The present disclosure relates to systems, devices, and methods for manufacturing nanobubbles.
Nanobubbles have recently gained increased attention due to their unique physicochemical properties, and many potential applications, such as detergent-free cleaning processes, tertiary oil recovery, foam fractionation, mineral flotation, food processing, intracellular drug delivery, mineral processing, biomedical engineering, medical, and environmental applications (e.g., water aeration). (Hofmann, A., et al., Role of bubble size for the performance of continuous foam fractionation in stripping mode. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2015, 473, 85-94; Oshita, S.; Liu, S. In Nanobubbles characteristics and its application to agriculture and foods, International Symposium on Agri-Foods for Health and Wealth, August, 2013; pp 5-8.) Several properties of nanobubbles include long residence times in the solutions, large specific areas, high gas internal pressure, charged surface, excellent stability against coalesces, collapse or burst, and the formation of bulk bubbles.
Nanobubbles are frequently generated in a solution by creating a cavitation through four common mechanisms: hydrodynamic, acoustic, particle, and optical type. Variations in the pressurized liquid flux, due to system geometry, cause the hydrodynamic cavitation. Conversely, the pressure variations in the acoustic cavitation are produced by passing the ultrasonic waves through a liquid. Optical cavitation is generated by passing high intensity (laser) light photons in the liquid. However, passing other elementary particles in the liquid, e.g., a proton in bubbles chamber, is referred to as particle cavitation. Hydrodynamic and acoustic cavitation may cause changes in the chemical and physical properties of the liquid; but, particle and optic cavitation do not cause any of these changes. Hydrodynamic cavitation is safer and more energy efficient than acoustic cavitation. Therefore, hydrodynamic cavitation is the most common usable type to generate micro nanobubbles.
Some distinctive designs of microbubbles generators include: swirl flow type, aura jet, cavitation nozzle, venturi type, original hydrodynamic reaction mixer, and depressurization-recirculation method. (Ushikubo, F. Y., et al., Evidence of the existence and the stability of nano-bubbles in water. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2010, 361, 31-37; Serizawa, A., et al., In Laminarization of micro-bubble containing milky bubbly flow in a pipe, The 3rd European-Japanese Two-phase Flow Group Meeting, Certosa di Pontignano, 2003; Yano, H.; Sakai, A., System and method for generating nanobubbles, U.S. Patent Application Publication No. 2014/0191425) For example, a high-speed swirl flow first dissolves the gas into the liquid by compressing air flow in the liquid, then releases the mixed compressed flow through a nozzle to create nanobubbles by cavitation. Alternatively, the pressure variations in the acoustic cavitation are produced by passing the ultrasonic waves into a liquid. In the depressurization-recirculation method, the gas dissolution in the liquid is increased at high pressure between 0.25-0.27 MPa that causes supersaturation, and then the mixed gas water solution is decompressed to atmosphere pressure causing the nucleation of micro nanobubbles, which are released through a nozzle. The micro nanobubbles are recirculated to break down the gas through the water vortex.
Some innovative methods have been used to generate nanobubbles, including: (1) ultra-sonication was used on a palladium electrode to produce nanobubbles with a mean diameter of 300-500 nm; (2) Oeffinger and Wheatley proved that ultra-sonication of a surfactant mixture with regular purging of octa-fluoropropane gas could produce nanobubbles with a mean diameter of 400-700 nm (Oeffinger, B. E.; Wheatley, M. A., Development and characterization of a nano-scale contrast agent. Ultrasonics 2004, 42, 343-347); (3) nanobubbles was generated through two steps. First, the air was injected into the solution inside a steel vessel for 25 minutes to reach a supersaturation status at an internal gauge pressure of 455 kPa. Second, the air-saturated solution was depressurized through the needle valve with 2 mm internal diameter at a speed flow of 0.1 L min−1. The generated nanobubbles diameters were between 200 nm to 720 nm (Calgaroto, S., et al., On the nanobubbles interfacial properties and future applications in flotation. Minerals Engineering 2014, 60, 33-40); and (4) Sang-Ryul Ryu injected a gas inside a bamboo filter to generate nanobubbles. (Sang-Ryul, R., Method and apparatus for generating nano-bubbles in liquid, U.S. Pat. No. 8,794,604)
Recently, the use of ceramic membranes as bubbling diffusers to generate ultra-small bubbles has gained attention. It has been widely investigated in several applications, including advanced oxidation processes in water and wastewater treatment, landfill leachate treatment, and activated sludge treatment. The use of micro-pores ceramic diffuser was also investigated at different flow rates 1, 2, and 3 L·m−1. The generated bubbles were in millimeters scale with the smallest bubble size of 0.51 mm. The narrow bubbles distribution was at a low flow rate. The greatest frequency of the smallest bubble size occurred at the lowest flowrate. (Siswanto, A., et al., In Investigation of Bubble Size Distributions in Oscillatory Flow at Various Flow Rates, The University of Sheffield Engineering Symposium Conference Proceedings Vol. 1, Sheffield: 2014)
The manufacture of nanobubbles using a ceramic membrane presents a challenge which must be addressed.
