Bulk-phase nanobubble preparation device

Abstract

The utility model relates to a bulk phase nanobubble preparation device, which is characterized in that electrolyte is aqueous solution contained in an electrolytic bath, and an anode electrolysis chamber and a cathode electrolysis chamber are independently arranged side by side and are communicated through a proton exchange membrane through which protons penetrate but which does not penetrate through gas molecules; the electrode is connected with the electrochemical workstation and inserted into the electrolyte to electrolyze the electrolyte to form bulk-phase nanobubbles, the ultrasonic device comprises an ultrasonic pool, and the electrolytic bath is contained in the ultrasonic pool and provides an ultrasonic field for the electrolyte through the ultrasonic pool so that the bulk-phase nanobubbles can be stripped from the electrode. The bulk phase nanobubbles include oxygen nanobubbles generated in the anode electrolysis chamber and hydrogen nanobubbles generated in the cathode electrolysis chamber. According to the bulk phase nanobubble preparation device disclosed by the utility model, oxygen nanobubbles and hydrogen nanobubbles can be stably and controllably generated in the anode electrolysis chamber and the cathode electrolysis chamber respectively at the same time, and the oxygen nanobubbles and the hydrogen nanobubbles with different concentrations can be prepared by regulating and controlling electrochemical parameters through the electrochemical workstation.

Description

Technical Field

[0001] The utility model relates to nano - bubbles, and more specifically to a bulk - phase nano - bubble preparation device. Background Art

[0002] Nano - bubbles are an emerging field developed in recent years. Due to their unique physical and chemical properties, they have attracted the attention of many theoretical scientists. At the same time, nano - bubbles have great application prospects in the application field. In order to conduct more in - depth research on nano - bubbles, a stable and controllable method for preparing bulk - phase nano - bubbles needs to be developed. For the preparation of bulk - phase nano - bubbles, it has always been a fundamental and important process. Nowadays, for the preparation of bulk - phase nano - bubbles, generally, there are the following methods: pressure change method, oscillation method, electromagnetic wave irradiation method, etc. Although the above - mentioned methods for preparing nano - bubbles have good single - ness and stability and are suitable for laboratory research. However, for the research of nano - bubbles, more importantly, it is possible to stably, efficiently and controllably prepare nano - bubbles. For this requirement, the above methods are somewhat insufficient. Summary of the Utility Model

[0003] In order to solve the problems in the prior art that the production of conventional nano - bubbles is not stable enough and cannot be controlled, etc., the utility model provides a bulk - phase nano - bubble preparation device.

[0004] According to the bulk - phase nano - bubble preparation device of the utility model, it includes an electrolysis device and an ultrasonic device. Among them, the electrolysis device includes an electrolyte solution, an electrolytic cell, electrodes and an electrochemical workstation. The electrolyte solution is an aqueous solution contained in the electrolytic cell. The electrolytic cell includes an anodic electrolysis chamber, a cathodic electrolysis chamber and a proton exchange membrane. The anodic electrolysis chamber and the cathodic electrolysis chamber are independently arranged side by side and are connected through a proton exchange membrane that allows protons to pass through but does not allow gas molecules to pass through. The electrodes are connected to the electrochemical workstation and inserted into the electrolyte solution to electrolyze and form bulk - phase nano - bubbles. The ultrasonic device includes an ultrasonic cell. The electrolytic cell is accommodated in the ultrasonic cell and the ultrasonic cell provides an ultrasonic field for the electrolyte solution to facilitate the stripping of bulk - phase nano - bubbles from the electrodes. The bulk - phase nano - bubbles include oxygen nano - bubbles generated in the anodic electrolysis chamber and hydrogen nano - bubbles generated in the cathodic electrolysis chamber.

[0005] In a preferred embodiment, the electrodes are composed of an anode electrode and a cathode electrode. Among them, the anode electrode is inserted into the electrolyte solution in the anodic electrolysis chamber and connected to the positive electrode of the electrochemical workstation, and the cathode electrode is inserted into the electrolyte solution in the cathodic electrolysis chamber and connected to the negative electrode of the electrochemical workstation.

[0006] In a preferred embodiment, the anode electrode and the cathode electrode are respectively grating electrodes including multiple titanium plates.

