TWI775548B - A manufacturing modus of a plasma-activated solution - Google Patents

Abstract

A manufacturing modus of a plasma-activated solution, by using the atmospheric pressure and non-equilibrium plasma jet, comprises: (a) providing a frequency adjustable atmospheric pressure plasma-preparation power supply; (b) providing a plasma generator; (c) introducing a reaction gas into the plasma generator and making the variable frequency type plasma-preparation power supply corresponds to a required plasma frequency so as to power to the plasma generator; and (d) being applied a working plasma to a working liquid such that the working liquid is changed to the plasma-activated solution.

Description

Manufacturing method of plasma activation solution

The present invention relates to a manufacturing method of an antibacterial activation solution, in particular to a manufacturing method of a plasma activation solution. The invention relates to a method for preparing plasma activation solution by frequency conversion type jet atmospheric plasma (DC PLASMA JET), especially by using the frequency conversion type jet atmospheric plasma system, various types of atmospheric plasma can be achieved, such as: dielectric layer Discharge type (DBD), corona type (CORONA), plasma torch type (TOURCH) and other types of atmospheric plasma types can produce the effect of plasma activation solution.

The process of using atmospheric plasma to chemically modify the surface of materials has been practiced for many years, but contacting the liquid with the gas-phase plasma will produce more chemical effects in the liquid. Depending on the type of excited plasma discharge, its energy, and the chemical composition of the surrounding environment (gas and liquid phase), various types of plasma chemical reactions can be initiated, and through these reactions many primary and secondary species can be formed in the gas. And, the plasma is discharged at the gas-liquid interface, and these gases can penetrate or dissolve into the liquid and initiate chemical and biological killing processes in the liquid. Plasma activated liquid is also known as plasma acid, plasma activated water (Plasma Activated Water, PAW) and the like. The plasma-activated liquid can be used in agricultural, food, biological and medical applications.

It can be known from the disclosure of the prior art that the type and concentration of the reactive species in the generated plasma activation solution are different according to the way of exciting the plasma and the introduction of the reactive gas. But in general, the plasma activation solution will contain reactive oxygen species (ROS, Reactive Oxygen Species) and reactive nitrogen species (RNS, Reactive Nitrogen Species). Reactive oxygen species (ROS) is a by-product of biological aerobic metabolism, including oxygen ions, peroxides, and oxygen-containing free radicals, such as OH ⁻ , etc.; reactive nitrogen species (RNS) refers to NO ⁻ and reactive oxygen species in A series of free radicals and nitro compounds with high oxidative activity are derived, including peroxynitrite (HOONO ⁻ ) and so on. This is the main chemical reaction leading to the formation of reactive oxygen species (ROS) and reactive nitrogen species (RNS) in plasma activation solutions with antibacterial activity.

Table 1 (summarizing part of the prior art, source: Thirumdas et al, review paper, 2018) shows that, in addition to the plasma excitation mechanism, the treatment time and characteristics such as the gas, liquid used, and whether the plasma flow penetrates An important factor in plasma activation of water. For example, the use of oxygen, helium as the working gas to activate water will result in the formation of many major products including: atomic oxygen, singlet oxygen, superoxide, ozone, hydroxyl (-OH) and atomic nitrogen; then, the The reaction continues to form secondary products including: hydrogen peroxide (H ₂ O ₂ ), peroxynitrite (ONOO ⁻ ), nitric oxide (NO), nitrate (NO ₃ ⁻ ), and nitrite (NO ₂ ⁻ ) ions. The concentrations of reactive oxygen species (ROS) and reactive nitrogen species (RNS) can be detected by measuring the changes in electrical conductivity and redox potential (ORP, mV). The higher the conductivity (EC, μs/cm), the higher the relative concentration of peroxynitrite ions; the higher the redox potential (ORP, mV), the higher the relative concentration of hydrogen peroxide and hydroxyl (Lukes et al. al., 2012). The half-life of peroxynitrite is very short. As the standing time of the plasma water increases, NO ₂ ⁻ is gradually converted into NO ₃ ⁻ , the conductivity (EC) gradually decreases, and the pH value also increases slowly. Hydrogen peroxide and hydroxyl have a long half-life, slow redox potential (ORP) decline, and can be stored for a longer time. According to the existing technology (Master's thesis of Jiaotong University, Instructor: Liao Yinghao, 2019), it is pointed out that after the plasma water is stored for 7 days, the sterilization rate will be greatly reduced, and it will not even be able to sterilize. That is to say, plasma activated water has its time-effectiveness and is not easy to store, which means that there will be no residual problems in application. [Table 1] Plasma excitation mechanism Plasma operating mode working gas Treated water category throughput Reaction time acidity pH Redox potential ORP mV Conductivity EC µS/cm references DC jet plasma deep into the water Air Deionized water 10cc 20 minutes 2.3 540 Shen et al. 2016 DC jet plasma water surface helium Deionized water 1cc 5 minutes 4.2 Ikawa et al. 2016 DC jet plasma water surface helium Deionized water 0.5cc 5 minutes 4.2 Xu et al. 2016 DC jet plasma water surface Helium/Oxygen Deionized water 80cc 15 minutes 3 550 450 Ma et al. 2015 Dielectric discharge deep into the water Air Deionized water 1.6 liters 25 minutes 3.53 125 511 Ma et al. 2016 Dielectric discharge water surface Air Deionized water 1cc 15 minutes 2.7 1028 Traylor et al. 2011

