the plasma reaction.
  • the water-permeable membrane decomposes the two electrodes of the yin and yang into an array-free sub-electrode, but the materials of all the sub-electrodes, The voltages are all the same. This ensures that the overall electric field is evenly distributed in the macroscopic field, and the electric field generated by the electrolysis is more uniform in the rising process, ensuring high efficiency of the discharge reaction.
  • the present invention compares with the discharge of the counter electrode without a water permeable membrane.
  • the volume of microbubbles generated by water electrolysis in a myriad of ultrafine pores is much smaller than that of the same area without permeable water.
  • the diaphragm opposes the volume of bubbles produced by the electrode, and the number of bubbles is much larger than it. This effectively increases the specific surface area of the gas-liquid two-phase contact.
  • the various oxidation factors (such as hydroxyl groups) generated by the plasma mainly occur at the contact surface of the gas-liquid two phases.
  • Conventional water plasma discharge technology in order to generate water plasma discharge, often introduces gas into the water through the outside, and applies high-intensity pulse voltage or high temperature conditions.
  • the invention innovates to guide the plasma discharge into the numerous small water storage spaces of the water permeable membrane, and relies on the gas generated by the hydroelectric analysis of hydrogen and oxygen evolution, and enters the membrane to induce the gasification of the water itself, thereby exciting the gas with a very small voltage.
  • the plasma discharge of water is not only due to the improvement of efficiency, but also effectively prevents the deterioration of biological indicators due to excessive current density.
  • the electrode diameter electrode curvature radius
  • the electrolytic gas generation cannot occur or the gas production efficiency is extremely low, and to a certain extent, an infinite number of small curvature radius electrodes in the micropores in the membrane are caused.
  • the tip discharge does not work properly. Therefore, after repeated trials by the inventors, it was confirmed that the water permeability pore diameter ranged from 2 mm to 1 nm.
  • the present invention provides a microporous membrane in the water permeable membrane outside the conventional electrolytic reaction process by disposing a water permeable membrane having a certain pore diameter between the anode and the anode.
  • the formation of a low-pressure cold plasma discharge reaction in the water body can efficiently generate a transient oxidation factor having bactericidal ability in water.
  • a large number of ultra-fine bubbles mainly composed of hydrogen are formed in the water, which ruptures and vibrates during the ascending process, which greatly reduces the adhesion of residual pesticides and vegetables, so that the pesticides are better dissolved in water and oxidized by water.
  • Degradation due to the strong penetrating power of hydrogen, can reach the fiber pores of vegetables to the depth, so that the oxidative degradation reaction is more complete and comprehensive.
  • Oxidation factor in water can enhance the washing and removing effect of pollutants in water; when used for cleaning fruits and vegetables, the smaller ⁇ , the more intense the related reaction, the better the washing and bactericidal degradation effect, and the strong bubbles between the cathode and the membrane. Scouring, flushing out calcium and magnesium ions and washing contaminants in the source water, but helping to prevent blockage between the cathode electrode and the membrane;
  • the apparatus of the invention increases the OH - concentration of the water after electrolysis while generating a large amount of high-concentration hydrogen bubbles, which greatly enhances the hydrolysis of the pesticide itself and further enhances the degradation effect of the pesticide, and the strong oxidizing factor has the function of killing bacteria.
  • the effect which is especially important for raw food;
  • the oxidative factor is an oxidative degradation of the pesticide or an accelerated reaction of natural hydrolysis, the nutrient composition and taste of the vegetables and fruits are effectively maintained.
  • the improvement of the present invention based on the above technical solution is that the distance between the cathode electrode and the anode electrode is greater than or equal to the thickness of the water permeable membrane and is less than or equal to 20 mm.
  • the membrane can be very thin (for example, ultrafiltration membrane can be 0.1mm ⁇ 0.3mm), the electrolysis voltage under the same working condition can be very low, even if it is only powered by a 3.7V lithium battery, it can form an operating current of 2 amps or more. The prior art is not possible. Conversely, the distance between the electrodes of the yin and yang is increased.
  • the generated oxidation factor is correspondingly reduced, especially the incidence of ozone-based strong oxidants is reduced.
  • ozone is produced in large quantities in the passage of oxygen through the discharge area in the form of bubbles.
  • the distance between the electrodes of yin and yang is increased, and the probability of oxygen evolution from the anode into the membrane in the plasma discharge state is reduced, and ozone is reduced in comparison.
  • the oxidative factors produced in water are more represented by hydroxyl-based transient oxidation factors.
  • the distance between the cathode electrode and the anode electrode is preferably equal to or greater than the thickness of the water-permeable membrane and less than or equal to 20 mm.
