Effects of Dielectric Barrier Discharge Plasma Treatment on Pentachlorophenol Removal of Granular Activated Carbon

The pentachlorophenol(PCP)adsorbed granular activated carbon(GAC)was treated by dielectric barrier discharge(DBD)plasma.The effects of DBD plasma on the structure of GAC and PCP decomposition were analyzed by N_2 adsorption,thermogravimetric,scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS)and gas chromatographymass spectrometry(GC-MS).The experimental data of adsorption kinetics and thermodynamics of PCP on GAC were fitted with different kinetics and isotherm models,respectively.The results indicate that the types of N_2 adsorption isotherm of GAC are not changed by DBD plasma,while the specific surface area and pore volume increase after DBD plasma treatment.It is found that the weight loss of the saturated GAC is the highest,on the contrary,the weight loss of DBD treated GAC is the least because of reduced PCP residue on the GAC.The XPS spectra and SEM image suggest that some PCP on the GAC is removed by DBD plasma,and the surface of GAC treated by DBD plasma presents irregular and heterogeneous morphology.The GC-MS identification of by-products shows that two main dechlorination intermediate products,tetrachlorophenol and trichlorophenol,are distinguished.The fitting results of experimental data of adsorption kinetics and thermodynamics indicate that the pseudo-first-order and pseudo-second order models can be used for the prediction of the kinetics of virgin GAC and DBD treated GAC for PCP adsorption,and the Langmuir isotherm model fits better with the data of adsorption isotherm than the Freundlich isotherm in the adsorption of PCP on virgin GAC and DBD treated GAC.     

Degradation of phenol using a combination of granular activated carbon adsorption and bipolar pulse dielectric barrier discharge plasma regeneration

A combined method of granular activated carbon (GAC) adsorption and bipolar pulse dielectric barrier discharge (DBD) plasma regeneration was employed to degrade phenol in water. After being saturated with phenol, the GAC was filled into the DBD reactor driven by bipolar pulse power for regeneration under various operating parameters. The results showed that different peak voltages, air flow rates, and GAC content can affect phenol decomposition and its major degradation intermediates, such as catechol, hydroquinone, and benzoquinone. The higher voltage and air support were conducive to the removal of phenol, and the proper water moisture of the GAC was 20％. The amount of H2O2 on the GAC was quantitatively determined, and its laws of production were similar to phenol elimination. Under the optimized conditions, the elimination of phenol on the GAC was confirmed by Fourier transform infrared spectroscopy,and the total removal of organic carbons achieved 50.4％. Also, a possible degradation mechanism was proposed based on the HPLC analysis. Meanwhile, the regeneration efficiency of the GAC was improved with the discharge treatment time, which attained 88.5％ after 100 min of DBD processing.     

Strengthening decomposition of oxytetracycline in DBD plasma coupling with Fe-Mn oxide-loaded granular activated carbon

A catalytic approach using a synthesized iron and manganese oxide-supported granular activated carbon (Fe-Mn GAC) under a dielectric barrier discharge (DBD) plasma was investigated to enhance the degradation of oxytetracycline (OTC) in water. The prepared Fe-Mn GAC was characterized by x-ray diffraction and scanning electron microscopy, and the results showed that the bimetallic oxides had been successfully spread on the GAC surface. The experimental results showed that the DBD + Fe-Mn GAC exhibited better OTC removal efficiency than the sole DBD and DBD + virgin GAC systems. Increasing the fabricated catalyst and discharge voltage was favorable to the antibiotic elimination and energy yield in the hybrid process. The coupling process could be elucidated by the ozone decomposition after Fe-Mn GAC addition, and highly hydroxyl and superoxide radicals both play significant roles in the decontamination. The main intermediate products were identified by HPLC-MS to study the mechanism in the collaborative system.     