Table 2 (Lukes et al., 2014) compares the chemical properties of plasma water generated by various plasma excitation mechanisms. The prior art also pointed out that the plasmonic excitation mechanism of the dielectric layer discharge (DBD) will generate higher reactive nitrogen species (RNS), with NO ₂ ⁻ /NO ₃ ⁻ concentrations of about 3.5 and 3.86 mM/L; DC Jet plasma can generate higher reactive oxygen species (ROS) reactive species, and the H ₂ O ₂ concentration is much higher than other excitation mechanisms, about 2.4 mM/L. Since different plasma excitation mechanisms produce different concentrations of reactive oxygen species (ROS) and reactive nitrogen species (RNS) reactive species, they sterilize through different chemical reactions, resulting in different antibacterial efficiencies and other secondary purposes . Therefore, different application requirements will require corresponding plasma excitation mechanisms, such as: medical applications, where high levels of hydrogen peroxide (H ₂ O ₂ ) of reactive oxygen species are expected to achieve the purpose of disinfection and sterilization; and, agricultural For the purpose, it is expected that the peroxynitrite/nitrite radical of the active nitrogen substance is high, in addition to sterilizing sand microorganisms, it can also impart the purpose of plant growth and germination at the same time. [Table 2] Plasma excitation mechanism Treated water category acidity pH H ₂ O ₂ NO ₂ ^- NO ₃ ^- references Dielectric discharge Deionized water 2.7 0.9 3.5 3.86 Traylor et al. 2011 DC jet plasma Deionized water 3.2 2.4 0.65 0.25 Liu et al. 2010 DC jet plasma brine 4.1 0.6 0.01 0.1 Gils et al. 2013 DC jet plasma Deionized water 3.3 0.7 0.2 1 Machala et al. 2013

Since plasma-activated water is rich in charged reactive oxygen species (ROS) and reactive nitrogen species (RNS) reactive species, it can be used as an alternative to food, crop and medical disinfection and sterilization, as well as to promote crop growth, germination and breeding. The source of industrial nitrogen fertilizer. Raw produce and fresh fruit are currently washed with high redox potential (ORP) sanitizing solutions to extend shelf life. But, more importantly, plasma-activated water is only obtained from natural air and water, which can replace traditional disinfection solutions with high oxidation-reduction potential (ORP) due to the addition of chemicals. Related literature: (1) Rohit Thirumdas, Anjinelyulu Kothakota, Uday Annapure, Kaliramesh Siliveru, Renald Blundell, Ruben Gatt, Vasilis P Valdramidis, (2018), Trends in food science & technology 77, 21-31; (2) P Lukes, E Dolezalova, I Sisrova, M Clupek, (2014), Aqueous-phase chemistry and bactericidal effects from an air discharge plasma in contact with water: evidence for the formation of peroxynitrite through a pseudo-second-order post -discharge reaction of H2O2 and HNO2, Plasma Sources Science and Technology 23 (1), 015019; (3) Shen, J., Tian, Y., Li, Y., Ma, R., Zhang, Q., Zhang, J., et al. (2016). Bactericidal effects against S. aureus and physicochemical properties of plasma activated water stored at different temperatures. Scientific Reports, 6; (4) Ikawa, S., Kitano, K., & Hamaguchi, S. (2010). Effects of pH on bacterial inactivation in aqueous solutions due to low-temperature atmospheric pressure plasma application. Plasma Processes and Polymers, 7(1) , 33–42; (5) Xu, Y., Tian, Y., Ma, R., Liu, Q., & Zhang, J. (2016). Effect of plasma activated water on the postharvest quality of button mushrooms, Agaricus bisporus. Food Chemistry , 197, 436–444; (6) Ma, R., Wang, G., Tian, Y., Wang, K., Zhang, J., & Fang, J. (2015). Non-thermal plasma-activated water inactivation of food-borne pathogen on fresh produce. Journal of Hazardous Materials, 300, 643–651; (7) Ma, R., Yu, S., Tian, Y., Wang, K., Sun, C., Li, X., et al. (2016). Effect of non-thermal plasma-activated water on Fruit decay and quality in postharvest Chinese bayberries. Food and Bioprocess Technology, 9(11), 1825–1834; (8) Traylor, MJ, Pavlovich, MJ, Karim, S., Hait, P., Sakiyama, Y., Clark, DS, et al. (2011). Long-term antibacterial efficacy of air plasma-activated water. Journal of Physics D: Applied Physics, 44(47), 472001; (9) Liu, Y., Ye, N., Liu, R., Chen, M., & Zhang, J. (2010). H2O2 mediates the regulation of ABA catabolism and GA biosynthesis in Arabidopsis seed dormancy and germination. Journal of Experimental Botany, 61(11), 2979–2990; (10) van Gils, CAJ, Hofmann, S., Boekema, BKHL, Brandenburg, R., & Bruggeman, PJ (2013). Mechanisms of bacterial inactivation in the liquid phase induced by a remote RF cold atmospheric pressure plasma jet. Journal of Physics D: Applied Physics, 46(17), 175203; (11) Machala Z, Tarabova B, Hensel K, Spetlikova E, Sikurova L and Lukes P. (2013). Formation of ROS and RNS in Water Electro‐S prayed through Transient Spark Discharge in Air and their Bactericidal Effects, Plasma Process. Polym. 10 649–59; (12) Mcferson, LL (1993). Understanding ORP's role in the disinfection process, Water Engineering and Management, 140, 29–31; (13) Lai Chengchun’s master’s thesis, supervisor Dr. Liao Yinghao, work and influence of cavity gas composition on plasma water characteristics, 2019.