  • a further improvement of the present invention based on the above technical solution is that the water permeable membrane is a non-conductive water permeable membrane. This is because, in most cases, it is desirable to have as many oxidizing factors as possible in the water.
  • the water-permeable separator having a good conductivity is likely to form a composite electrode with a similar electrode at the time of discharge reaction, affecting the effect of the discharge reaction in water and the type of the product, and has many uncontrollable factors. Therefore, a non-conductive water-permeable separator is preferable.
  • a further improvement of the above technical solution of the present invention is that the cathode electrode is provided with a first through hole, and the first through hole has a hole diameter of 1 mm or more.
  • a further improvement of the above technical solution of the present invention is that the water permeable membrane has a second through hole, and the second through hole has a diameter larger than 2 mm.
  • the water permeable membrane is a single layer water permeable membrane or a multilayer water permeable membrane.
  • One specific material of the water permeable membrane is that the single layer water permeable membrane is an ultrafiltration membrane or a single layer water permeable membrane made of a carbonaceous material.
  • the second technical solution of the present invention is that the electrolysis power source is a DC or alternating pulse power source with a high level and a narrow pulse width.
  • the third technical solution of the present invention is that the water container is provided with a pulsator, and the electrolysis unit is evenly arranged along the circumference of the pulsator in the water container.
  • FIG. 1 is a schematic view showing the internal structure of a fruit and vegetable washing machine in accordance with a first embodiment of the present invention.
  • Figure 2 is a plan view of Figure 1.
  • FIG. 3 is a schematic structural view of the electrolytic unit of FIG. 1.
  • Figure 4 is an exploded view of Figure 3.
  • the fruit and vegetable washing machine of this embodiment includes a water holding container 10 and an electrolytic power source.
  • An electrolytic unit 20 is provided in the water container 10 of the present embodiment.
  • the electrolytic cell 20 includes a pair of cathode electrodes 2 and anode electrodes 3.
  • An electrolytic power source is used to supply power to the cathode electrode 2 and the anode electrode 3.
  • a water permeable membrane 4 is provided between each pair of the cathode electrode 2 and the anode electrode 3.
  • the water permeable membrane 4 of the present embodiment adopts a single-layer PVDF ultrafiltration membrane (polyvinylidene fluoride membrane) having an average water permeability of 0.03 ⁇ m; of course, the water permeable membrane 4 of the present embodiment can also adopt a permeable membrane of other materials, and the average
  • the water permeable aperture may be between 2 mm and less and 1 nm or more.
  • the water permeable membrane 4 of the present embodiment is in close contact with the cathode electrode 2 and the anode electrode 3 at the same time, and the distance between the water permeable membrane 4 and the anode and cathode electrodes is zero.
  • the cathode electrode 2 and the anode electrode 3 of the present embodiment each use an inert electrode made of a titanium-based platinum group oxide (coating thickness: 0.8 mm), the cathode electrode 2 has a circular shape, and the anode electrode 3 has a circular shape. Flaky.
  • the cathode electrode 2 is provided with a first through hole 21, and the surface of the anode electrode is not opened.
  • the water permeable membrane 4 of the present embodiment is a non-conductive water permeable membrane.
  • the electrolysis power supply of the embodiment adopts a DC pulse power supply with a high-level narrow pulse width regulation voltage of 30 volts, and an alternating pulse power supply can also be used.
  • the cathode electrode 2 and the anode electrode 3 of the present embodiment are placed in parallel in the electrolytic cell 20, and the cathode electrode 2 is located above the anode electrode 3.
  • a pulsator 11 is disposed, and the electrolysis unit 20 is evenly arranged along the circumference of the pulsator 11 in the water container.
  • the electrolysis unit 20 of the present embodiment is used for the water electrolysis experiment.
  • the volume of the water container is 600 ⁇ 240 ⁇ 360 mm
  • the source water is tap water
  • TDS 160 mg/L
  • the water container is filled with water of about 4 liters
  • the electrolysis time is 30 minutes. The water sample was taken every 5 minutes.
  • the bubble from the water is zero - the maximum relative bubble content in the experiment is divided into 0 to 5 grades;
  • the electrolytic unit 20 of the present invention is dedicated to a fruit and vegetable washing machine, and the focus is on the macroscopic effect of the change trend of the oxidation factor. Therefore for Simplify the repetitive experimental workload and develop a titration solution that qualitatively understands the total amount of oxidizing factors in water. After self-made titration of the droplets into the water, observe the yellowing degree of the water color, and divide it into 5 grades to qualitatively determine the oxidative factor content in the water:
  • the color is the yellowest - the corresponding oxidation factor in the water is the most, set to 5;
  • the degree of color change from colorless to color yellow is set to 1, 2, 3, and 4 levels.