[0007] In a preferred embodiment, a porous structure is formed on the surface of each titanium plate.

[0008] In a preferred embodiment, a platinum coating is formed on the surface of each titanium plate.

[0009] In a preferred embodiment, a plurality of through holes are respectively provided on the wall plate of the anode electrolysis chamber adjacent to the cathode electrolysis chamber and the wall plate of the cathode electrolysis chamber adjacent to the anode electrolysis chamber. The proton exchange membrane is sandwiched between the anode electrolysis chamber and the cathode electrolysis chamber to communicate the anode electrolysis chamber and the cathode electrolysis chamber through the through holes.

[0010] In a preferred embodiment, the proton exchange membrane is a nafion117 proton exchange membrane.

[0011] According to the bulk-phase nanobubble preparation device of the present invention, oxygen nanobubbles and hydrogen nanobubbles can be stably and controllably generated in the anode electrolysis chamber and the cathode electrolysis chamber respectively and simultaneously, impurities and pollution are not easily generated, the process is easy to control, and high-concentration nanobubbles can be generated on a large scale at low cost. Electrochemical parameters are regulated by an electrochemical workstation to prepare oxygen nanobubbles and hydrogen nanobubbles with different concentrations. Description of the Drawings

[0012] Figure 1 is a schematic structural diagram of a bulk-phase nanobubble preparation device according to a preferred embodiment of the present invention.

[0013] Figure 2 is a concentration comparison diagram of nanobubbles in the untreated KOH electrolyte solution, the anode electrolysis chamber solution after electrolysis and ultrasonic treatment for 30 min, the cathode electrolysis chamber solution after electrolysis and ultrasonic treatment for 30 min, the degassed anode electrolysis chamber solution after electrolysis and ultrasonic treatment for 30 min, and the degassed cathode electrolysis chamber solution after electrolysis and ultrasonic treatment for 30 min in Example 1.

[0014] Figure 3 is a particle size distribution comparison diagram of nanobubbles in the untreated KOH electrolyte solution, the anode electrolysis chamber solution after electrolysis and ultrasonic treatment for 30 min, and the cathode electrolysis chamber solution after electrolysis and ultrasonic treatment for 30 min in Example 1.

[0015] Figure 4 is the concentration of nanobubbles in the anode electrolysis chamber and the cathode electrolysis chamber at different electrolysis times. Detailed Embodiments

[0016] The following is combined with the drawings to give the preferred embodiments of the present invention and describe them in detail.

[0017] As Figure 1As shown, the bulk nanobubble preparation device according to a preferred embodiment of the present invention includes an electrolysis device 1 and an ultrasonic device 2. Among them, the electrolysis device 1 includes an electrolyte solution 11, an electrolytic cell 12, an electrode 13, and an electrochemical workstation 14. The electrolyte solution 11 is an aqueous solution contained in the electrolytic cell 12. The electrode 13 is connected to the electrochemical workstation 14 and inserted into the electrolyte solution 11 to electrolyze and form bulk nanobubbles. The ultrasonic device 2 includes an ultrasonic cell 21. The electrolytic cell 12 is accommodated in the ultrasonic cell 21, and the ultrasonic cell 21 provides an ultrasonic field for the electrolyte solution 11 to facilitate the stripping of the bulk nanobubbles from the electrode 13. The bulk nanobubbles are oxygen nanobubbles and hydrogen nanobubbles. Thus, the bulk nanobubble preparation device of the present invention can simultaneously and respectively stably, efficiently, and controllably generate oxygen nanobubbles and hydrogen nanobubbles. And, by controlling the electrolysis voltage (1V - 10V) and the electrolysis reaction time (5min - 60min), oxygen nanobubbles and hydrogen nanobubbles with different concentrations and / or different particle sizes are respectively generated.

[0018] Among them, the total concentration of the bulk nanobubbles in the electrolyte solution 11 > 10 7 per milliliter. It should be understood that the concentration of the bulk nanobubbles in the electrolyte solution 11 can be controlled by adjusting the electrolysis time of the electrolysis device 1. In this embodiment, the electrolyte solution is an aqueous KOH solution. It should be understood that the aqueous KOH solution is only an example rather than a limitation, and other aqueous solutions, such as an aqueous H2SO4 solution, are also feasible.