Therefore, the purpose of the present invention is to provide a method for producing a plasma activation solution, whereby the specified polar functional groups ( polar-functional groups, such as: -OH, -CH, -NH, -COOH...), and then undergo a plasmonic chemical reaction with water. It is possible to manufacture plasma activation solutions rich in various reactive oxygen species (ROS) and reactive nitrogen species (RNS) without the need for various types of plasma mechanisms, especially by mass-produced methods to meet the needs of various industries.

The technical means adopted by the present invention to solve the problems of the prior art is to provide a manufacturing method of a plasma activation solution, comprising: (a) providing a frequency conversion type plasma preparation power supply, the working voltage of which is greater than 6,000 volts and the working current is less than 1 Ampere; (b) providing a plasma generator having an insulating sleeve, an inner core, a nozzle, and a vortex generating structure, the insulating sleeve enclosing a reaction gas accommodating space, the inner core being disposed in the reaction gas accommodating space and It is electrically connected to one pole of the variable frequency plasma preparation power supply, the nozzle is arranged at the lead-out end of the reaction gas containing space and is electrically connected to the other pole of the variable frequency plasma preparation power supply, and the nozzle is connected to the A plasma generating space is formed between the inner cores, and the eddy current generating structure is arranged corresponding to the inner core and is used for guiding the gas flow from the reaction gas accommodating space through the inner core to the plasma generating space, and making the gas flow in the plasma generating space. The plasma generating space forms a vortex flow region below the standard atmospheric pressure; (c) introducing the reaction gas into the plasma generator and making the variable frequency plasma preparation power supply supply power to the plasma generation corresponding to the desired plasma frequency device, wherein the reaction gas system introduced into the plasma generator is guided from the reaction gas accommodating space through the vortex generating structure to flow through and cool the inner core in a vortex flow and form the inner body in the plasma generating space A vortex flow region, the vortex flow region is used to lengthen the electron mean free path, so as to facilitate the dissociation of the reaction gas, and the reaction gas is dissociated into gas ions and electrons in the plasma generating space to form a working plasma; and ( d) applying the working plasma to the working fluid to convert the working fluid into a plasma-activated fluid.

In an embodiment of the present invention, a method for manufacturing a plasma activation solution is provided, wherein in step (c), when supplying power, the operating power of the variable-frequency plasma preparation power supply is 300 watts to 1,000 watts. The working frequency of the variable frequency plasma preparation power source is 15 kHz to 40 kHz, and the working current of the variable frequency plasma preparation power source is 0.3 amperes to 0.7 amperes.

In an embodiment of the present invention, a method for manufacturing a plasma activation solution is provided, wherein in step (b), the nozzle of the plasma generator is a cathode, and the inner core is an anode.

In an embodiment of the present invention, a method for manufacturing a plasma activation solution is provided, wherein in step (c), the reactive gas is air, and under one of the power supply conditions of the desired plasma frequency, the reactive gas is dissociating oxygen molecules into oxygen ions to become the working plasma of oxygen, and in step (d), the working plasma of oxygen causes the working liquid to transform into the plasma activation liquid with reactive oxygen species; or, step (c) ), the reaction gas is air, and under another power supply condition of the desired plasma frequency, the reaction gas dissociates nitrogen molecules into nitrogen ions to become the working plasma of nitrogen, and in step (d), nitrogen The working plasma transforms the working liquid into the plasma activation liquid with active nitrogen species.

In an embodiment of the present invention, a method for manufacturing a plasma activation solution is provided, wherein in step (c), the reactive gas is air, and under one of the power supply conditions of the desired plasma frequency, the reactive gas is dissociating oxygen molecules into oxygen ions to become the working plasma of oxygen, and, under another power supply condition of the desired plasma frequency, the reaction gas dissociates nitrogen molecules into nitrogen ions to become the working plasma of nitrogen, And in step (d), the working plasma of oxygen and the working plasma of nitrogen make the working liquid change into the plasma activation liquid with active oxygen species and active nitrogen species.

In an embodiment of the present invention, a method for manufacturing a plasma activation liquid is provided, wherein in step (d), the working liquid is tap water, filtered water, deionized water, reverse osmosis water, well water, salt water , edible oil, essence, essential oil, lotion or hydrosol.

In an embodiment of the present invention, a method for manufacturing a plasma activation solution is provided. Before step (c), the method further includes: providing a venturi, respectively connected to the outlet end of the plasma generator and the outlet of the working fluid. a fluid source, and in step (d), the working plasma is continuously flowed into the venturi from the plasma generator, and by pressure changes as the working plasma passes through the throat of the venturi The working fluid is drawn continuously into the venturi to be applied to the working fluid to continuously output the plasma activation fluid.

