CN114713158A - Plasma processing method for enhancing killing capability of chemical solution - Google Patents

Plasma processing method for enhancing killing capability of chemical solution Download PDF

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CN114713158A
CN114713158A CN202210337197.2A CN202210337197A CN114713158A CN 114713158 A CN114713158 A CN 114713158A CN 202210337197 A CN202210337197 A CN 202210337197A CN 114713158 A CN114713158 A CN 114713158A
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plasma
chemical solution
solution
chemical
generating device
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卢新培
李宜谦
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873Materials to be treated
    • B01J2219/0877Liquid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0894Processes carried out in the presence of a plasma

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention discloses a plasma processing method for enhancing the killing capacity of a chemical solution, which uses plasma to process the chemical solution, wherein the chemical solution comprises at least one of sodium hydroxide, hydrogen peroxide, sodium nitrite, ethanol, potassium permanganate, hypochlorous acid and hydrochloric acid, the chemical solution contains a large amount of chemical particles, has certain chemical properties, and has oxidizability, and various active nitrogen and oxygen substances generated by the plasma can completely and completely react with the particles in the chemical solution or accelerate the original reaction rate, so that the solution obtains stronger chemical activity, the pH value is reduced, and the oxidation-reduction potential is greatly increased; after their treatment with plasma, solutions can be obtained which possess a greater chemical activity, a greater redox potential, a greater killing power than plasma-activated water.