Systems, devices, and methods for manufacturing nanobubbles are provided herein.
One aspect of the present disclosure relates to a system for manufacturing nanobubbles. In one embodiment, the system includes a medium, wherein in the medium is a liquid medium or a semi-liquid medium. A device is immersed in the medium. The device includes a ceramic membrane having a first surface and an opposing second surface, and pores extending through the membrane from the first surface to the second surface, and a hydrophobic porous coating layer disposed on the first surface of the membrane. The system includes a gas source for providing a gas to the medium. The gas enters pores on the second surface of the membrane and exits the device in the form of nanobubbles.
Another aspect of the present disclosure relates to a device for manufacturing nanobubbles. In one embodiment, the device includes a ceramic membrane having a first surface and an opposing second surface, and pores extending therethrough between the first surface and the second surface. The second surface of the ceramic membrane defines a plenum having a first opening and an opposing second opening. The plenum is fluidly coupled to the pores at the second surface of the membrane. A hydrophobic porous coating layer is disposed on the first surface of the membrane.
Yet another aspect of the present disclosure relates to a method of manufacturing nanobubbles. In one embodiment, the method includes flowing a gas into a medium containing a device immersed therein. The device includes a ceramic membrane having a first surface and an opposing second surface, and pores extending therethrough between the first surface and the second surface. The second surface of the ceramic membrane defines a plenum having a first opening and an opposing second opening. The plenum is fluidly coupled to the pores at the second surface of the membrane. A hydrophobic porous coating layer is disposed on the first surface of the membrane. The method includes generating nanobubbles of the gas by flowing the gas through the first and second openings into the plenum, and subsequently through the pores of the membrane at the second surface, wherein the gas exits the device as nanobubbles.
The following detailed description of systems and methods for producing nanobubbles designs refers to the accompanying drawings that illustrate exemplary embodiments consistent with these systems and methods. Other embodiments are possible, and modifications may be made to the embodiments within the spirit and scope of the methods and systems presented herein. Therefore, the following detailed description is not meant to limit the devices described herein. Rather, the scope of these devices is defined by the appended claims.
The system 100 can includes subsystems and components to measure and control process variables, such as flowrate and gas pressure, as necessary to achieve effective generation of nanobubbles. For instance, the system 100 can include a gas pressure regulator 108 to control the pressure of the gas supplied from the gas source 102. The system 100 can include a gas flow meter 110 to control the flow rate of the gas entering the medium 104. The system can include one or more sensors or other detection means (not illustrated in
The ceramic membrane 114 can be made of a ceramic material that is inert to the gas and the medium 104. Exemplary ceramic materials can include Al2O3, TiO2, Si3N4, and stainless steel. The ceramic membrane may be impermeable to the gas except through the pores 122. The pores 122 can have a diameter of about 100 nanometers (nm) or less. In an embodiment, the pores 122 can range from about 20 to about 500 nm. A thickness of the membrane can range from about 5 mm to about 1 cm. The diameter of the plenum can range from about 2 cm to about 10 cm. The width of the membrane as defined between the first opening 124 and the second opening 126 ranges from about 5 cm to about 20 cm. Thickness, diameter and width can be adjusted as necessary to produce nanobubbles on a scale of the desired application.
The first surface 118 of the membrane 114 is coated the hydrophobic coating layer 116. The hydrophobic coating layer 116 is used to adjust hydrophobicity of the first surface 118 to control the size of the nanobubbles being produced.
γSV=γSL+γLV cos θ
From the geometry relation shown in
2R·sin θ=D or R=D/(2·sin θ)
If the pore size (D) increases, the size of the bubble generated increases. If the surface becomes more hydrophobic (i.e., θ increases), then the size of the bubble decreases. The maximum bubble size that can be generated is equal to the pore size, when θ is close to 90° and sin θ=1. According to this analysis, adjusting the hydrophobicity of the surface by using the hydrophobic porous coating layer 116 can be used to achieve different sizes of nanobubbles. The hydrophobicity of the coating layer, as indicated by the value of θ, may range from 60-150°. The nanobubble size is observed to decrease by about 50% or more, under the same injected gas pressure, in the presence of the hydrophobic coating layer. Shrinking membrane pore size alone does not appear to reduce nanobubble sizes.