[0019] Among them, the electrolytic cell 12 includes an anodic electrolysis chamber 121, a cathodic electrolysis chamber 122, and a proton exchange membrane 123. Among them, the anodic electrolysis chamber 121 and the cathodic electrolysis chamber 122 are independently arranged side by side. A number of through holes are respectively provided on the wall plate of the anodic electrolysis chamber 121 adjacent to the cathodic electrolysis chamber 122 and on the wall plate of the cathodic electrolysis chamber 122 adjacent to the anodic electrolysis chamber 121. The proton exchange membrane 123 is sandwiched between the anodic electrolysis chamber 121 and the cathodic electrolysis chamber 122 to facilitate the passage of protons but not gas molecules. In this embodiment, the OH - / H2O in the electrolyte solution 11 in the anodic electrolysis chamber 121 will undergo an oxidation reaction and lose electrons, thereby generating oxygen nanobubbles. The H2O / H +A reduction reaction will occur, electrons will be obtained, and finally hydrogen nanobubbles will be obtained. In this way, the anode electrolysis chamber 121 and the cathode electrolysis chamber 122 are closely installed and firmly fixed, and are separated by a proton exchange membrane 123 in the middle, so that oxygen nanobubbles can be prepared in the anode electrolysis chamber 121 while hydrogen nanobubbles can be prepared in the cathode electrolysis chamber 122. In this embodiment, the internal dimensions of the electrolysis chambers 121 and 122 are 60mm * 60mm * 60mm, and the dimensions of the through holes thereon are 20mm * 20mm respectively. In this embodiment, the proton exchange membrane 123 is a nafion117 proton exchange membrane.

[0020] Among them, the electrode 13 is composed of an anode electrode 131 and a cathode electrode 132. Among them, the anode electrode 131 is inserted into the electrolyte 11 of the anode electrolysis chamber 121 and connected to the positive pole of the DC power supply of the electrochemical workstation 14, and the cathode electrode 132 is inserted into the electrolyte 11 of the cathode electrolysis chamber 122 and connected to the negative pole of the DC power supply of the electrochemical workstation 14. The anode electrode 131 and the cathode electrode 132 are respectively grating electrodes, including multiple titanium plates 13a, and a porous structure is formed on the surface of each titanium plate 13a to increase the contact area between the electrode 13 and the electrolyte 11, thereby improving the electrolysis efficiency. In this embodiment, a platinum coating is formed on the surface of each titanium plate 13a to save costs. The purpose of using a platinum-coated electrode is that metallic platinum has higher electrode potential stability in electrochemical reactions and is not prone to reaction during electrolysis.

[0021] Preparation of Instruments and Equipment

[0022] The ultrapure water used in the experiment all comes from ELGA LabWater (ELGA Classic - PURELAB).

[0023] Before use, the electrolytic cell 12 and the electrode 13 are both cleaned with deionized water and ethanol, and then dried in a vacuum drying oven before use.

[0024] Equipment such as beakers and syringes involved in the experiment are all ultrasonically cleaned with deionized water in advance and dried in a vacuum drying oven before use.

[0025] The dynamic light scattering device uses a Nanosight NS300 system, equipped with a sample cell and a cover plate. The sample cell and the cover plate are cleaned with deionized water and ethanol before use. Environmental conditions: The temperature is controlled at room temperature, and the pressure is one standard atmosphere.

[0026] Experiment Preparation

[0027] A KOH electrolyte solution with a concentration of 100 mmol / L is prepared using potassium hydroxide (KOH, analytical pure, ≥99%).

[0028] Assemble the electrolysis device 1 and add 215 ml of 100 mmol / L KOH electrolyte solution to the anodic electrolysis chamber 121 and the cathodic electrolysis chamber 122 respectively.

[0029] Place the entire electrolytic cell 12 of the electrolysis device 1 into the ultrasonic device 2, and the ultrasonic parameters are (100 W 40 kHz).

[0030] Put the anode electrode 131 into the anodic electrolysis chamber 121, put the cathode electrode 132 into the cathodic electrolysis chamber 122, and connect the electrode 13 to the electrochemical workstation 14.

[0031] Set the constant electrolysis voltage during electrolysis to 10 V, turn on the ultrasonic device 2 and the electrochemical workstation 14, and start the electrochemical ultrasound (EC-U) experiment.

