In recent years, people are increasingly interested in CO2 hydrogenation to produce value-added chemicals and fuels ( CH4, CH3OH, etc.). In the quest for an efficient treatment in CO2 methanation and methanolization, several technologies have been practiced, and DBD plasma technology gain attention due to its easily handling, mild operating conditions, strong activation ability, and high product selectivity. In addition, its reaction mechanism and the effect of packing materials and reaction parameters are still controversial. To address these problems efficiently, a summary of the reaction mechanism is presented. A discussion on plasma-catalyzed CO2 hydrogenation including packing materials, reaction parameters, and optimizing methods is addressed. In this review, the overall status and recent findings in DBD plasma-catalyzed CO2 hydrogenation are presented, and the possible directions of future development are discussed.
The purpose of this study was to compare the efficiency of air and oxygen injected into the underwater non-thermal dielectric barrier discharge plasma (DBD plasma) device used to remove five types of antibiotics (tetracycline, doxycycline, oxytetracycline, clindamycin, and erythromycin) artificially contained in the fish farm discharge water. The voltage given to generate DBD plasma was 27.8 kV, and the measurement intervals were 0, 0.5, 1, 2, 4, 8, 16 and 32 minutes. Tetracycline antibiotics significantly decreased in 4 minutes when air was injected and were reduced in 30 seconds when oxygen was injected. After the introduction of air and oxygen at 32 minutes, 78.1% and 95.8% of tetracycline were removed, 77.1% and 96.3% of doxycycline were removed, and 77.1% and 95.5% of oxytetracycline were removed, respectively. In air and oxygen, 59.6% and 83.0% of clindamycin and 53.3% and 74.3% of erythromycin were removed, respectively. The two antibiotics showed lower removal efficiency than tetracyclines. In conclusion, fish farm discharge water contains five different types of antibiotics that can be reduced using underwater DBD plasma, and oxygen gas injection outperformed air in terms of removal efficiency.
Tributyl phosphate (TBP) is a well-known and important compound in the nuclear industry for the nuclear fuel reprocessing, and it is also used in a various field such as plastic industry as antifoaming agent. Untreated organic pollutants in TBP can remain in the soil water and cause serious environmental pollution, thus it should be degraded through environmentally friendly methods. The non-thermal plasma-based advanced oxidation process (AOP) is one of the most widely studied and best developed processes owing to its simple structure and ease of operation. In this study, a plasma-based AOP was stably generated using submerged multi-hole dielectric barrier discharge (DBD) and applied to relatively high concentration of TBP solution. A submerged DBD plasma system was designed to directly interact with water, thereby producing reactive oxygen species (ROS) and functioning as a powerful oxidizer. Additionally, UV, O3, and H2O2 are generated by the developed plasma system without using any other additives to produce OH radicals for degrading organic pollutants; therefore, this system circumvents the use of complex and advanced oxidation processes. The electrical properties and concentrations of the active species were analyzed to establish optimal plasma operating conditions for degrading TBP solution. The results were analyzed by measuring the total organic carbon (TOC) and changes in solution properties. Based on these results, a degradation mechanism of TBP solution is proposed. After 50 min of plasma treatment, the concentration of TOC was gradually decreased. Consequently, we found that plasma-based AOP using submerged multi-hole DBD has advantages as an alternative technology for degrading organic pollutants such as TBP solution.
This study investigated the degradation characteristics and biodegradability of phenol, refractory organic matters, by injecting MgO and CaO-known to be catalyst materials for the ozonation process-into a Dielectric Barrier Discharge (DBD) plasma. MgO and CaO were injected at 0, 0.5, 1.0, and 2 g/L, and the pH was not adjusted separately to examine the optimal injection amounts of MgO and CaO. When MgO and CaO were injected, the phenol decomposition rate was increased, and the reaction time was found to decrease by 2.1 to 2.6 times. In addition, during CaO injection, intermediate products combined with Ca2+ to cause precipitation, which increased the COD (chemical oxygen demand) removal rate by approximately 2.4 times. The biodegradability of plasma treated water increased with increase in the phenol decomposition rate and increased as the amount of the generated intermediate products increased. The biodegradability was the highest in the plasma reaction with MgO injection as compared to when the DBD plasma pH was adjusted. Thus, it was found that a DBD plasma can degrade non-biodegradable phenols and increase biodegradability.