One method to form the hydrophobic porous coating layer 116 is described herein. The membrane 114 can be cleaned to remove contaminants from the surfaces thereof. One exemplary cleaning process is sonication of the membrane in water or another medium that is inert to the membrane 114. Sonication may be performed for about 15 minutes, or a length of time sufficient to clean the surfaces of the membrane 114. After sonication, rigorous water cleanings of the surfaces can further be used if necessary. The plenum 122 is then isolated from exposure to the formation process, for example, by capping the first and second openings 124, 126 to prevent solution from entering the plenum 122. In one embodiment, rubber caps can be inserted into the openings 124, 126 to isolate the plenum 122. The membrane 114 is placed into a solution that includes the hydrophobic molecule. The solution can include a solvent, such as methanol or ethanol. The membrane 114 may be immersed in the solvent for about 24 hours, or an appropriate time to ensure coating with the hydrophobic molecule. The solution can be stirred while the membrane 114 is immersed to facilitate good dispersion of the hydrophobic molecule in the solution and chemisorption of the molecule to the first surface 118 of the membrane 114. Upon removal from the solution, the membrane can be rinsed up to several times with water and/or ethanol to remove excess molecules that didn't attach to the first surface 118. The membrane 114 can be dried at a suitable temperature, for example about 60° C. for about 24 hours.
One exemplary method to produce nanobubbles is described herein with reference to the system 100. The gas is injected into the medium 104 through the conduit 103 at a gas pressure sufficient to produce nanobubbles of a desired size. Exemplary gases may include, but are not limited to, high-purity air, oxygen, hydrogen, carbon dioxide, nitrogen and helium. In some embodiments, the gas is injected at a pressure ranging from 200-500 kPa. In one embodiment, the pressure is about 60 pounds per square inch (psi) or about 414 kilopascal (kPa). The pressure regulator can be monitored and adjusted to maintain the desired gas pressure. The flow rate of the gas in the conduit 103 can be controlled by adjusting the flow meter 110, which does not affect the nanobubble size in water. In one embodiment, the flow rate is about 0.024 L·min−1 cm−2. The flow rate can be monitored and adjusted to maintain the desired flow rate as discussed herein. The gas leaves the conduits 105, 107 and enters the openings 124, 126, respectively of the plenum 123. From the plenum 123 the gas enters the pores 122 at the second surface 120 of the membrane 114. The gas exits the pores 122 as nanobubbles. In some embodiments, the size of the nanobubbles may range from about 100 nm to about 300 nm, following a normal size distribution. The size of the nanobubbles can be controlled by several factors as discussed herein, such as gas pressure, pore size of the membrane, hydrophobicity of the coating layer, and properties (e.g., surface tension and viscosity) of the medium. The produced nanobubbles in water suspension could be readily applied to any target system such as water, soil, or food through injection, spraying or immersion for water treatment, purification, remediation, pathogen mitigation, or agricultural applications.
Based on the above-mentioned generation method (e.g., using a tubular ceramic membrane of 100 nm pore size with a stearic acid coating), air nanobubbles (ANBs) were prepared in deionized water at injection air pressures ranging from 69 kPA to 414 kPA over periods of up to 120 minutes with results shown in
Following the same generation method as described in this patent,
The nanobubble water has demonstrated positive impacts seed germination and vegetable plants growth. Specifically, pure air, oxygen, nitrogen, and carbon dioxide nanobubbles in water were prepared using the same generation method as in Example 1 (e.g., using a tubular ceramic membrane of 100-nm pore size with a stearic acid coating). The water filled with different nanobubbles was used to irrigate plants of lettuce, carrot, fava bean, and tomato. The seeds in water containing NBs exhibited 6-25% higher germination rates. Especially, nitrogen NBs exhibited considerable effects in the seed germination, whereas air and carbon dioxide NBs did not significantly promote germination. The growth of stem length, diameter, leave numbers, and leave width were promoted by NBs (except air).
While exemplary embodiments have been described herein, it is expressly noted that these embodiments should not be construed as limiting, but rather that additions and modifications to what is expressly described herein also are included within the scope of the invention. Moreover, it is to be understood that the features of the various embodiments described herein are not mutually exclusive and can exist in various combinations and permutations, even if such combinations or permutations are not made express herein, without departing from the spirit and scope of the invention.
The present application claims priority to U.S. provisional application No. 62/560,948, filed Sep. 20, 2017, which is incorporated herein by reference.
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20190083945 A1 | Mar 2019 | US |
Number | Date | Country | |
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62560948 | Sep 2017 | US |