In an embodiment of the present invention, a method for manufacturing a plasma activation liquid is provided, wherein in step (d), the working plasma is applied to the working liquid in a manner that the nozzle of the plasma generator is immersed in the working liquid The working liquid, or the working plasma is applied to the working liquid in a non-contact manner in which the nozzle of the plasma generator is spaced from the liquid level of the working liquid.

In an embodiment of the present invention, a method for manufacturing a plasma activation solution is provided, wherein in step (b), a bypass channel is provided in the nozzle of the plasma generator, and in step (c), adding Liquid is injected into the plasma generator through the bypass channel, the additive liquid is dissociated in the plasma generating space, the additive liquid is water or the plasma activation liquid, and in step (d), the dissociated additive A liquid is applied to the working liquid in coordination with the working plasma.

In an embodiment of the present invention, a method for manufacturing a plasma activation solution is provided, wherein in step (d), the working liquid is transformed into the plasma activation solution in a plasma reaction tank, and the working liquid input device is connected to The plasma reaction tank is used to input the working liquid, and the exhaust pipe of the plasma reaction tank is communicated with the working liquid input device to guide the gas ions in the working plasma into the working liquid input device so as to work in the working liquid. Before the liquid enters the plasma reaction tank, the gas ions are pre-applied to shorten the time required for converting the working liquid into the plasma activation liquid, and the plasma reaction tank is connected to the output pipeline of the plasma activation liquid to provide the electricity. Output of slurry activation solution.

The present invention dissociates nitrogen molecules (N2) and oxygen molecules (O2) in different proportions in the air by accelerating electrons with high voltage and changing the excitation mechanism of the plasma frequency to produce a designated polar-functional group (polar-functional group). , for example: OH-, CH-, NH-, COOH-, O-...etc.). Instead of using brute force to increase the wattage and amperage to break the bonds, we can find the vibration frequency between molecules, and use the resonance effect to assist in the breaking of bonds, selectively producing various chemical radicals (radical). The plasma operating power of the present invention is 350 to 1,000 watts, the current does not exceed 1 ampere (Amp), and the voltage is greater than 6,000 volts. Moreover, the working plasma of the present invention is not a spark discharge (ARCING FREE), and it is directly immersed in the working liquid to produce a plasma activation solution, and there is no industrial safety concern of electric shock (this is because the existing atmospheric plasma technology cannot The slurry generator plugs directly into the water, or can only be used with laboratory grade 10cc water for plasma production considerations).

Embodiments of the present invention will be described below with reference to FIGS. 1 to 19 . This description is not intended to limit the embodiments of the present invention, but is an example of the present invention.

As shown in FIG. 1 to FIG. 3 , a method 100 for manufacturing a plasma activation solution according to an embodiment of the present invention includes: (a) providing a variable frequency plasma preparation power source 1 ; (b) providing a plasma generation (c) introducing reactive gas A into the plasma generator 2 and causing the variable frequency plasma preparation power supply 1 to supply power to the plasma generator 2 corresponding to the desired plasma frequency; and, (d) applying power to the plasma generator 2 The working plasma P is applied to the working fluid F to transform the working fluid F into the plasma activation fluid L. The following Table 3 summarizes the characteristics of the embodiment of the present invention for manufacturing the plasma activation solution, which is only used to help understand the technical content of the present invention and is not used to limit the scope of the patent application of the present invention. [table 3] Plasma excitation mechanism Plasma operating mode working gas Treated water category throughput Reaction time acidity pH Redox potential ORP mV Conductivity EC µS/cm DC jet plasma deep into the water Air reverse osmosis water/filtered water/tap water 3 liters 2/3.5/14 minutes <2.6 540 DC jet plasma deep into the water Air filtered water 1 liter 50 seconds <2.6 643 DC jet plasma deep into the water Air filtered water 1 liter 6 minutes 13 seconds <2.6 1024 DC jet plasma deep into the water Air reverse osmosis water 1 liter 6 seconds/30 seconds <2.0 601/646 DC jet plasma deep into the water Air reverse osmosis water 1 liter 30 seconds <2.0 1030

As shown in FIG. 2, in step (a), the working voltage of the variable frequency plasma preparation power source 1 is greater than 6,000 volts and the working current is less than 1 ampere.

As shown in FIGS. 2 and 3 , in step (b), the plasma generator 2 includes an insulating casing 21 , an inner core 22 , a nozzle 23 , and a vortex generating structure 24 . The insulating sleeve 21 encloses the reaction gas accommodating space 210 . The inner core 22 is disposed in the reaction gas accommodating space 210 and is electrically connected to one pole of the variable frequency plasma preparation power source 1 . The nozzle 23 is disposed at the lead-out end of the reaction gas accommodating space 210 and is electrically connected to the other pole of the variable frequency plasma preparation power source 1 , and a plasma generating space 230 is formed between the nozzle 23 and the inner core 22 . The eddy current generating structure 24 is disposed corresponding to the inner core 22 and is used for guiding the gas flow from the reaction gas accommodating space 210 through the inner core 22 to the plasma generating space 230 , and making the gas flow in the plasma generating space 230 . A region of vortex flow with sub-atmospheric pressure is formed.

Further, as shown in FIG. 3, according to a method 100 for manufacturing a plasma activation solution according to an embodiment of the present invention, in step (b), the nozzle 23 of the plasma generator 2 is a cathode, and the inner core is Body 22 is the anode.