Sodium dodecylbenzen sulfonate (DBS) and linear alkylbenzene sulfonate (LAS) are widely used in dishwashing products. Residual levels of these surfactants are commonly found on the surfaces of dishware following dishwashing. Residual surfactants and detergents can act as potential toxicants and may pose health risks. This study explored the applicability of dielectric barrier discharge plasma (DBDP) for the degradation of residual surfactants in order to minimize their harmful effects. The plasma was generated using 10 kV pulsed DC power supply at different input currents (2.0-3.0 A) and at various inter-electrode gaps (2.0-3.0 mm). Under simulatory treatment conditions, diluted surfactants (DBS and LAS) and DBS-containing dishwashing detergents dispersed on slide glasses were exposed to DBDP for predetermined periods of time. Results indicated that, under optimal treatment conditions of 3.0 A current and 2.0 mm inter-electrode gap, tested surfactants and surfactants in detergents were degraded in the range of 60- 70% following the plasma treatment for 120 min. Modeling of degradation kinetics indicated that Weibull distribution was the best-fit model, and decimal degradation times (δ) were calculated. Pure surfactants were degraded at relatively higher level than surfactants in detergents. Among these anionic surfactants, DBS was more rapidly degraded than LAS by plasma treatment.
This objective of this study was to investigate the degradation characteristics of phenol, a refractory substance, by using a submerged dielectric barrier discharge (DBD) plasma reactor. To indirectly determine the concentration of active species produced in the DBD plasma, the dissolved ozone was measured. To investigate the phenol degradation characteristics, the phenol and chemical oxygen demand (COD) concentrations were evaluated based on pH and the discharge power. The dissolved ozone was measured based on the air flow rate and power discharged. The highest dissolved ozone concentration was recorded when the injected air flow rate was 5 L/min. At a discharge power of 40W as compared to 70W, the dissolved ozone was approximately 2.7 – 6.5 times higher. In regards to phenol degradation, the final degradation rate was highest at about 74.06%, when the initial pH was 10. At a discharged power of 40W, the rate of phenol decomposition was observed to be approximately 1.25 times higher compared to when the discharged power was 70W. It was established that the phenol degradation reaction was a primary reaction, and when the discharge power was 40W as opposed to 70W, the reaction rate constant(k) was approximately 1.72 times higher.
Stream of afterglow of an atmospheric pressure plasma can conveniently be used for large scale decontamination operations. In the present study, an afterglow dielectric-barrier discharge air plasma (ADDAP) was used to inactivate Escherichia coli O157:H7 as a model microorganism for studying the plasma inactivation effect. The plasma was generated at current levels in the range of 0.4 - 0.8 A. The power consumption of ADDAP generation system ranged 169.5 - 221.9 W with respect to the current intensity range. At this current level, the temperature observed in the treatment chamber remained less than 30℃. Regarding chemical composition of ADDAP in the treatment chamber, NOx species were predominantly generated. The levels of NOx species increased as the current intensity increases and the maximum NO and NO2, concentrations noted were 6 and 4 ppm, respectively, but that of CO was less than 1 ppm level at 0.8 A. Upon treating with the ADDAP generated at 0.4 - 0.8 A for 180 min, E. coli O157:H7 showed 1.24 – 2.71 log reductions. The inactivation patterns exhibited better fit to Weibull-tail model. The comparison of delta values indicated that superior inactivation effects were observed as the current intensity increased.
Residual detergents and surfactants on utensils have brought about health issues because they can be absorbed to human digestion system together with containing foods. In the present study, a dielectric barrier discharge plasma (DBDP) was used to explore the applicability of non-thermal plasma for the degradation of residual surfactants and dishwashing detergents in order to reduce the intake of the residues remaining on utensils as the result of incomplete rinsing during dishwashing procedures. DBDP was generated at current intensity 2.0 - 3.0 A, and electrode gap 2.5 mm. Diluted dishwashing detergents and surfactants were spotted on slide glasses and exposed to DBDP for different periods of time. The results indicated that the dishwashing detergents and surfactants were degraded by 46.9 - 84.3% after up to 120 min treatments. Weibull equation was the best fit model to the degradation patterns of surfactants, and the decimal degradation time(δ) of 180.2 - 688.9 min were observed according to currents. Surfactants contained in detergents were degraded more effectively than the surfactants themselves. Among the anion surfactants, DDBS was more rapidly degraded than LAS and ABS.