  • the water permeable membrane 4 of the present embodiment was subjected to water electrolysis separately from the three cases in which the water permeable membrane was removed or replaced with an ionic membrane, and the comparative experimental conditions were:
  • the ionic membrane adopts a neutral ion membrane, and the distance between the ion membrane and the anode and cathode is 1 mm, respectively;
  • the water permeable membrane 4 is a PVDF ultrafiltration membrane
  • the electrolysis current was 300 mA in both cases and electrolysis was carried out for 15 minutes.
  • the results of Experiment 2 are shown in Table 2.
  • the fruit and vegetable washing machine of this embodiment is basically the same as that of the first embodiment, and the variation different from the first embodiment is: 1) the electrolytic unit 20 includes two pairs of the cathode electrode 2 and the anode electrode 3; 2) the water-permeable membrane 4 and the anode and the cathode electrode The spacing is 1mm; 3) the two ends of the water-permeable membrane 4 are respectively beyond the cathode and the anode; 4) each pair of the cathode electrode 2 and the anode electrode 3 are parallel and horizontally placed in the water quality adjusting unit 20, and the two pairs of cathode electrodes 2 and the anode electrode 3 are provided on the upper and lower sides of the partition plate (not shown).
  • the fruit and vegetable washing machine of this embodiment is basically the same as the first embodiment, and the variation different from the first embodiment is: 1) the anode electrode 3 is an inert electrode made of a carbonaceous material such as graphite or activated carbon; 2) the water permeable membrane 4 is A single-layer water-permeable membrane made of a carbonaceous material such as graphite or activated carbon; 3) a distance ⁇ 1 between the water-permeable membrane 4 and the anode electrode 3 is 8 mm; 4) a distance ⁇ 2 between the water-permeable membrane 4 and the cathode electrode 2 is 0.05 mm.
  • the fruit and vegetable washing machine of this embodiment is basically the same as the second embodiment, and the changes different from the second embodiment are: 1) the first through hole 21 is opened in the cathode electrode 2, and the through hole diameter is 1 mm; 2) the water permeable membrane 4 It is the same length as the cathode electrode 2 and the anode electrode 3; 3) the water-permeable membrane 4 is in close contact with the anode electrode 3 but separated from the cathode electrode 2, and the distance ⁇ 2 between the water-permeable membrane 4 and the cathode electrode 2 is 2 mm.
  • the fruit and vegetable washing machine of this embodiment is basically the same as that of the fourth embodiment, and the variation of the fourth embodiment is: 1) the water permeable membrane 4 is provided with a second through hole 41 having a diameter of ⁇ 2.1 mm (see FIG. 4), and the second through hole 41 is the same number as the first through hole 21 and substantially concentrically aligned; 2) the distance ⁇ 2 between the water permeable membrane 4 and the cathode electrode 2 is 3 mm.
  • the fruit and vegetable washing machine of this embodiment is a variation based on the third embodiment, and is different from the third embodiment in that: 1) the cathode electrode 2 and the anode electrode 3 are both wafer plane electrodes, each having a diameter of 48 mm and a thickness of 1 Millimeter; 2) The cathode electrode 2 is uniformly provided with a comb-shaped first through hole 21; 3) The water permeable membrane 4 has the following three options and settings:
  • the first layer adopts PVDF ultrafiltration membrane, the average permeability pore diameter is 0.03 micron, the thickness is 0.5mm, no opening, close to the anode electrode;
  • the second layer adopts the average permeability pore size 0.05 micron PVDF ultrafiltration membrane a thickness of 0.5 mm, cut into a wafer film of the same size as the cathode electrode 2 and having a comb-shaped second through hole 41, which is in close contact with the cathode electrode; the comb-shaped second through hole 41 and the comb-shaped first through hole 21 are positioned The direction is vertical.
  • the first layer is made of activated carbon fiber cloth, the specific surface area is 1200m 2 /g, the thickness is about 1.8mm after pressing the water
  • the second layer intermediate layer
  • PVDF ultrafiltration membrane the average is permeable.
  • the hole diameter is 0.03 ⁇ m, the thickness is 0.5 mm, and the hole is not opened
  • the third layer is a PVDF ultrafiltration membrane with an average permeability of 0.05 ⁇ m, the thickness is 0.5 mm, and is cut into the same size as the cathode electrode 2 and has a comb-shaped second through hole.
  • the wafer film of 41 is in close contact with the cathode electrode; the comb-shaped second through hole 41 is perpendicular to the position of the comb-shaped first through hole 21.