As shown in FIG. 2 and FIG. 3 , in step (c), the reaction gas A introduced into the plasma generator 2 is guided from the reaction gas accommodating space 210 through the vortex generating structure 24 to flow in a vortex It flows through and cools the inner core 22 in a manner to form the vortex flow region in the plasma generating space 230 . The vortex flow region is used to lengthen the electron mean free path to facilitate the dissociation of the reaction gas A, which is dissociated into gas ions and electrons in the plasma generating space 230 to form a working plasma P.

As shown in FIG. 2 , according to the manufacturing method 100 of the plasma activation solution according to an embodiment of the present invention, in step (c), when power is supplied, the operating power of the variable frequency plasma preparation power supply 1 is 300 watts to 1 kilowatt. Moreover, the working frequency of the variable frequency plasma preparation power source 1 is 15 kHz to 40 kHz, and the working current of the variable frequency plasma preparation power source 1 is 0.3 amperes to 0.7 amperes.

Specifically, as shown in FIG. 3 , according to a method 100 for manufacturing a plasma activation solution according to an embodiment of the present invention, in step (c), the reactive gas A is air, and in one of the desired plasma Under the power supply condition of the frequency, the reaction gas A dissociates oxygen molecules into oxygen ions to become the working plasma P of oxygen; and in step (d), the working plasma P of oxygen makes the working liquid F become active This plasma activation solution L of oxygen species (ROS). Or, in step (c), the reaction gas A is air, and under another power supply condition of the desired plasma frequency, the reaction gas A dissociates nitrogen molecules into nitrogen ions to become the working plasma P of nitrogen gas ; and in step (d), the working plasma P of nitrogen causes the working liquid F to transform into the plasma activation liquid L with reactive nitrogen species (RNS).

The manufacturing method of the plasma activation solution L is not limited to the above. According to the manufacturing method 100 of the plasma activation solution according to an embodiment of the present invention, in step (c), the reactive gas A is air, and under one of the power supply conditions of the desired plasma frequency, the reactive gas A is The working plasma P that dissociates oxygen molecules into oxygen ions to become oxygen; and, under another power supply condition of the desired plasma frequency, the reaction gas A dissociates nitrogen molecules into nitrogen ions to become the working plasma of nitrogen. Pulp P. And, in step (d), the working plasma P of oxygen and the working plasma P of nitrogen make the working liquid F transform into the plasma activation liquid L having active oxygen species and active nitrogen species. Of course, the present invention is not limited to the reaction gas A being air, and the reaction gas A can also be argon gas.

As shown in FIG. 1 and FIG. 2 , according to a method 100 for manufacturing a plasma activation liquid according to an embodiment of the present invention, in step (d), the working liquid F is tap water, filtered water, and deionized water , reverse osmosis water, well water, salt water, edible oil, essence, essential oil, lotion or hydrosol.

In detail, as shown in FIG. 1 and FIG. 2, the main configuration of the plasma activation solution manufacturing equipment of the present invention is: the working fluid input device R is connected to the plasma reaction tank S to input the working fluid F; The plasma reaction tank S has an exhaust pipe V to discharge gas, and the plasma reaction tank S has a high water level sensor HS, a low water level sensor LS and an overflow control device K; and, the output of the plasma activation solution The pipeline T is connected to the plasma reaction tank S.

As shown in FIG. 4 , in the method 100 for manufacturing a plasma activation solution according to an embodiment of the present invention, before step (c), further comprising: providing venturi tubes 3 connected to the plasma generator 2 respectively. an outlet end and a fluid source of the working liquid F; and, in step (d), the working plasma P is continuously flowed into the venturi 3 from the plasma generator 2, where the working plasma P passes through When the throat 31 of the venturi 3 is drawn, the working fluid F is continuously drawn into the venturi 3 by pressure changes and applied to the working fluid F, so as to continuously output the plasma activation fluid L.

As shown in FIG. 2 and FIG. 5 , according to a method 100 for manufacturing a plasma activation liquid according to an embodiment of the present invention, in step (d), the nozzle 23 of the plasma generator 2 and the working liquid are The working plasma P is applied to the working liquid F in a non-contact manner in which the liquid surface of F is spaced apart. Alternatively, as shown in FIGS. 2 and 6 , in step (d), the working plasma P is applied to the working fluid so that the nozzle 23 of the plasma generator 2 is immersed in the working fluid F liquid F.

As shown in FIG. 5 and FIG. 6 , according to a method 100 for manufacturing a plasma activation solution according to an embodiment of the present invention, in step (b), it further includes that the nozzle 23 of the plasma generator 2 is disposed beside the nozzle 23 . Channel 23B. In step (c), the additive liquid D is injected into the plasma generator 2 through the bypass channel 23B, the additive liquid D is dissociated in the plasma generating space 230, and the additive liquid D is water or the plasma is activated Liquid L. And, in step (d), the dissociated additive liquid D is applied to the working liquid F in conjunction with the working plasma P.

As shown in FIG. 7, in the embodiment of the present invention, the plasma generator 2 can also be inclined with respect to the liquid level of the working liquid F in the plasma reaction tank S and be immersed in the working liquid F, Instead, the working plasma is applied to the working liquid F.