본 연구는 대기압 유전체장벽방전 플라즈마 처리에 따른 식품유해 미생물 사멸효과를 조사하기 위해 수행되었다. 플라즈마 처리 시, 활성종 생성 및 농도에 영향을 미치는 노출시간, 노출거리, 산소비율, 전력 변화에 따른 E. coli의 사멸효과를 조사한 결과, E. coli의 사멸율은 플라즈마 처리를 위한 노출시간, 산소비율, 전력의 증가에 따라 증가한 반면, 노출거리의 증가에 따라서는 사멸율이 감소하였다. 이 결과는 미생물 시료가 플라즈마에 노출되는 시간이 증가됨으로서 시료 내 NO 농도가 증가되고, E.coli의 사멸율 역시 증가되는 결과로 뒷받침할 수 있고, 미 생물 사멸효과를 높이기 위해서는 활성종의 농도가 증가 되어야 함을 의미한다. E. coli와 함께 B. cereus, B. subtilis, B. thuringiensis, B. atrophaeus를 대상으로 대기압 유전체 장벽방전 플라즈마에 의한 살균효과를 조사한 결과, 72.3~91.3%의 높은 사멸율을 나타내었다. 이러한 결과로 미루어, 대기압 유전체장벽방전 플라즈마기술은 다양한 미생물에 적용될 수 있는 유용한 살균기술임을 확인하였다.
This work investigated the decomposition of aqueous anatoxin-a originated from cyanobacteria using an underwater dielectric barrier discharge plasma system based on a porous ceramic tube and an alternating current (AC) high voltage. Plasmatic gas generated inside the porous ceramic tube was uniformly dispersed in the form of numerous bubbles into the aqueous solution through the micro-pores of the ceramic tube, which allowed an effective contact between the plasmatic gas and the aqueous anatoxin-a solution. Effect of applied voltage, treatment time and the coexistence of nutrients such as NO3 -, H2PO4 - and glucose on the decomposition of anatoxin-a was examined. Chemical analyses of the plasma-treated anatoxin-a solution using liquid chromatography-mass spectrometry (LC-MS) and ion chromatography (IC) were performed to elucidate the mineralization mechanisms. Increasing the voltage improved the anatoxin-a decomposition efficiency due to the increased discharge power, but the energy required to remove a given amount of anatoxin-a was similar, regardless of the voltage. At an applied voltage of 17.2 kV (oxygen flow rate: 1.0 L min-1), anatoxin-a at an initial concentration of 1 mg L-1 (volume: 0.5 L) was successfully treated within 3 min. The chemical analyses using LC-MS and IC suggested that the intermediates with molecular weights of 123~161 produced by the attack of plasma-induced reactive species on anatoxin-a molecule were further oxidized to stable compounds such as acetic acid, formic acid and oxalic acid.