  • the fruit and vegetable washing machine of this embodiment selects different water permeable membranes 4 for water electrolysis experiments as follows:
  • the volume of the water container 1 is 500 ⁇ 500 ⁇ 1500 mm
  • the above-mentioned single-layer separator and combined separator were respectively electrolyzed for 15 minutes, and the electrolysis current was maintained at 300 mA during the electrolysis.
  • the experimental results are shown in Table 4.
  • the fruit and vegetable washing machine of the present invention is not limited to the specific technical solutions described in the above embodiments, for example: 1)
  • the water permeable membrane 4 may be a two-layer water permeable membrane formed by superposing an activated carbon fiber membrane (felt) and an ultrafiltration membrane.
  • the activated carbon fiber membrane is adjacent to the anode electrode 3 (toward the anode electrode 3) and covers the entire surface of the anode electrode 3, and the ultrafiltration membrane facing the cathode electrode 2 (facing away from the anode electrode 3) covers a part of the surface of the anode electrode 3 (the anode electrode faces)
  • the entire surface of the side of the cathode electrode 2) or the entire surface of the anode electrode 3, and both ends of the ultrafiltration membrane slightly exceed the anode electrode; 2) both the anode electrode 3 and the cathode electrode 2 are coated with a platinum group oxide
  • the inert electrodes (with a coating thickness of 0.8 mm) are all in the form of a circular sheet; 3) the first through holes 21 opened in the cathode electrode 2 may have a diameter of 1.5, 2 mm, etc.; 4) the water permeable membrane 4
  • the aperture having the second through hole 41 may be 2.5, 3 mm, etc.; 5) the pitch of the cathode electrode 2

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Abstract