As shown in FIG. 8 , the configuration of another manufacturing equipment of the plasma activation solution of the present invention is: the working fluid input device R is connected to the temporary storage tank, and the temporary storage tank is provided with a high water level sensor HS and a low water level sensor HS. The water level sensor LS; the exhaust pipe V is arranged between the temporary storage tank and the plasma reaction tank S, and the working liquid F is input into the plasma reaction tank S from the temporary storage tank through the exhaust pipe V and the connecting pipe ; The plasma generator 2 is arranged in the connecting pipe, and when the working liquid F passes through the connecting pipe, the working plasma is applied to the working liquid F to produce a plasma activation liquid L; and, the plasma activation liquid L is collected in the plasma reaction tank S, and the plasma activation solution L is output from the output pipeline T connected to the plasma reaction tank S.

According to the manufacturing method 100 of the plasma activation solution according to an embodiment of the present invention, in the step (d), the working liquid F is transformed into the plasma activation solution L in the plasma reaction tank S. The working liquid input device R is connected to the plasma reaction tank S to input the working liquid F, and the exhaust pipe V of the plasma reaction tank S is communicated with the working liquid input device R (not shown in the drawings of the present invention) and Guide the gas ions in the working plasma P into the working liquid input device R to pre-apply the gas ions before the working liquid F enters the plasma reaction tank S, so as to shorten the transformation from the working liquid F to the plasma Time required to activate solution L. In addition, the plasma reaction tank S is connected to the output pipeline T of the plasma activation solution to provide the output of the plasma activation solution L.

As shown in Figures 9 to 11, acidity (pH), oxidation-reduction potential (ORP), temperature, and electrical conductivity (EC) vary with the generation time of the plasma activation solution. Acidification occurs due to the reaction between the plasma-forming chemicals and water, and pH is a measure of the concentration of hydrogen ions in a solution. As the treatment time increased, the pH of the plasma activation solution decreased rapidly and then reached a stable range. Oxidation-reduction potential (ORP) is a measure of the ability of a solution to oxidize or reduce another species and depends on the concentration of the oxidant and its strength. Redox potential is considered to be an important factor affecting microbial inactivation, which disrupts the cell membrane and defense mechanisms of microorganisms (Mcerson, 1993). Oxidation-reduction potential (ORP) increases rapidly with pH up to 5.5, and then tends to stabilize. Conductivity is a measure of the electrolyte content in water. The reactive species ROS and RNS generated during the treatment of the plasma activation solution are easily dissolved in water and greatly improve the conductivity of the plasma activation solution. The conductivity increases proportionally with time, which has an absolute relationship with the plasmonic excitation mechanism. As mentioned in Table 2 of the prior art, the H ₂ O ₂ produced by the DC jet plasma is high, so the oxidation-reduction potential (ORP) rises rapidly; the DBD dielectric layer plasma produces a high NOx ^- concentration, and the conductivity easier to rise. The present invention belongs to DC jet plasma, so no matter what kind of water quality is treated, the NOx-generating mechanism is poor and can only increase linearly with time. This is the fate of traditional DC jet plasma. As shown in Figures 9 to 11, the purer the water quality, the faster the maximum redox potential (ORP) is reached. With the method of the present invention, reverse osmosis water (Fig. 9) in 2 minutes, filtered water (Fig. 10) in 3.5 minutes, and tap water (Fig. 11) in 14 minutes, even when using a 3-liter capacity Reaching 90% of the ORP maximum, these results are far more efficient than the prior art (Table 1, small capacity and long processing time).

As shown in Figure 12, using the oxidation-reduction potential (ORP) as an indicator, the larger the volume of the treatment liquid (eg tap water), the longer the treatment time. However, the three volumes (1 liter, 2 liters and 3 liters) of working fluids processed can achieve an efficiency of about 1 liter per 5 minutes, which is far more advanced than that shown in Table 1 of the prior art.

As shown in Fig. 13 to Fig. 15, the feature of the present invention lies in the variable frequency plasma technology. Taking reverse osmosis water with 1 liter of liquid as an example: adjust the plasma frequency to dissociate when there is a lot of oxygen in the air (the amount of oxygen in the air). working plasma), the redox potential (ORP) can reach 90% of the maximum value of 586mV within 30 seconds (Fig. 14), and the maximum occurs at 643mV at 50 seconds. In the formation of redox potential, the working plasma of oxygen is 4 times faster than that of dissociating nitrogen in air (the working plasma of nitrogen reaches 584mV after 165 seconds), as shown in the ORP change in Figure 14 shown. When the plasma frequency is adjusted to the working plasma of nitrogen with more nitrogen molecules in the dissociated air, the working plasma of nitrogen does perform better in EC, and the slope of conductivity increases rapidly, and the two reach the maximum value of 1024us/ The time in cm differs by 30%, as shown in Figure 15. Therefore, the indicators required for different applications are not the same, but all can speed up the generation of ORP or EC values by changing the plasma frequency.

As shown in Fig. 16 and Fig. 17, in order to take into account the maximum ORP value and the accelerated EC value, the feature of the present invention is the variable frequency plasma technology. When the ORP reaches the maximum value, the plasma frequency is changed to a nitrogen plasma with more dissociated nitrogen molecules. When the plasma frequency is changed, the maximum ORP value can be maintained and the generation of EC value can be accelerated. The EC value still exhibits a proportional relationship with the time of applying the plasma, which is shorter than the plasma generation time of the DBD dielectric layer of the prior art.