Ozone generation enhanced by silica catalyst in packed-bed DBD reactor

In this paper, three dielectric barrier discharge(DBD) configurations, which were plain DBD with no packing, DBD with packed pure quartz fibers and DBD with packed loaded quartz fibers, were employed to investigate the effect and catalytic mechanism of catalyst materials in a packed-bed ozone generator. From the experimental results, it was clear that the DBD configuration with packed pure fibers and packed loaded fibers promotes ozone generation. For the packed-bed reactor, ozone concentration and ozone yield were enhanced by an increase of electric field in the discharge gap with the packed-bed effect. Meanwhile, the enhancement of ozone concentration and yield for the DBD reactor packed by loaded fibers with silica nanoparticles was due to the catalysis of silica nanoparticles on the fiber surface. The adsorption of silica nanoparticles on the fiber surface can prolong the retention time of active species and enhance surface reactions.     

Regeneration of Acid Orange 7 Exhausted Granular Activated Carbon Using Pulsed Discharge Plasmas

In this paper, a pulsed discharge plasma(PDP) system with a multi-needle-to-plate electrodes geometry was set up to investigate the regeneration of acid orange 7(AO7) exhausted granular activated carbon(GAC). Regeneration of GAC was studied under different conditions of peak pulse discharge voltage and water p H, as well as the modification effect of GAC by the pulse discharge process, to figure out the regeneration efficiency and the change of the GAC structure by the PDP treatment. The obtained results showed that there was an appropriate peak pulse voltage and an optimal initial p H value of the solution for GAC regeneration. Analyses of scanning electron microscope(SEM), Boehm titration, Brunauer-Emmett-Teller(BET), Horvath-Kawazoe(HK), and X-ray Diffraction(XRD) showed that there were more mesopore and macropore in the regenerated GAC and the structure turned smoother with the increase of discharge voltage;the amount of acidic functional groups on the GAC surface increased while the amount of basic functional groups decreased after the regeneration process. From the result of the XRD analysis,there were no new substances produced on the GAC after PDP treatment.     

Experimental study on the parameter optimization and application of a packed-bed dielectric barrier discharge reactor in diesel particulate filter regeneration

To compensate for the shortcomings of the thermal and catalytic regeneration of the diesel particulate filter(DPF),a self-designed packed-bed dielectric barrier discharge(DBD)reactor for DPF regeneration was developed.The DBD reactor with the main active substance of nonthermal plasma(NTP)as the target parameter was optimized by adjusting the feed gas,packing particles(material or size),and cooling water temperature.Moreover,a set of optimal working parameters(gas source,O2;packing particles,1.2-1.4 mm ZrO2;and cooling water temperature,20℃)was selected to evaluate the effect of different O3 concentrations on DPF regeneration.The research results showed that selecting packing particles with high dielectric constant and large particles,as well as reducing the cooling water temperature,with oxygen as the feed gas,contributed to an increase in O3 concentration.During DPF regeneration,the following changes were observed:the power of the NTP reactor decreased to lower than 100 W,the O3 concentration increased from 15 g m-3 to 45 g m-3,the CO and CO2 volume fractions of the particulate matter decomposition products increased,and the peak regeneration temperature increased to 173.4℃.The peak temperature arrival time was 60 min earlier,indicating that the regeneration rate of DPF increased with the increase in O3 concentration.However,the O3 utilization rate(the amount of carbon deposit removed per unit volume O3)initially increased and then decreased;when the O3 concentration was set to 25 g m-3,the highest O3 utilization rate was reached.The packed-bed DBD technology contributed to the increase in the concentration of NTP active substances and the regeneration efficiency of DPF.It provides a theoretical and experimental basis for high-efficiency regeneration of DPF at low temperatures(＜200℃).     

Water Content Effect on Oxides Yield in Gas and Liquid Phase Using DBD Arrays in Mist Spray

Electric discharge in and in contact with water can accompany ultraviolet (UV) radiation and electron impact,which can generate a large number of active species such as hydroxyl radicals (OH),oxygen radical (O),ozone (O3) and hydrogen peroxide (H2O2).In this paper,a non thermal plasma processing system was established by means of dielectric barrier discharge (DBD) arrays in water mist spray.The relationship between droplet size and water content was examined,and the effects of the concentrations of oxides in both treated water and gas were investigated under different water content and discharge time.The relative intensity of UV spectra from DBD in water mist was a function of water content.The concentrations of both O3 and nitrogen dioxide (NO2) in DBD room decreased with increasing water content.Moreover,the concentrations of H2O2,O3 and nitrogen oxides (NOx) in treated water decreased with increasing water content,and all the ones enhanced after discharge.The experimental results were further analyzed by chemical reaction equations and commented by physical principles as much as possible.At last,the water containing phenol was tested in this system for the concentration from 100 mg/L to 9.8 mg/L in a period of 35 min.     