一种果蔬清洗机，属于电解设备技术领域。该果蔬清洗机包括盛水容器（10）和电解电源，盛水容器（10）内设置有至少一个电解单元（20），电解单元（20）包括至少一对阴电极（2）和阳电极（3），电解电源用于对所述阴电极（2）和阳电极（3）供电；成对的阴电极（2）和阳电极（3）之间设有透水性隔膜（4），透水性隔膜（4）的透水孔径小于等于2毫米且大于等于1纳米。该果蔬清洗机可将源水制成富含大量超微氢气泡具有强还原能力和杀菌能力的富氢水，可安全降解果蔬等食品中残留农药、杀虫剂。

Description

果蔬清洗机 技术领域
本发明涉及一种果蔬清洗机，属于电解设备技术领域。
背景技术
蔬菜及瓜果中残留的农药和有毒重金属或无机物，日益为民众所担忧。所以才有了有机蔬菜的热卖与追捧。但是有机蔬菜的价格是普通蔬菜的3-10倍，对于一般收入的大众来说，常年食用有机蔬菜经济压力过大。另一方面，国家对有机蔬菜没有统一的标准，大多自称有机蔬菜的销售商都是商家的个人行为。实际是否真的“有机”令人困扰。
伴随着市场的需要，以及满足消费大众的需求。市场已推出能够降解农药的蔬菜水果的清洗商品机。主要有以下两种：
机械式果蔬清洗机：以水流循环冲洗方式或超声波震动的方式去除附着在蔬菜水果表面的农药等，缺点是去除农药效率低。
臭氧型果蔬清洗机：通过产生臭氧，利用臭氧的强氧化作用，降解农药效率优于机械式果蔬清洗机。然而，臭氧氧化的致命问题是伴有刺鼻异味，尤其是可能生成强致癌物——溴酸盐。此外，臭氧对于果蔬中残留重金属的去除效果不佳。
发明内容
本发明解决的技术问题是：提出一种可高效、安全降解果蔬等食品中残留农药、杀虫剂，从而有益健康的果蔬清洗机。
为了解决上述技术问题，本发明提出的技术方案是：一种果蔬清洗机，包括盛水容器和电解电源，所述盛水容器内设置有至少一个电解单元，所述电解单元包括至少一对阴电极和阳电极，所述电解电源用于对所述阴电极和阳电极供电；成对的阴电极和阳电极之间设有透水性隔膜，所述透水性隔膜的透水孔径小于等于2毫米且大于等于1纳米。
上述技术方案中所述透水性隔膜也叫透水膜，是指透水孔径从毫米级到纳米级(本发明限定透水孔径范围是2毫米-1纳米)的透水隔膜，包括日常水处理使用的各种过滤膜，如：超滤膜(UF)、纳滤膜(NF)和微滤膜(MF)，等。
上述本发明公开的果蔬清洗机技术方案的工作机理及有益效果陈述如下。
本发明装置中的透水性隔膜并非常规采用的离子膜，而是在水电解领域中从未用过的一种隔离膜，本发明人创新地将透水性隔膜引入电解单元中作为阴、阳电极间的隔离膜。由此我们认为本发明的电解单元在工作时的反应过程除了常规电解反应过程 以外，产生了一个新的重要反应过程，即水体低压冷等离子放电反应过程。具体分析如下：
1、电极尖端直径曲率与透水膜孔隙直径的等效模型
在水体放电中，诱发水中等离子体产生往往需要给予一个激发的初始高电压，影响初始电压主要因素之一即为放电电极的参数。在同等条件下电极材质、放电间距、电极直径(电极曲率半径)对初始激发电压都有影响。随着电极直径的减小，起始激发电压降低。从另一个角度说，在外加相同电压条件下，电极直径越小越有利于增强离子体通道中自由基产生的剧烈程度。在本发明中，阴阳电极之间有一层透水性隔膜，隔膜拥有无数个透水直径很小(毫米级乃至纳米级)的孔隙，从宏观看可视为将大范围电极的水中放电反应等效分解为无数个极小曲率半径电极的尖端放电。进而极大的降低了激发等离子体反应的初始电压。
水中电解时会生成大量超微气泡，其中有氢气泡也有氧气泡。而气泡的局部放电能大大增加反应活性分子的生成并且易于产生羟基等自由基，从而提高水中放电的反应效率。但是在气泡中产生放电需要气泡中的场强高于水中，要求整体电场较均匀；在本发明中，透水性隔膜将阴阳两组大电极分解为无数组子电极，但是所有子电极的材质、电压均相同。这就保证在宏观领域整体电场均匀排布，电解所产生的气泡在上升过程中所受电场较均匀，保证了放电反应的高效率。
2、增大接触面积，提高水中反应效率
众所周知，总体积相同的同等物体，被分成的个体越多总体的比表面积越大。同理，本发明与不加透水性隔膜的对电极放电情况对比，在产生等量气体的情况下，在无数个超微孔隙内水电解所产生的微气泡体积远远小于同等面积不加透水隔膜对电极电解所产生的气泡体积，而气泡数量也远远多于它。这就有效增加了气液两相接触的比表面积。而我们知道，等离子体次生成的各种氧化因子(如：羟基)主要发生在气液两相的接触面。也就是说：气液两相的接触面积越大，氧化因子的生成越多和反应越充分，水中有机物的降解、微生物杀菌效果更加优良，更进一步提高了水中放电反应的最终效率。
传统的水体等离子放电技术，为产生水体等离子放电，往往通过外部向水中导入气体，并施以加高强度脉冲电压或高温条件。本发明则创新将等离子放电引导到透水性隔膜的无数微小蓄水空间进行，依靠对水电解析氢、析氧反应生成的气体，进入膜中诱发水体自身气化，进而以极小电压激发出高效的水体等离子放电，其意义不仅在于效率的提高，还有效防止了因电流密度过大易导致生物性指标的恶化。