As shown in Figure 18, under the working conditions of injecting the essence (or hydrosol) with a flow rate of 2 to 10 ml/sec (the essence or hydrosol is passed through the nozzle shown in Figure 5 or Figure 6 23 side channel 23B injection), the working plasma of nitrogen (N1 to N3) can immediately produce a plasma activation solution with a higher EC value; the working plasma of oxygen (O1 to O3) has a higher ORP value. However, in general, the ORP, pH, and EC values of all the indicators of the plasma activation solution cannot immediately reach the optimal index values of the aforementioned plasma activation solution, but they all reach 90% of the maximum value in an instant.

As shown in Fig. 19, the plasma generator was directly immersed into a reaction tank with 1 liter of reverse osmosis water (specifically, the reverse osmosis water was The side channel 23B of the nozzle 23 shown in Fig. or Fig. 6 is injected), and the air outlet of the reaction tank is introduced into the water inlet tank to prepare the reserve water in advance. The working time only takes 30 seconds to make the three indicators (that is, ORP, pH value and EC value) all meet the standard, of which ORP only takes 6 seconds to reach more than 600mV, and the temperature of the reaction tank is only 38 degrees C . Plasma activation fluid made of such a composite variable frequency plasma can be used in industry, agriculture, or even medical treatment.

The above descriptions and descriptions are only descriptions of preferred embodiments of the present invention. Those with ordinary knowledge in the art can make other modifications according to the scope of the patent application defined below and the above descriptions, but these modifications should still be It is within the scope of the right of the present invention for the inventive spirit of the present invention.

100: Manufacturing method of plasma activation solution 1: Frequency conversion plasma preparation power supply 2: Plasma generator 21: Insulation kit 210: Reactive gas accommodation space 22: Kernel body 23: Nozzle 230: Plasma Generation Space 23B: Bypass 24: Eddy current generation structure 3: Venturi 31: Throat neck A: Reactive gas D: add liquid F: working fluid HS: High Water Level Sensor K: overflow control device L: Plasma activation solution LS: Low Water Level Sensor P: working plasma R: Working fluid input device S: Plasma reaction tank T: The output pipe of the plasma activation solution V: exhaust pipe (a): Step (b): step (c): step (d): step

[FIG. 1] is a schematic flowchart showing a method for manufacturing a plasma activation solution according to an embodiment of the present invention; [Fig. 2] is a schematic diagram showing the manufacturing equipment of the plasma activation solution according to the embodiment of the present invention; [FIG. 3] is a schematic cross-sectional view showing the plasma generator in the manufacturing equipment of the plasma activation solution according to the embodiment of the present invention; [FIG. 4] is a schematic cross-sectional view showing the plasma generator assembling a venturi in the manufacturing equipment of the plasma activation solution according to the embodiment of the present invention; [Fig. 5] is a schematic cross-sectional view showing a plasma generator provided with a bypass channel in the manufacturing equipment of the plasma activation solution according to the embodiment of the present invention; [Fig. 6] is another cross-sectional schematic diagram showing a plasma generator provided with a bypass channel in the manufacturing equipment of the plasma activation solution according to the embodiment of the present invention; [Fig. 7] is a schematic diagram showing that the plasma generator is immersed in the working liquid in an oblique insertion manner in the equipment for manufacturing the plasma activation liquid according to the embodiment of the present invention; [Fig. 8] is a schematic diagram showing another manufacturing equipment of the plasma activation solution according to the embodiment of the present invention; [Fig. 9] is a schematic diagram showing the index generation of the plasma activation solution (working liquid is 3 liters of reverse osmosis water) according to an embodiment of the present invention over time; [Fig. 10] is a schematic diagram showing the index generation of the plasma activation solution (the working fluid is 3 liters of filtered water) according to an embodiment of the present invention; [Fig. 11] is a schematic diagram showing the index generation of the plasma activation solution (the working fluid is 3 liters of tap water) according to the embodiment of the present invention; [Fig. 12] is a schematic diagram showing the index generation of the plasma activation fluid (working fluid of 3 volumes, 1 liter, 2 liter and 3 liter) over time according to an embodiment of the present invention; [Fig. 13] is a schematic diagram showing the summation of the indicators of the plasma activation solution (different plasma frequencies) generated over time according to the embodiment of the present invention; [Fig. 14] is one of the schematic diagrams showing the generation of indexes of the plasma activation solution (different plasma frequencies) over time according to an embodiment of the present invention; [Fig. 15] is the second schematic diagram showing the generation of indicators of the plasma activation solution (different plasma frequencies) over time according to the embodiment of the present invention; [Fig. 16] is the third schematic diagram showing the generation of indexes of the plasma activation solution (different plasma frequencies) over time according to the embodiment of the present invention; [Fig. 17] is the fourth schematic diagram showing the generation of indexes of plasma activation solutions (different plasma frequencies) over time according to an embodiment of the present invention; [Fig. 18] is a schematic diagram showing the relationship between the plasma activation solution (the working liquid is the essence of cosmetics) and the plasma frequency according to the embodiment of the present invention; and [FIG. 19] is a schematic diagram showing the generation of a plasma activation solution according to an embodiment of the present invention.