Description

Plasma processing method for enhancing killing capability of chemical solution
Technical Field
The invention belongs to the field of plasmas, and particularly relates to a plasma processing method for enhancing the killing capability of a chemical solution.
Background
The atmospheric pressure non-equilibrium plasma is plasma generated under atmospheric pressure, and can react with air to generate a plurality of active components such as ozone, hydroxyl radicals, excited nitrogen molecules and the like when being discharged in the air. The active components diffuse to the gas-liquid interface and can react with the liquid to generate a new liquid-phase active nitrogen-oxygen product in the liquid. The active oxygen mainly comprises hydroxyl free radical, singlet oxygen, superoxide anion free radical, hydrogen peroxide and the like, and the active nitrogen mainly comprises nitrite, nitrate radical, peroxynitrous acid and the like. Many of these reactive nitrogen oxide particles are highly oxidative and cytotoxic, causing oxidative stress on the bacteria, resulting in bacterial death.
The disinfectants on the market at present have various problems, such as iodine and phenols, and have the problems of difficult biodegradation and toxicity to the environment. Hypochlorites and hydroperoxides are unstable and easily degraded, and may be decomposed during use. The stable alcohol disinfectant has the problem of insignificant sterilizing capability. There is a need to find a new, green, powerful "disinfectant".
Disclosure of Invention
In view of the above-mentioned drawbacks or needs for improvement in the prior art, the present invention provides a plasma treatment method for enhancing the killing ability of a chemical solution, which has the advantages of environmental friendliness, high efficacy, and the like, and can reduce the use of a disinfectant that is difficult to biodegrade.
To achieve the above object, according to a first aspect of the present invention, there is provided a plasma treatment method for enhancing a killing capability of a chemical solution, comprising:
s1, placing the chemical solution in a container; wherein the chemical solution comprises: at least one of sodium hydroxide, hydrogen peroxide, sodium nitrite, ethanol, potassium permanganate, hypochlorous acid or hydrochloric acid;
and S2, processing the solution by using a plasma generating device to obtain the chemical solution after plasma processing.
Preferably, the vessel is grounded to provide a ground electrode for plasma discharge.
Preferably, one end of the ground line is connected to the chemical solution, and the other end is grounded to provide a ground electrode for plasma discharge.
Preferably, the plasma generating device is a dielectric barrier discharge plasma generating device, a sliding arc discharge plasma generating device or a jet array discharge plasma generating device.
Preferably, the driving power supply of the plasma generating device is a nanosecond pulse power supply, a microsecond pulse power supply, an alternating current power supply or a direct current power supply.
Preferably, the working gas of the plasma generating device is nitrogen, air, helium or argon.
According to a second aspect of the present invention there is provided a chemical solution prepared using a method as described in the first aspect.
According to a third aspect of the present invention, there is provided a plasma processing system for enhancing the killing power of a chemical solution, comprising: the plasma array device, the direct-current low-voltage power supply, the boosting module, the container and the grounding wire;
the container is used for containing a chemical solution to be treated, and the grounding wire is connected with the solution to be treated and the ground to provide a ground electrode for the discharge of the plasma array device;
the plasma array device is driven by a direct-current low-voltage power supply through a boosting module to generate plasma so as to treat the chemical solution in the container.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
1. the invention provides a plasma processing method for enhancing the killing capacity of a chemical solution, which uses plasma to process the chemical solution, wherein the chemical solution comprises at least one of sodium hydroxide, hydrogen peroxide, sodium nitrite, ethanol, potassium permanganate, hypochlorous acid and hydrochloric acid, the chemical solution contains a large amount of chemical particles, and the chemical solution has certain chemical properties, some of the chemical solutions also have oxidability, various active nitrogen and oxygen substances generated by the plasma can completely and completely react with the particles in the chemical solution, or the original reaction rate is accelerated, so that the solution obtains stronger chemical activity, the pH value is reduced, and the oxidation-reduction potential is greatly increased; after their treatment with plasma, solutions can be obtained which possess a greater chemical activity, a greater redox potential, a greater killing power than plasma-activated water.
2. The plasma processing method for enhancing the killing capability of the chemical solution can greatly improve the killing capability of the chemical solution in a short time, and has the advantages of stability, greenness, environmental protection and the like; thereby reducing the use of disinfectant which is difficult to biodegrade and achieving the aim of environmental protection; the operation process is simple, and large-scale treatment of chemical solution can be realized by developing a large-area array plasma treatment device so as to meet the requirements of commercial application and industrial application.
Drawings
FIG. 1 is a schematic diagram showing a plasma bare needle discharge device, a DBD discharge device, and an air plasma array discharge device (a), (b), and (c), respectively;
fig. 2 is a schematic diagram of a plasma processing system with enhanced chemical solution killing capabilities according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The embodiment of the invention provides a plasma processing method for enhancing the killing capacity of a chemical solution, which comprises the following steps:
s1, placing the chemical solution in a container; wherein the chemical solution comprises: at least one of sodium hydroxide, hydrogen peroxide, sodium nitrite, ethanol, potassium permanganate, hypochlorous acid or hydrochloric acid.
Specifically, a volume of chemical solution is removed and placed in a container. The container should ensure reliable grounding as a ground electrode for the plasma.