Effects of O2 addition on the plasma uniformity and reactivity of Ar DBD excited by ns pulsed and AC power supplies

Dielectric barrier discharges (DBDs) have been widely used in ozone synthesis, materials surface treatment, and plasma medicine for their advantages of uniform discharge and high plasma-chemical reactivity. To improve the reactivity of DBDs, in this work, the O₂ is added into Ar nanosecond (ns) pulsed and AC DBDs. The uniformity and discharge characteristics of Ar ns pulsed and AC DBDs with different O₂ contents are investigated with optical and electrical diagnosis methods. The DBD uniformity is quantitatively analyzed by gray value standard deviation method. The electrical parameters are extracted from voltage and current waveforms separation to characterize the discharge processes and calculate electron density n_e. The optical emission spectroscopy is measured to show the plasma reactivity and calculate the trend of electron temperature T_e with the ratio of two emission lines. It is found that the ns pulsed DBD has a much better uniformity than AC DBD for the fast rising and falling time. With the addition of O₂, the uniformity of ns pulsed DBD gets worse for the space electric field distortion by O₂⁻, which promotes the filamentary formation. While, in AC DBD, the added O₂ can reduce the intensity of filaments, which enhances the discharge uniformity. The ns pulsed DBD has a much higher instantaneous power and energy efficiency than AC DBD. The ratio of Ar emission intensities indicates that the T_e drops quickly with the addition of O₂ both ns pulsed and AC DBDs and the ns pulsed DBD has an obvious higher T_e and n_e than AC DBD. The results are helpful for the realization of the reactive and uniform low temperature plasma sources.     

铀在木纤维上的吸附行为及机理分析

为了解木纤维对铀的吸附特性,通过静态吸附实验,研究了木纤维的粒度、吸附时间、用量、温度及溶液的pH值和初始浓度等因素对模拟含铀废水中U(Ⅵ)去除率的影响,并从热力学和动力学方面对吸附过程进行了分析。结果表明:溶液初始pH≈3时,木纤维对铀的吸附平衡时间为4h,且吸附剂粒径越小、温度越高、用量越大,越有利于铀的去除;铀在木纤维上的吸附过程符合Langmuir等温吸附方程,吸附动力学过程可用准二级吸附动力学模型描述,表明化学吸附主要受动力学控制;木纤维吸附铀是自发的吸热反应。SEM、FT-IR和EDS分析结果表明,木纤维吸附铀后表面形态发生了改变,且在吸附过程中铀主要与木纤维表面活性基团螯合并形成配合物,存在表面络合吸附行为;吸附铀前后的能谱对比分析表明,吸附过程中存在离子交换行为。因此,木纤维对铀的吸附机理是以离子交换和表面络合吸附为主、物理吸附为辅的混合吸附过程。     

Regulation characteristics of oxide generation and formaldehyde removal by using volume DBD reactor

Discharge plasmas in air can be accompanied by ultraviolet(UV) radiation and electron impact,which can produce large numbers of reactive species such as hydroxyl radical(OH·),oxygen radical(O·),ozone(O3),and nitrogen oxides(NOx),etc.The composition and dosage of reactive species usually play an important role in the case of volatile organic compounds(VOCs) treatment with the discharge plasmas.In this paper,we propose a volume discharge setup used to purify formaldehyde in air,which is configured by a plate-to-plate dielectric barrier discharge(DBD) channel and excited by an AC high voltage source.The results show that the relative spectral-intensity from DBD cell without formaldehyde is stronger than the case with formaldehyde.The energy efficiency ratios(EERs) of both oxides yield and formaldehyde removal can be regulated by the gas flow velocity in DBD channel,and the most desirable processing effect is the gas flow velocity within the range from2.50 to 3.33 m s-1.Moreover,the EERs of both the generated dosages of oxides(O3 and NO2) and the amount of removed formaldehyde can also be regulated by both of the applied voltage and power density loaded on the DBD cell.Additionally,the EERs of both oxides generation and formaldehyde removal present as a function of normal distribution with increasing the applied power density,and the peak of the function is appeared in the range from 273.5 to 400.0 W l-1.This work clearly demonstrates the regulation characteristic of both the formaldehyde removal and oxides yield by using volume DBD,and it is helpful in the applications of VOCs removal by using discharge plasma.     