[0032] Formation of Nanobubbles

[0033] The electrolysis of the aqueous solution by the DC power supply decomposes it into oxygen and hydrogen, and a large number of O2 and H2 molecules will be formed on the surfaces of the anode electrode 131 and the cathode electrode 132 respectively. The gas molecules on the electrode surface are stripped off under the action of the ultrasonic field, so that an oxygen nanobubble aqueous solution and a hydrogen nanobubble aqueous solution are produced in the anodic electrolysis chamber 121 and the cathodic electrolysis chamber 122 respectively.

[0034] After the experiment, use a clean syringe to suck the solutions in the anodic electrolysis chamber 122 and the cathodic electrolysis chamber 122, inject them into the sample cell, observe with dynamic light scattering, and save the images and data.

[0035] Observation of the Number and Size of Nanobubbles

[0036] Use a dynamic light scattering (DLS) system equipped with a nanoparticle tracking analysis system (NTA) to observe the nanobubbles. The specific operation is as follows: Turn on the main program NTA program. Click capture to enter the video capture interface. Optionally, try to set the camera level to a higher position first. Place the sample cell on the microscope stage, and the blue laser should be in the emitting state (if not, click the camera level in the NTA software Capture interface to a higher position to excite the laser); adjust the position of the sample cell back and forth, left and right, and adjust the focal length up and down until the blue laser beam can be observed, and finely adjust the focal length and position using the observed image of the NTA software. Subsequently, the nanobubbles can be measured and observed.

[0037] Verification of Nanobubbles

[0038] To verify that the nanoparticles measured in the experiment are nanobubbles, we conducted three groups of control experiments, and the experimental results are asFigure 2 shown.

[0039] In the first experimental group, 100 mmol / L KOH electrolyte solution was electrolyzed at a constant voltage of 10 V for 30 min. Finally, the oxygen nanobubble aqueous solution and the hydrogen nanobubble aqueous solution in the anodic electrolysis chamber and the cathodic electrolysis chamber were taken for NTA measurement, respectively.

[0040] In a second control experiment, the oxygen nanobubble and hydrogen nanobubble solutions prepared above were completely frozen at -20°C (approximately 2 hours). They were then degassed in a vacuum drying oven to below 0.1 atmosphere for 6 hours. The degassed solutions were then measured using the NTA system.

[0041] The third group of control experiments: The NTA system was used to directly measure the 100mmol / L KOH electrolyte solution that had not been electrolyzed.

[0042] The nanoparticle contents measured in the second and third control experiments were significantly lower than the nanoparticle contents measured in the first experimental group, proving that nanobubbles were prepared in the present invention.

[0043] Example 1: Preparation of Nanobubbles with an Electrolysis Time of 30 min

[0044] A 100mmol / L KOH electrolyte solution was added to the anode and cathode chambers, and the entire electrolysis device was placed in an ultrasonic environment. The constant voltage of the DC power supply was adjusted to 10V, the electrochemical workstation and ultrasound were turned on, and electrolysis began. The electrolysis lasted for 30 minutes. During the experiment, a large number of small bubbles were observed on the electrode surfaces in the anode and cathode chambers. After the reaction was completed, a small amount of solution was drawn from the anode and cathode chambers with a glass syringe, added to the liquid tank, and observed using dynamic light scattering, and the corresponding images were saved. The specific parameters of the Nanosight NS300 were Screen Gain 11 and Camera Level 9 during observation, Screen Gain 16 and Detection Threshold 2 when processing the image, and try not to choose a position close to the edge during observation. After taking the average value after multiple measurements, it was found that the number of oxygen nanobubbles in the anode chamber was approximately (5.0±0.12)×10 7 The number of hydrogen nanobubbles in the cathode chamber is about (1.8±0.16)×10 8 About pcs / ml.