(a): Step

(b): step

(c): step

(d): step

Claims (9)

A method for manufacturing a plasma activation solution, comprising: (a) providing a variable-frequency plasma preparation power source with an operating voltage greater than 6,000 volts and an operating current less than 1 ampere; (b) providing a plasma generator having an insulating kit, an inner core, a nozzle, and a vortex generating structure, the insulating sleeve encloses a reactive gas accommodating space, the inner core is arranged in the reactive gas accommodating space and is electrically connected to one of the poles of the variable frequency plasma preparation power supply, the The nozzle is arranged at the lead-out end of the reaction gas accommodating space and is electrically connected to the other pole of the variable frequency plasma preparation power supply, and a plasma generation space is formed between the nozzle and the inner core, and the eddy current generation structure is arranged corresponding to In the inner core, it is used to guide the gas flow from the reaction gas accommodating space through the inner core to the plasma generation space, and make the gas flow in the plasma generation space to form a vortex flow region with a pressure lower than the standard atmosphere; ( c) introducing a reactive gas into the plasma generator and making the variable frequency plasma preparation power supply supply power to the plasma generator corresponding to a desired plasma frequency, wherein the reactive gas system introduced into the plasma generator is supplied from the plasma generator The reaction gas accommodating space is guided by the vortex generating structure to flow through and cool the inner core in a vortex flow manner, and the vortex flow region is formed in the plasma generating space, and the vortex flow region is used to lengthen the electron mean freedom a path to facilitate the dissociation of the reactive gas, the reactive gas is dissociated into gas ions and electrons in the plasma generating space to form a working plasma; and (d) applying the working plasma to the working liquid to make the working liquid Converting into a plasma activation solution, wherein in step (d), the working liquid is transformed into the plasma activation solution in a plasma reaction tank, and a working liquid input device is connected to the plasma reaction tank to input the working liquid, And the exhaust pipe of the plasma reaction tank is communicated with the working liquid input device to guide the gas ions in the working plasma into the working liquid input device to pre-apply the gas before the working liquid enters the plasma reaction tank ions to shorten by The time required for the working liquid to transform into the plasma activation solution, and the plasma reaction tank is connected to the output pipeline of the plasma activation solution to provide the output of the plasma activation solution. The manufacturing method of the plasma activation solution as claimed in claim 1, wherein in step (c), when supplying power, the operating power of the variable frequency plasma preparation power source is 300 watts to 1,000 watts, and the variable frequency plasma preparation power The working frequency of the power source is 15 kHz to 40 kHz, and the working current of the variable frequency plasma preparation power source is 0.3 amperes to 0.7 amperes. The manufacturing method of the plasma activation solution according to claim 1, wherein in step (b), the nozzle of the plasma generator is a cathode, and the inner core is an anode. The method for producing a plasma activation solution according to claim 1, wherein in step (c), the reactive gas is air, and under one of the power supply conditions of the desired plasma frequency, the reactive gas is dissociated into oxygen molecules as Oxygen ions become the working plasma of oxygen, and in step (d), the working plasma of oxygen causes the working liquid to transform into the plasma activation liquid with reactive oxygen species; or, in step (c), the The reactive gas is air, and under another power supply condition of the desired plasma frequency, the reactive gas dissociates nitrogen molecules into nitrogen ions to become the working plasma of nitrogen, and in step (d), the working plasma of nitrogen is The slurry transforms the working liquid into the plasma activation liquid with reactive nitrogen species. The method for producing a plasma activation solution according to claim 1, wherein in step (c), the reactive gas is air, and under one of the power supply conditions of the desired plasma frequency, the reactive gas is dissociated into oxygen molecules as Oxygen ions to become the working plasma of oxygen, and, under another power supply condition of the desired plasma frequency, the reaction gas dissociates nitrogen molecules into nitrogen ions to become the working plasma of nitrogen, and step (d ), the working plasma of oxygen and the working plasma of nitrogen make the working liquid change into the plasma activation liquid with reactive oxygen species and reactive nitrogen species. The manufacturing method of the plasma activation liquid according to claim 1, wherein in step (d), the working liquid is tap water, filtered water, deionized water, reverse osmosis water, well water, salt water, edible oil, Serum, essential oil, toner or hydrosol. The manufacturing method of the plasma activation solution as claimed in claim 1, before step (c), further comprising: providing a venturi, respectively connected to the outlet end of the plasma generator and the fluid source of the working fluid, and In step (d), the working plasma is continuously flowed into the venturi from the plasma generator, and when the working plasma passes through the throat of the venturi, the working liquid is pulled by pressure changes Continuously entering the venturi to be applied to the working fluid to continuously output the plasma activation fluid. The method for producing a plasma activation liquid as claimed in claim 1, wherein in step (d), the working plasma is applied to the working liquid in such a way that the nozzle of the plasma generator is immersed in the working liquid, Alternatively, the working plasma is applied to the working liquid in a non-contact manner in which the nozzle of the plasma generator is spaced from the liquid level of the working liquid. The method for producing a plasma activation solution as claimed in claim 1, wherein in step (b), it further comprises setting a bypass channel in the nozzle of the plasma generator, and in step (c), passing the additive liquid through the bypass channel The channel is injected into the plasma generator, the addition liquid is dissociated in the plasma generation space, the addition liquid is water or the plasma activation liquid, and in step (d), the dissociated addition liquid is matched with the work Plasma is applied to the working liquid.

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