Effect of plasma treatment on the seed germination and seedling growth of radish (Raphanus sativus)

The effect on the germination and seedling growth of radish (Raphanus sativus) seeds were examined employing a dielectric barrier discharge (DBD) at atmospheric pressure and room temperature for various treatment time. DBD plasma using argon gas of flow rate 2 l m−1 was employed in this study. Radish seeds were treated with DBD plasma for 1–5 min, respectively. Germination characteristics, seedling growth parameters, the contact angle of the seed coat, water uptake capacity, mass loss, the temperature of the seeds, chlorophyll, and carotenoid contents of the seedlings were measured before and after the DBD plasma treatments. Plasma treatment of radish seeds significantly increased germination-related characters, including germination percentage, fresh and dry weight, vigor index, and total carotenoids contents. However, the cumulative production rate was found to be decreased. Results from the experiment indicate an acceleration in the water uptake of the radish seeds and make the seed surface hydrophilic by plasma treatment. Scanning electron microscopy analysis showed that etching effects on the seed coat occurred after the argon plasma treatments, which affected the wettability of the radish seed. The experimental findings showed that seeds being treated by DBD plasma for 2 and 3 min had a positive effect on the germination and seedling growth of radish.     

Generation of reactive species in atmospheric pressure dielectric barrier discharge with liquid water

Atmospheric pressure helium/water dielectric barrier discharge(DBD) plasma is used to investigate the generation of reactive species in a gas–liquid interface and in a liquid. The emission intensity of the reactive species is measured by optical emission spectroscopy(OES)with different discharge powers at the gas–liquid interface. Spectrophotometry is used to analyze the reactive species induced by the plasma in the liquid. The concentration of OH radicals reaches 2.2 μm after 3 min of discharge treatment. In addition, the concentration of primary longlived reactive species such as H_2O_2, NO_3~- and O_3 are measured based on plasma treatment time.After 5 min of discharge treatment, the concentration of H_2O_2, NO_3~-, and O_3 increased from 0 mg?·?L~(-1) to 96 mg?·?L~(-1), 19.5 mg?·?L~(-1), and 3.5 mg?·?L~(-1), respectively. The water treated by plasma still contained a considerable concentration of reactive species after 6 h of storage. The results will contribute to optimizing the DBD plasma system for biological decontamination.     

Improving the surface flashover performance of epoxy resin by plasma treatment:a comparison of fluorination and silicon deposition under different modes

This work treats the Al2O3-ER sample surface using dielectric barrier discharge fluorination(DBD-F),DBD silicon deposition(DBD-Si),atmospheric-pressure plasma jet fluorination(APPJ-F)and APPJ silicon deposition(APPJ-Si).By comparing the surface morphology,chemical components and electrical parameters,the diverse mechanisms of different plasma modification methods used to improve flashover performance are revealed.The results show that the flashover voltage of the DBD-F samples is the largest(increased by 21.2％at most),while the APPJ-F method has the worst promotion effect.The flashover voltage of the APPJ-Si samples decreases sharply when treatment time exceeds 180 s,but the promotion effect outperforms the DBD-Si method during a short modified time.For the mechanism explanation,firstly,plasma fluorination improves the surface roughness and introduces shallow traps by etching the surface and grafting fluorine-containing groups,while plasma silicon deposition reduces the surface roughness and introduces a large number of shallow traps by coating SiOx film.Furthermore,the reaction of the DBD method is more violent,while the homogeneity of the APPJ modification is better.These characteristics influence the effects of fluorination and silicon deposition.Finally,increasing the surface roughness and introducing shallow traps accelerates surface charge dissipation and inhibits flashover,but too many shallow traps greatly increase the dissipated rate and facilitate surface flashover instead.     