[0045] Separate the aqueous solutions in the anodic electrolysis chamber and the cathodic electrolysis chamber and place them in two beakers. Then seal the beakers with tape and make several small openings at the sealed parts to keep the air pressure inside the beakers the same as that outside and keep the solution surface clean. Then place the two beakers in a -20 °C environment until they are completely frozen (about 2 hours); then place them in a vacuum drying oven, start the vacuum pump, evacuate for 6 hours at 0.1 atmospheric pressure, and then take them out. Observe the solutions in the beakers with a dynamic light scattering system. The specific parameters of the Nanosight NS300 are Screen Gain 11 and Camera Level 9 during observation, Screen Gain 16 and Detection Threshold 2 when processing the images, and try not to select positions close to the edge during observation. After multiple measurements and taking the average value, the number of degassed oxygen nanobubbles in the anodic chamber is observed to be (1.4 ± 0.23) × 10 7 per ml; the number of degassed hydrogen nanobubbles in the cathodic chamber is observed to be (1.9 ± 0.4) × 10 7 per ml.

[0046] Directly use a glass syringe to suck the un-electrolyzed 100 mmol / L KOH electrolyte solution and add it to the liquid cell, and observe it with dynamic light scattering. The specific parameters of the Nanosight NS300 are Screen Gain 11 and Camera Level 9 during observation, Screen Gain 16 and Detection Threshold 2 when processing the images, and try not to select positions close to the edge during observation. After multiple measurements and taking the average value, the number of nanobubbles in the original electrolyte solution is observed to be approximately (1.0 ± 0.38) × 10 7 per ml.

[0047] As Figure 2 shown, through comparison, it is found that the nanoparticle concentrations in the two control experiments are both in the range of 1 × 10 7 per ml to 2 × 10 7 per ml, which are significantly lower than the experimental values of (5.0 ± 0.12) × 10 7 per ml in the anodic electrolysis chamber and (1.8 ± 0.16) × 10 8 per ml in the cathodic electrolysis chamber. Thus, it can be proved that what is generated in the experiment is indeed nanobubbles rather than nano-scale pollutants.

[0048] Figure 3It is a comparison of the particle size distributions of hydrogen nanobubbles and oxygen nanobubbles obtained by experimental electrolysis with those of nanobubbles in an unelectrolyzed 100 mmol / L KOH electrolyte solution. Through comparison, it is found that the particle size distribution of nanobubbles in the unelectrolyzed 100 mmol / L KOH electrolyte solution is mainly between 80 - 150 nm, while the particle size distribution of oxygen nanobubbles obtained after 30 minutes of electrolysis is mainly between 40 - 120 nm, and the particle size distribution of hydrogen nanobubbles obtained after 30 minutes of electrolysis is mainly between 80 - 300 nm.

[0049] Example 2: Preparation of Nanobubbles with an Electrolysis Time of 5 min

[0050] Change the electrolysis time to 5 minutes, and repeat the experiment in Example 1. The experiment measures that at this time, the number of oxygen nanobubbles in the anode chamber is approximately (2.4 ± 0.15) × 10 7 per ml or so, and the number of hydrogen nanobubbles in the cathode chamber is approximately (4.8 ± 0.19) × 10 7 per ml or so.

[0051] Example 3: Preparation of Nanobubbles with an Electrolysis Time of 15 min

[0052] Change the electrolysis time to 5 minutes, and repeat the experiment in Example 1. The experiment measures that at this time, the number of oxygen nanobubbles in the anode chamber is approximately (4.0 ± 0.21) × 10 7 per ml or so, and the number of hydrogen nanobubbles in the cathode chamber is approximately (9.4 ± 0.60) × 10 7 per ml or so.

[0053] Example 4: Preparation of Nanobubbles with an Electrolysis Time of 25 min

[0054] Change the electrolysis time to 25 minutes, and repeat the experiment in Example 1. The experiment measures that at this time, the number of oxygen nanobubbles in the anode chamber is approximately (4.4 ± 0.17) × 10 7 per ml or so, and the number of hydrogen nanobubbles in the cathode chamber is approximately (1.5 ± 0.12) × 10 8 per ml or so.

[0055] Example 5: Preparation of Nanobubbles with an Electrolysis Time of 35 min

[0056] Change the electrolysis time to 35 minutes, and repeat the experiment in Example 1. The experiment measures that at this time, the number of oxygen nanobubbles in the anode chamber is approximately (4.9 ± 0.19) × 10 7 per ml or so, and the number of hydrogen nanobubbles in the cathode chamber is approximately (1.8 ± 0.16) × 10 8 per ml or so.