本发明装置中，如果透水性隔膜透水孔径过大(即微孔空间过大)等效于变相增大了电极直径(电极曲率半径)致使水中放电起始激发电压增高，并且使产生气泡体积变大减小了气液两相接触反应的比表面积。而透水性隔膜透水孔径过小(即微孔空间过小)，会使电解产气无法发生或是产气效率极其低下，小到一定程度会导致隔膜内各微孔中无数个小曲率半径电极的尖端放电无法正常进行。因此，经过发明人的反复试验，确定透水孔径范围是2毫米-1纳米。
概括上述本发明的果蔬清洗机技术方案的有益效果是：本发明通过将具有一定孔径的透水性隔膜设置在阴、阳极之间，在常规电解反应过程以外带来了在透水性隔膜内微孔中形成水体低压冷等离子放电反应，从而可以高效的在水中生成具杀菌能力的暂态氧化因子。
具体实用效果是：
1)水中形成有大量以氢气为主的超微气泡，在上升过程中不断破裂产生振动,极大的降低了残留农药与蔬菜的附着力使农药更好的溶入水而被水中的氧化因子降解，由于氢气具有极强的穿透力,可以深度到达蔬菜的纤维孔隙中,从而使氧化降解反应更加充分和全面。
2)水中氧化因子可强化对水中污染物的洗涤清除效果；当用于果蔬清洗时，δ越小，相关反应越激烈，洗涤、杀菌降解效果越好，而且由于阴极和膜之间有强烈气泡冲刷，将源水中的钙镁离子及洗涤污染物冲出，反而有助于防止阴电极和膜之间的阻塞；
3)本发明装置在产生大量高浓度氢气泡的同时电解后的水中OH-浓度增大，这都大大加强了农药本身水解作用更进一步加强了农药的降解效果，另外强氧化因子具有杀灭细菌的效果，这对食物生吃尤为重要；
4)无论是氧化因子对农药的氧化降解还是自然水解的加速反应都有效保持蔬菜水果的营养成分和口感。
本发明在上述技术方案基础上的改进是：所述阴电极和阳电极的间距大于等于所述透水性隔膜的厚度且小于等于20毫米。
本发明装置中，同等电压情况下，阴阳电极间的距离越小(极端情况下阴阳电极间的距离＝膜的厚度)水中电场强度越大，电极间的等离子通道更易形成，冷等离子体产生效率更高，生成的氧化因子越多。而且膜可以很薄(例如超滤膜可做到0.1mm～0.3mm)，同等工況下的电解电压可以很低，甚至仅仅以一块3.7V锂电池供电，可以形成2安培以上的工作电流，现有技术是无法做到的。反之，拉大阴阳电极间的距离， 生成的氧化因子相应减少，尤其是臭氧类强氧化剂的生成几率下降了。我们知道，臭氧大量产生于氧气以气泡形式通过放电区域。阴阳电极间距离增大，阳极析出氧气进入处于等离子放电状态的膜中的几率减少，对比而言臭氧就减少了。水中所生成的氧化因子，更多地表现为羟基类暂态氧化因子。但是间距过大又带来效率的降低，甚至膜中放电过程无法进行。因此，经过发明人的反复试验，在果蔬清洗机中，阴电极和阳电极的间距大于等于所述透水性隔膜的厚度且小于等于20毫米为最佳。
本发明在上述技术方案基础上的进一步改进是：所述透水性隔膜是非导电性的透水性隔膜。这是因为，多数情况下，希望水中产生的氧化因子越多越好。导电性较好的透水性隔膜在放电反应时容易与相近的电极形成复合电极而影响水中放电反应的效果和生成物的种类，不可控因素较多，因此优选非导电性的透水性隔膜。
上述本发明技术方案的更进一步改进是：所述阴电极上开有第一通孔，所述第一通孔的孔径大于等于1毫米。通过这样的改进，可以有利于阴极反应更充分进行，并将阴电极与隔离膜之间区域产生的氢气泡更好导出。
上述本发明技术方案的再进一步改进是：所述透水性隔膜开有第二通孔，所述第二通孔的孔径大于2毫米。通过这样的改进可以有利于产生的气泡更好的导出，尤其是在阴阳电极与透水性隔膜间距较小时其气泡导出效果更好。第二通孔与透水性隔膜自身的透水孔区别在于：透水孔是隔膜自身固有的，第二通孔则是另外单独制作的。
上述本发明技术方案完善一是：所述透水性隔膜是单层透水性隔膜或者是多层透水性隔膜。其中透水性隔膜的一种具体材料是：所述单层透水性隔膜是超滤膜或采用碳质材料制成的单层透水性隔膜。
上述本发明技术方案的完善二是：所述电解电源是高电平窄脉宽的直流或交变脉冲电源。
上述本发明技术方案的完善三是：所述盛水容器内设有波轮，所述电解单元沿盛水容器内的波轮周圈均匀布置。
附图说明
下面结合附图对本发明的果蔬清洗机作进一步说明。
图1是本发明实施例一的果蔬清洗机的内部局部结构示意图。
图2是图1的俯视图。
图3是图1的电解单元的结构示意图。
图4是图3的爆炸图。
具体实施方式
实施例一
本实施例的果蔬清洗机，参见图1和图2，包括盛水容器10和电解电源。本实施例的盛水容器10内设置有一个的电解单元20。