And S2, processing the solution by using a plasma generating device to obtain the chemical solution after plasma processing.
Specifically, the solution is directly treated for a period of time by using plasma, and the treated solution is collected and stored in a dark place at a low temperature.
The activating chemical solution obtained after plasma treatment can be directly used or stored under the condition of low temperature and light resistance.
The plasma processing method for enhancing the killing capability of the chemical solution is characterized in that the chemical solutions such as sodium hydroxide, hydrogen peroxide, sodium nitrite, ethanol, potassium permanganate and hydrochloric acid are processed by using the plasma, the solutions have a large amount of chemical particles, and after the plasma is used for short-time processing, the particles existing in the chemical solutions can continuously react with the particles generated by the plasma in a liquid phase, so that the chemical solutions have stronger chemical properties and sterilizing and disinfecting capabilities.
The chemical solution is not limited to sodium hydroxide, hydrogen peroxide, sodium nitrite, ethanol, potassium permanganate, hydrochloric acid, and the like, and other chemical solutions may be selected as the solution to be treated. By "possessing greater chemical activity" is meant that the solution being treated will possess a lower pH, a higher redox potential, and a richer content of active particles. These are the key points for the plasma activated solution to have a stronger killing power.
It is understood that the plasma is not used to treat the chemical solution too long or too short. Too short a treatment time may result in an insignificant increase in the killing capacity of the chemical solution, while too long a treatment time may reduce the efficiency of the treatment, typically within 10 minutes.
Preferably, the plasma generating device is a dielectric barrier discharge plasma generating device, a sliding arc discharge plasma generating device or a jet array discharge plasma generating device.
Specifically, the plasma processing apparatus used may be various, and as shown in fig. 1 (a), (b), and (c), the plasma bare needle discharge apparatus, the DBD discharge apparatus, and the air plasma array discharge apparatus are respectively used. The drawings are merely exemplary, and the plasma discharge devices that can be used are not limited to the three types of the drawings.
Preferably, the driving power supply of the plasma generating device is a nanosecond pulse power supply, a microsecond pulse power supply, an alternating current power supply or a direct current power supply.
Specifically, the plasma generation device may be driven by different power sources, including nanosecond pulse power source, microsecond pulse power source, alternating current power source, direct current power source, and the like.
Preferably, the working gas of the plasma generating device is nitrogen, air, helium or argon.
Specifically, the working gas used by the plasma generating device may be various, including nitrogen, air, helium, argon, and the like.
Preferably, the vessel is grounded to provide a ground electrode for plasma discharge.
Preferably, one end of the ground line is connected to the chemical solution, and the other end is grounded to provide a ground electrode for plasma discharge.
An embodiment of the present invention provides a plasma processing system for enhancing killing ability of a chemical solution, including: the plasma array device, the direct-current low-voltage power supply, the boosting module, the container and the grounding wire;
the container is used for containing chemical solution to be treated, and the grounding wire is connected with the solution to be treated and the ground to provide a ground electrode for discharging of the plasma array device;
the plasma array device is driven by a direct-current low-voltage power supply through a boosting module to generate plasma so as to treat the chemical solution in the container.
As shown in fig. 2, the plasma activating liquid system for enhancing the killing ability of the chemical solution is mainly composed of a dc-driven air plasma array device 3 and the chemical solution 5 to be treated. The plasma device is driven by a direct current low voltage power supply 1 through a boost module 2. The solution to be treated is contained in a container and is connected to the ground and the solution by a ground wire 4. The boosting module diagram is 1000 times of boosting modules, and can boost low-voltage direct-current voltage of several volts to a kilovolt level; the air plasma array device is used for generating plasma; and the grounding wire is used for connecting the solution to be treated and the ground.
It should be noted here that some plasma treatment modes, such as rare gas jet discharge, do not require grounding of the solution, as long as the requirement of grounding of the container holding the solution is met. In the plasma discharging process, the plasma can continuously react with air to generate a large amount of active nitrogen oxygen substances, and the substances can further react with the solution to be treated, so that the killing capacity of the chemical solution is greatly improved.
The embodiment of the invention also provides a chemical solution prepared by the method in any embodiment.
The technical solution of the present invention is further illustrated by the following specific examples.
Example one
A portable large area plasma air jet array apparatus was used to treat a 240. mu. mol/L hydrogen peroxide solution for 1 minute at a discharge voltage of 10 kV. The chemical solution was tested for changes in particles, pH and redox potential before and after treatment as shown in table 1.
TABLE 1
Various index parameters Before plasma treatment After plasma treatment
Nitrite radical 0μmol/L 64μmol/L
Nitrate radical 0μmol/L 478μmol/L
Peroxy compoundHydrogenation of hydrogen 240μmol/L 427μmol/L
Redox potential 272mV 413mV
pH value 6.8 3.38
It was found that after the plasma treatment, the pH of the hydrogen peroxide solution was greatly lowered to a concentration of 1.58X 10 hydrogen ions-7The mol/L is increased to 4.17 multiplied by 10-4mol/L. The redox potential increased 141 mV. Using the solution pair 107The treatment with the CFU/ml solution of Escherichia coli shows that the plasma treated solution can achieve about 4 orders of magnitude of sterilization effect, while the hydrogen peroxide solution without plasma treatment can kill only about a few tenths of orders of magnitude of bacteria. From this result, it was found that the treatment with plasma greatly improved the killing ability of the hydrogen peroxide chemical solution.