비열 처리 기술인 유전체 장벽 방전 저온 플라즈마(dielectric barrier discharge cold plasma, DBD-CP)를 이용하여 양 파 분말에 접종된 Salmonella Enteritidis, Escherichia coli O157:H7, 그리고 Listeria monocytogenes의 저해 효과를 조사 하였다. DBD-CP 처리 조건으로서 DBD-CP 형성 가스는 헬륨이었고, 독립 변인은 처리 전압(4, 5, 6, 7, 8, 그리고 9 kV)과 처리 시간(5, 10, 12, 15, 그리고 20분)이었다. 미생물 저해율과 양파 분말의 표면 온도를 종속 변인으로 하여 DBD-CP 최적화 조건을 확립하였고, 이를 바탕으로 S. Enteritidis 저해율에 대한 예측 모델을 구축하였다. 또한 양파 분말의 입자 크기와 수분활성도(Aw)에 따른 S. Enteritidis 저해 효과를 알아보았다. 또다른 처리 조건으로서 헬륨-물 혼 합 가스를 형성 가스로 사용하여 9 kV에서 5분 동안 주파수(15, 25, 그리고 35 kHz)에 따른 미생물 저해율과 시료 표면 온도에 대한 영향을 관찰하였다. DBD-CP 처리에 의해 양파 분말에 접종된 S. Enteritidis, E. coli O157:H7, 그리고 L. monocytogenes는 각각 ≤2.3 ± 0.1, ≤1.4 ± 0.2, 그리고 ≤0.7 ± 1.2 log CFU/cm 2까지 저해되었고, 시료의 최고 온도는 38.5 ± 1.52℃이었다. 양파 분말에 접종된 S. Enteritidis의 저해율에 대한 DBD-CP 최적 조건은 9 kV와 20분이었고, S. Enteritidis 저해율을 가장 적절하게 예측한 모델은 Fermi’s model (R 2 =0.93)이었다. 수분활성도가 0.4, 0.8인 양파 분말의 S. Enteritidis 저해율은 각각 2.3 ± 0.1, 1.8 ± 0.1 log CFU/cm 2로 유의적인 차이가 없었고(p>0.05), 입자 크기가 0.25, 1.00 cm 2인 양파 분말의 S. Enteritidis 저해율은 각각 2.3 ± 0.1, 1.0 ± 0.5 log CFU/cm 2로 입자의 크기가 작을수록 저해율이 높았다. 헬륨-물 혼합 가스로 DBD-CP 처리시 모든 식중독균에서 주파수가 작을수록 저해율이 증가하였고, 헬륨의 단 독 처리에 비해 미생물 저해율이 유의적으로 증가하였다(p<0.05). 현 연구를 통해 DBD-CP 처리 기술은 분말 식품의 품질 보존 및 미생물 안전성을 향상시키기 위한 살균 방법으로서의 가능성을 보여주었다.
Atmospheric pressure plasma is used in the biological and medical fields. Miniaturization and safety are important in the application of apply atmospheric plasma to bio devices. In this study, we made a small, pocket-sized inverter for the discharge of atmospheric plasma. We used pulse power to control the neutral gas temperature at which the, when plasma was discharged. We used direct current of 5 V of bias(voltage). The output voltage is about 1 to 2 kilo volts the frequency is about 80 kilo hertz. We analyzsed the characteristics of the atmospheric plasma using OES(Optical emission spectroscopy) and the Current-Voltage characteristic of pulse power. By calculating of the current voltage characteristics, we were able to determine that, when the duty ratio increased, the power that actually effects the plasma discharge also increased. To apply atmospheric plasma to human organisms, the temperature is the most important factor, we were able to control the temperature by modulating the pulse power duty ratio. This means we can use atmospheric plasma on the human body or in other areas of the medical field.
식품의 열에 의한 손상을 줄이고 안전성을 높이기 위한 비열살균기술로 유전체장벽방전 플라즈마(DBDP) 이용 가능성을 타진하기 위하여 E. coli에 대한 살균효과를 전류세기와 전극간격을 달리하여 조사하였다. DBDP 살균효과는 초기에는 크게 나타나다가 이후 감소하는 2 구간으로 구성된 1차 반응으로 나타났고, 전류세기에 따라 살균효과가 증가하였다. 전극간격에 따른 살균력은 2.65 mm에서 가장 높았으며, 3.33 mm, 1.85 mm 순으로 감소하였다. DBDP 살균패턴은 Singh-Heldman 모델에 적합하였으며, 시료를 고정하고 DBDP를 처리한 경우 곡선형상계수(n)는 0.545-0.783 범위의 값을, D'-value는 0.565-3.268min의 값을 보였다. 최소 D'-value는 전극간격 2.65mm, 전류 1.25 A에서 나타나 가장 우수한 살균력을 보이는 조건으로 확인되었다. DBDP 처리 시 시료를 이동시키면 고정하여 처리한 경우에 비하여 살균효과는 크게 향상되었으며, 양방향 이동식 처리가 단일방향 이동식 처리에 비하여 양호한 살균력을 보였다.