如图3和图4所示，电解单元20包括一对阴电极2和阳电极3。电解电源用于对阴电极2和阳电极3供电。每对的阴电极2和阳电极3之间设有透水性隔膜4。
本实施例的透水性隔膜4采用平均透水孔径0.03微米的单层PVDF超滤膜(聚偏二氟乙烯膜)；当然本实施例的透水性隔膜4也可以采用其他材质的透水过滤膜，平均透水孔径在小于等于2毫米且大于等于1纳米之间均可。
本实施例的透水性隔膜4同时紧贴在阴电极2和阳电极3上，透水性隔膜4与阴阳电极的间距为0。
本实施例的阴电极2和阳电极3均采用钛基覆涂铂族氧化物(涂层厚度为0.8毫米)制成的惰性电极，阴电极2呈圆形片状，阳电极3呈圆形片状。阴电极2上开有第一通孔21，阳电极的表面不开孔。
本实施例的透水性隔膜4是非导电性的透水性隔膜。
本实施例的电解电源采用高电平窄脉宽稳压30伏的直流脉冲电源，也可以采用交变脉冲电源。
本实施例的阴电极2和阳电极3在电解单元20内平行放置，阴电极2位于阳电极3的上方。
本实施例的盛水容器10内设有波轮11，电解单元20沿盛水容器内的波轮11周圈均匀布置。
一、实验1
采用本实施例的电解单元20进行水电解实验，盛水容器容积为600×240×360毫米，源水是自来水，TDS＝160mg/L，盛水容器注水约4升，电解时间为30分钟，每5分钟取水样测定一次。
以下实验中，水中气泡量(强度)以及水中氧化因子多少采用定性观测方法
①水中气泡量(强度)的目测分级：
从水中气泡为零～实验中相对气泡含量最大，分为0～5级；
②水中氧化因子的测定
如前所述，由于氧化因子在水中存留时间极为短暂，现有的检测方法(例如化学反应法和捕获法)的分析选择性和可信度还难以令人满意。同时考虑到本发明的电解单元20系专用于果蔬清洗机，侧重关心的是氧化因子的变化趋势级宏观作用。因此为 简化重复实验工作量，专门研发了定性了解水中氧化因子总量的滴定液。通过自制滴定液滴定到水中后，观察水体颜色的变黄程度，分为5级，定性判定水中氧化因子含量：
无色——对应水中氧化因子基本为零，设为0级；
颜色最黄——对应水中氧化因子相对最多，设为5级；
从无色到颜色最黄中间颜色变化的程度不同分设为1、2、3和4级。
实验1结果如下表1：
表1
Figure PCTCN2015076236-appb-000001
实验结果分析
随电解时间的增加，水中氧化因子量均呈正比例增长。
二、实验2
无隔膜/离子膜/透水性隔膜的对比
将本实施例的透水性隔膜4与拿掉透水性隔膜或更换为离子膜的三种情况分别进行水电解，对比实验条件是：
1)拿掉阴电极2与阳电极3之间的透水性隔膜4，使阴电极2与阳电极3之间形成无隔离膜状态，阴电极2与阳电极3之间的间距为2.0毫米(用绝缘垫圈定位，保持间距不变)；
2)离子膜采用中性离子膜，离子膜与阴阳极间距分别是1毫米；
3)透水性隔膜4采用PVDF超滤膜；
4)实验源水为市售RO纯水机的出水，TDS＝200mg/L，pH＝7.6，向容器注入水约5升。
保持三种情况下电解电流均为300毫安，电解15分钟，实验2结果示于表2。
表2
Figure PCTCN2015076236-appb-000002
三、实验3
测验阴电极与透水性隔膜之间间距范围变化对装置工作特性的影响
将本实施例的阴电极2与透水性隔膜4之间的间距δ2分别调整为：δ2＝10、7、4、1、0毫米五种情况。其他实验条件与上述实验2相同，实验3结果示于表3。
表3
Figure PCTCN2015076236-appb-000003
实施例二
本实施例的果蔬清洗机与实施例一基本相同，与实施例一不同的变化是：1)电解单元20包括两对阴电极2和阳电极3；2)透水性隔膜4与阴、阳电极的间距都是1mm；3)透水性隔膜4两端分别超出阴、阳电极一小段；4)每对阴电极2和阳电极3在水质调节单元20内相互平行且水平放置，两对阴电极2和阳电极3设于隔板上下两侧(图中未示出)。
实施例三
本实施例的果蔬清洗机与实施例一基本相同，与实施例一不同的变化是：1)阳电极3是采用石墨、活性炭等碳质材料制成的惰性电极；2)透水性隔膜4是采用石墨、活性炭等碳质材料制成的单层透水性隔膜；3)透水性隔膜4与阳电极3的间距δ1是8mm；4)透水性隔膜4与阴电极2的间距δ2是0.05mm。
实施例四
本实施例的果蔬清洗机与实施例二基本相同，与实施例二不同的变化是：1)在阴电极2上开有第一通孔21，通孔孔径取1mm；2)透水性隔膜4与阴电极2、阳电极3同长；3)透水性隔膜4紧贴阳电极3但与阴电极2分离，透水性隔膜4与阴电极2的间距δ2是2mm。
实施例五