Example two
A mixed solution of 0.001mol/L hydrochloric acid and 240. mu. mol/L hydrogen peroxide was treated for 1 minute at a discharge voltage of 10kV using a portable large-area plasma air jet array apparatus. The chemical solution was tested for changes in particle, pH and redox potential before and after treatment as shown in table 2.
TABLE 2
Various index parameters Before plasma treatment After plasma treatment
Nitrite radical 0μmol/L 20μmol/L
Nitrate radical 0μmol/L 680μmol/L
Hydrogen peroxide 240μmol/L 389μmol/L
Redox potential 356mV 440mV
pH value
3 2.82
It was found that the pH of the mixed solution of hydrochloric acid and hydrogen peroxide was lowered by 0.18 after the plasma treatment, and the hydrogen ion concentration in the solution was from 1X 10-3mol/L was changed to 1.51X 10-3mol/L. The redox potential increased by 84 mV. Using the solution pair 107The Escherichia coli solution of CFU/ml is treated, and the complete killing of the Escherichia coli can be realized by using the mixed solution after plasma treatment, while the bacteria of which the number is only a few orders of magnitude can be killed by using the mixed solution without plasma treatment. From the above results, hydrochloric acid and sulfuric acid were obtainedThe hydrogen oxide mixed solution has weak killing capacity, and the killing capacity of the chemical solution can be greatly improved after the plasma treatment.
EXAMPLE III
A mixed solution of 0.001mol/L hydrochloric acid, 240. mu. mol/L hydrogen peroxide and 110. mu. mol/L nitrite was treated for 1 minute at a discharge voltage of 10kV using a portable large-area plasma air jet array apparatus. The chemical solution was tested for changes in particle, pH and redox potential before and after treatment as shown in table 3.
TABLE 3
Various index parameters Before plasma treatment After plasma treatment
Nitrite radical 110μmol/L 45μmol/L
Nitrate radical 0μmol/L 691μmol/L
Hydrogen peroxide 240μmol/L 339μmol/L
Redox potential 350mV 451mV
pH value
3 2.85
It was found that the pH of the mixed solution of hydrochloric acid, hydrogen peroxide and nitrite was lowered by 0.15, i.e., the hydrogen ion concentration in the solution was from 1X 10 after the plasma treatment-3mol/L becomes 1.41X 10-3mol/L. The redox potential was increased by 101 mV. Using the solution pair 107The treatment of CFU/ml colibacillus solution is found to realize the complete killing of colibacillus by using the solution after plasma treatment, and the mixed solution of hydrochloric acid, hydrogen peroxide and nitrite which is not subjected to plasma treatment can only kill bacteria of several orders of magnitude. From this result, it was found that the plasma greatly improved the killing ability of the mixed solution.
Example four
A portable large area plasma air jet array apparatus was used to treat 5%, 10%, 15% concentration gradient alcohol solutions for 2 minutes at a discharge voltage of 10 kV. Followed by treatment 10 with the activating solution8CFU/ml E.coli, the results are shown in Table 4.
TABLE 4
Figure BDA0003574814940000081
Figure BDA0003574814940000091
It was found that these concentration gradients of alcohol showed a greater increase in the bactericidal effect after 2 minutes of plasma treatment than before treatment.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. A plasma processing method for enhancing the killing power of a chemical solution, comprising:
treating the chemical solution in the container by using a plasma generating device to obtain the chemical solution after plasma treatment;
wherein the chemical solution comprises: at least one of sodium hydroxide, hydrogen peroxide, sodium nitrite, ethanol, potassium permanganate, hypochlorous acid or hydrochloric acid.
2. The method of claim 1, wherein the vessel is grounded to provide a ground electrode for the plasma discharge.
3. The method of claim 1, wherein one end of the ground line is connected to the chemical solution and the other end is grounded to provide a ground electrode for the plasma discharge.
4. The method of claim 1, wherein the plasma generating device is a dielectric barrier discharge plasma generating device, a sliding arc discharge plasma generating device, or a fluidic array discharge plasma generating device.
5. The method of claim 1, wherein the driving power of the plasma generating device is a nanosecond pulse power, a microsecond pulse power, an alternating current power, or a direct current power.
6. The method of claim 1, wherein the working gas of the plasma generating device is nitrogen, air, helium, or argon.
7. A chemical solution prepared by the method of any one of claims 1-6.
8. A plasma processing system for enhancing the killing power of a chemical solution, comprising: the plasma array device, the direct-current low-voltage power supply, the boosting module, the container and the grounding wire;
the container is used for containing chemical solution to be treated, and the grounding wire is connected with the solution to be treated and the ground to provide a ground electrode for discharging of the plasma array device;
the plasma array device is driven by a direct-current low-voltage power supply through a boosting module to generate plasma so as to treat the chemical solution in the container.
CN202210337197.2A 2022-03-31 2022-03-31 Plasma processing method for enhancing killing capability of chemical solution Pending CN114713158A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2357957A1 (en) * 2000-10-02 2002-04-02 Ethicon, Inc. Power system for sterilization systems employing low frequency plasma
CN103747606A (en) * 2013-12-27 2014-04-23 华中科技大学 Circuit generated low temperature plasma
CN107406280A (en) * 2014-12-15 2017-11-28 埃因霍温科技大学 Plasma-activated water
CN112689372A (en) * 2020-12-10 2021-04-20 西安交通大学 Method for restoring/enhancing chemical activity of plasma activation solution

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2357957A1 (en) * 2000-10-02 2002-04-02 Ethicon, Inc. Power system for sterilization systems employing low frequency plasma
CN103747606A (en) * 2013-12-27 2014-04-23 华中科技大学 Circuit generated low temperature plasma
CN107406280A (en) * 2014-12-15 2017-11-28 埃因霍温科技大学 Plasma-activated water
CN112689372A (en) * 2020-12-10 2021-04-20 西安交通大学 Method for restoring/enhancing chemical activity of plasma activation solution

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Application publication date: 20220708