비열살균기술로서 저온플라즈마 활용 가능성을 탐색하고자 유전체장벽 방전 플라즈마(DBDP)생성장치를 제작하여 최적 플라즈마생성 조건을 도출하고 Staphylococcus aureus를 대상으로 살균성능을 조사하였다. DBDP생성장치는 전력공급장치, 변압기, 전극, 시료처리부 등 네 부분으로 구성하였다. 인가전압은 단상 200 V AC를 사용하고, 변압기를 통하여 10.0-50.0 kV로 변환하고 10.0-50.0 kHz의 주파수의 펄스 구형파를 유전체인 세라믹 블록 내에 장치한 전극에 투입함으로써 상압에서 플라즈마를 생성하였다. 주파수를 올림에 따라 높은 전류가 유입되었고, 이에 비례하여 전력소비량이 증가하였다. 전류세기 1.0-2.0 A, 주파수 32.0-35.3 kHz 범위에서 균일하고 안정적인 플라즈마 발생이 이루어졌으며 시료를 투입하지 않은 상태에서의 최적 전극간격은 1.85 mm 이었다. 전극간격을 높임에 따라 소비 전력이 증가하였으나 시료 처리에 적합한 전극간격은 2.65 mm였다. DBDP 처리에 의한 온도상승은 최대 20oC에 불과하여 열에 의한 생물학적 효과는 무시할 수 있었으며 따라서 비열기술임이 확인되었다. Staphylococcus aureus를 대상으로 DBDP 처리할 경우 초기 5분 동안은 살균치가 직선적인 증가를 보이다가 이후 다소 완만해지는 경향을 보였으며 1.25 A에서 10분간 처리 시 살균치는 5.0을 상회하였다.
This study was conducted to investigated the possibility of inactivating wilt germs (Fusarium oxysporum f. sp. radicis lycopersici) using Dielectric Barrier Discharge (DBD) plasma in a hydroponic system. Recirculating hydroponic cultivation system for inactivation was consisted of planting port, LED lamp, water tank, and circulating pump for hydroponic and DBD plasma reactor. Two experiments were conducted: batch and intermittent continuous process. The effect of plasma treatment on Total Residual Oxidants (TRO) concentration change, Fusarium inactivation and growth of lettuce were investigated. In the batch experiment, most of the Fusarium was inactivated at a TRO concentration of 0.15 mg/L or more at four-day intervals. There was no change in lettuce growth after two times of plasma treatment for one week. The intermittent continuous experiment consisted of 30-minute, 60-minute, and 90-minute plasma treatment in 2 day intervals and 30-minute treatment a one-day; most of the Fusarium was inactivated only by treatment for 30-minute every two days. However, if inactivation under 101 CFU/mL is required, it will be necessary to treat for 60 minutes in 2 day intervals. The plasma treatment caused no damage to the lettuce, except the 30 min plasma treatment ay the one-day interval. It was considered that the residual TRO concentration was higher than that of the other treatments.
Many chemically active species such as ·H, ·OH, O3, H2O2, hydrated e-, as well as ultraviolet rays, are produced by Dielectric Barrier Discharge (DBD) plasma in water and are widely use to remove non-biodegradable materials and deactivate microorganisms. As the plasma gas containing chemically active species that is generated from the plasma reaction has a short lifetime and low solubility in water, increasing the dissolution rate of this gas is an important challenge. To this end, the plasma gas and water within reactor were mixed using the air-automizing nozzle, and then, water-gas mixture was injected into water. The dissolving effect of plasma gas was indirectly confirmed by measuring the RNO (N-Dimethyl-4-nitrosoaniline, indicator of the formation of OH radical) solution. The plasma system consisted of an oxygen generator, a high-voltage power supply, a plasma generator and a liquid-gas mixing reactor. Experiments were conducted to examine the effects of location of air-automizing nozzle, flow rate of plasma gas, water circulation rate, and high-voltage on RNO degradation. The experimental results showed that the RNO removal efficiency of the air-automizing nozzle is 29.8% higher than the conventional diffuser. The nozzle position from water surface was not considered to be a major factor in the design and operation of the plasma reactor. The plasma gas flow rate and water circulation rate with the highest RNO removal rate were 3.5 L/min and 1.5 L/min, respectively. The ratio of the plasma gas flow rate to the water circulation rate for obtaining an RNO removal rate of over 95% was 1.67 ~ 4.00.