本实施例的果蔬清洗机与实施例四基本相同，与实施例四的变化是：1)透水性隔膜4开有直径φ2.1mm的第二通孔41(见图4)，第二通孔41与第一通孔21数量相同且基本同心对齐；2)透水性隔膜4与阴电极2的间距δ2是3mm。
实施例六
本实施例的果蔬清洗机，是实施例三基础上的变化，与实施例三不同的是：1)阴电极2和阳电极3均为圆片平面电极，尺寸均为直径48毫米，厚度1毫米；2)阴电极2均布开有梳状第一通孔21；3)透水性隔膜4有以下三种选择和设置：
①单层PVDF超滤膜，平均透水孔径0.03微米，厚度为0.5mm，不开孔，紧贴阴阳电极。
②两层膜叠加组合：第一层采用PVDF超滤膜，平均透水孔径0.03微米，厚度为0.5mm，不开孔，紧贴阳电极；第二层采用平均透水孔径0.05微米PVDF超滤膜片，厚度0.5mm，剪切成与阴电极2相同尺寸并开有梳状第二通孔41的圆片膜，紧贴阴电极；梳状第二通孔41与梳状第一通孔21位置方向相垂直。
③三层膜叠加组合：第一层采用活性炭纤维布，比表面积1200m2/g，浸水紧压后厚度约1.8毫米紧贴阳电极；第二层(中间层)采用PVDF超滤膜，平均透水孔径0.03微米，厚度为0.5mm，不开孔；第三层采用平均透水孔径0.05微米PVDF超滤膜片，厚度0.5mm，剪切成与阴电极2相同尺寸并开有梳状第二通孔41的圆片膜，紧贴阴电极；梳状第二通孔41与梳状第一通孔21位置方向相垂直。
关于透水性隔膜单层或多层组合对本实施例装置工作特性的影响的实验
本实施例的果蔬清洗机分别选择不同透水性隔膜4进行水电解实验如下：
1、实验条件
1.1盛水容器1的容积为500×500×1500毫米
1.2电解单元20，采用直流稳压电源；
1.3其他实验条件和检测方法与实施例一相同。
源水为市供自来水，TDS＝160mg/L，pH＝7.5，向容器注入水约5升。分别以上述单层隔离膜及组合隔离膜，各电解15分钟，电解过程中电解电流均保持为300毫安，实验结果示于表4。
表4
Figure PCTCN2015076236-appb-000004
本发明的果蔬清洗机不局限于上述实施例所述的具体技术方案，比如：1)透水性隔膜4可以是由活性炭纤维膜(毡)和超滤膜叠加复合而成的二层透水性隔膜，活性炭纤维膜靠近阳电极3(朝向阳电极3)并且包覆阳电极3的全部表面，朝向阴电极2(背离阳电极3)的超滤膜包覆阳电极3的部分表面(阳电极朝向阴电极2一侧的全部表面)或包覆阳电极3的全部表面，并且超滤膜的两端略微超出阳电极；2)阳电极3与阴电极2均采用钛基覆涂铂族氧化物(涂层厚度为0.8毫米)制成的惰性电极，均呈圆形片状；3)阴电极2上开有的第一通孔21的孔径可以是1.5、2mm等；4)透水性隔膜4开有第二通孔41的孔径可以是2.5、3mm等；5)阴电极2和阳电极3的间距大于等于透水性隔膜4的厚度且小于等于20毫米；6)电解单元20是两个、四个或更多个；7)本发明的上述各个实施例的技术方案彼此可以交叉组合形成新的技术方案，等等。凡采用等同替换形成的技术方案均为本发明要求的保护范围。

Claims (10)

  1. 一种果蔬清洗机，包括盛水容器和电解电源，其特征在于：所述盛水容器内设置有至少一个电解单元，所述电解单元包括至少一对阴电极和阳电极，所述电解电源用于对所述阴电极和阳电极供电；成对的阴电极和阳电极之间设有透水性隔膜，所述透水性隔膜的透水孔径小于等于2毫米且大于等于1纳米。
  2. 根据权利要求1所述果蔬清洗机，其特征在于：所述阴电极和阳电极的间距大于等于所述透水性隔膜的厚度且小于等于20毫米。
  3. 根据权利要求1或2所述果蔬清洗机，其特征在于：所述透水性隔膜是非导电性的透水性隔膜。
  4. 根据权利要求3所述果蔬清洗机，其特征在于：所述阴电极上开有第一通孔，所述第一通孔的孔径大于等于1毫米。
  5. 根据权利要求3所述果蔬清洗机，其特征在于：所述透水性隔膜开有第二通孔，所述第二通孔的孔径大于2毫米。
  6. 根据权利要求3所述果蔬清洗机，其特征在于：所述透水性隔膜是单层透水性隔膜。
  7. 根据权利要求6所述果蔬清洗机，其特征在于：所述单层透水性隔膜是超滤膜或采用碳质材料制成的单层透水性隔膜。
  8. 根据权利要求3所述果蔬清洗机，其特征在于：所述透水性隔膜是多层透水性隔膜。
  9. 根据权利要求3所述果蔬清洗机，其特征在于：所述电解电源是高电平窄脉宽的直流或交变脉冲电源。
  10. 根据权利要求1或2所述果蔬清洗机，其特征在于：所述盛水容器内设有波轮，所述电解单元沿盛水容器内的波轮周圈均匀布置。
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