[0057] Example 6: Preparation of Nanobubbles with an Electrolysis Time of 45 min

[0058] Change the electrolysis time to 25 min, and repeat the experiment in Example 1. It is measured that at this time, the number of oxygen nanobubbles in the anode chamber is approximately (4.8 ± 0.18) × 10 7 per ml, and the number of hydrogen nanobubbles in the cathode chamber is approximately (1.8 ± 0.09) × 10 8 per ml.

[0059] Example 7: Preparation of Nanobubbles with an Electrolysis Time of 60 min

[0060] Change the electrolysis time to 25 min, and repeat the experiment in Example 1. It is measured that at this time, the number of oxygen nanobubbles in the anode chamber is approximately (4.8 ± 0.21) × 10 7 per ml, and the number of hydrogen nanobubbles in the cathode chamber is approximately (1.8 ± 0.11) × 10 8 per ml.

[0061] Figure 4 The concentrations of oxygen nanobubbles and hydrogen nanobubbles generated by electrolysis at different electrolysis times are given. It can be seen that oxygen nanobubbles and hydrogen nanobubbles can be generated during the electrolysis time of 5 min - 60 min. The highest concentration of oxygen nanobubbles is approximately (4.9 ± 0.12) × 10 7 per ml, and the highest concentration of hydrogen nanobubbles is approximately (1.84 ± 0.16) × 10 8 per ml.

[0062] The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Various changes can be made to the above embodiments of the present invention. That is, all simple, equivalent changes and modifications made according to the claims and the content of the specification of the present invention application fall within the scope of the claims of the present invention patent. The content not described in detail in the present invention is all conventional technical content.

Claims

1. A bulk-phase nanobubble preparation device, characterized in that, The bulk nanobubble preparation device includes an electrolysis device and an ultrasonic device. Among them, the electrolysis device includes an electrolyte solution, an electrolytic cell, electrodes, and an electrochemical workstation. The electrolyte solution is an aqueous solution contained in the electrolytic cell. The electrolytic cell includes an anodic electrolysis chamber, a cathodic electrolysis chamber, and a proton exchange membrane. The anodic electrolysis chamber and the cathodic electrolysis chamber are independently arranged side by side and are connected through a proton exchange membrane that allows protons to pass through but does not allow gas molecules to pass through. The electrodes are connected to the electrochemical workstation and inserted into the electrolyte solution to electrolyze and form bulk nanobubbles. The ultrasonic device includes an ultrasonic cell. The electrolytic cell is accommodated in the ultrasonic cell, and the ultrasonic cell provides an ultrasonic field for the electrolyte solution to facilitate the stripping of the bulk nanobubbles from the electrodes. The bulk nanobubbles include oxygen nanobubbles generated in the anodic electrolysis chamber and hydrogen nanobubbles generated in the cathodic electrolysis chamber.

2. The bulk nanobubble preparation device according to claim 1, characterized in that, The electrodes are composed of an anode electrode and a cathode electrode. Among them, the anode electrode is inserted into the electrolyte solution in the anodic electrolysis chamber and connected to the positive electrode of the electrochemical workstation, and the cathode electrode is inserted into the electrolyte solution in the cathodic electrolysis chamber and connected to the negative electrode of the electrochemical workstation.

3. The bulk nanobubble preparation device according to claim 2, characterized in that, The anode electrode and the cathode electrode are respectively grating electrodes including multiple titanium plates.

4. The bulk nanobubble preparation device according to claim 3, wherein, A porous structure is formed on the surface of each titanium plate.

5. The bulk nanobubble preparation device according to claim 3, wherein A platinum coating is formed on the surface of each titanium plate.

6. The bulk nanobubble preparation device according to claim 1, characterized in that, A number of through holes are respectively provided on the wall plate of the anodic electrolysis chamber adjacent to the cathodic electrolysis chamber and on the wall plate of the cathodic electrolysis chamber adjacent to the anodic electrolysis chamber. The proton exchange membrane is sandwiched between the anodic electrolysis chamber and the cathodic electrolysis chamber to connect the anodic electrolysis chamber and the cathodic electrolysis chamber through the through holes.

7. The bulk nanobubble preparation device according to claim 1, characterized in that, The proton exchange membrane is a nafion117 proton exchange membrane.

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