磁性功能改性杯[4]芳烃胺肟衍生物及其对铀的吸附特性

以氨基化改性磁性纳米Fe_3O_4粒子为载体,将杯[4]芳烃胺肟衍生物进行磁性功能化改性,制备得到立体构象稳定、与UO_2~(2+)空间配位构型匹配的杯[4]芳烃胺肟衍生物磁性功能材料(MFM-AOCA)。并采用红外光谱、扫描电镜进行了结构表征。考察了溶液pH值、铀初始浓度、MFM-AOCA用量和吸附时间等因素对吸附的影响。结果表明:杯[4]芳烃胺肟衍生物磁性功能修饰后,具有较大的比表面积,其吸附铀的最佳条件是pH值为3.5、铀初始浓度为40 mg/L、吸附剂用量为40 mg和吸附时间为3.5 h。吸附动力学模型和吸附等温模型研究表明,MFM-AOCA对铀的吸附动力学过程符合准二级动力学模型,所得到的相关系数大于0.99;吸附等温线符合Langmuir等温线模型,其最大理论吸附量为141.28 mg/g。使用3种不同的解吸剂对MFM-AOCA解吸再生6次后,其对铀的吸附率均在80%以上,说明该MFMAOCA具有良好的再生性能。     

磁性氧化石墨烯/壳聚糖纳米复合材料的制备及其对UO_2~(2+)的吸附性能

以氧化石墨烯和壳聚糖为原料,1-乙基-(3-二甲基氨基丙基)3-乙基碳二亚胺盐酸盐(EDC)和N-羟基琥珀酰亚胺(NHS)为活化剂,超声法制备了磁性氧化石墨烯/壳聚糖纳米复合材料(MCGO),并研究了其对水溶液中UO_2~(2+)的吸附性能。SEM、FT-IR和XRD分析结果表明,成功制得了MCGO,且负载的Fe_3O_4尺寸为nm级。在温度为288K、pH=5.5、UO_2~(2+)初始浓度为160 mg/L、吸附时间为1.5h时,MCGO吸附容量为266.67mg/g。对实验数据进行热力学和动力学模型拟合,结果表明,MCGO吸附行为符合Langmuir模型和准二级动力学模型,且吸附为吸热自发过程。MCGO第1次重复利用率高达98.47%,经过6次吸附-脱附后,重复利用率仍有74.43%,具有较好的重复利用性。     

Investigation on discharge characteristics of a coaxial dielectric barrier discharge reactor driven by AC and ns power sources

A coaxial dielectric barrier discharge(DBD) reactor with double layer dielectric barriers has been developed for exhaust gas treatment and excited either by AC power or nanosecond(ns)pulse to generate atmospheric pressure plasma. The comparative study on the discharge characteristics of the discharge uniformity, power deposition, energy efficiency, and operation temperature between AC and ns pulsed coaxial DBD is carried out in terms of optical and electrical characteristics and operation temperature for optimizing the coaxial DBD reactor performance. The voltages across the air gap and dielectric layer and the conduction and displacement currents are extracted from the applied voltages and measured currents of AC and ns pulsed coaxial DBDs for the calculation of the power depositions and energy efficiencies through an equivalent electrical model. The discharge uniformity and operating temperature of the coaxial DBD reactor are monitored and analyzed by optical images and infrared camera. A heat conduction model is used to calculate the temperature of the internal quartz tube. It is found that the ns pulsed coaxial DBD has a much higher instantaneous power deposition in plasma, a lower total power consumption, and a higher energy efficiency compared with that excited by AC power and is more homogeneous and stable. The temperature of the outside wall of the AC and ns pulse excited coaxial DBD reaches 158 ℃ and 64.3 ℃ after 900 s operation, respectively.The experimental results on the comparison of the discharge characteristics of coaxial DBDs excited by different powers are significant for understanding of the mechanism of DBDs,reducing energy loss, and optimizing the performance of coaxial DBD in industrial applications.     

有机改性蛭石吸附U(Ⅵ)的行为及机理研究

通过静态吸附实验，研究了用十六烷基三甲基溴化铵（HDTMA•Br）改性的蛭石对U(Ⅵ)的吸附行为，以及有机改性蛭石（吸附剂）用量、pH值、铀初始质量浓度、吸附时间等因素对有机改性蛭石吸附U(Ⅵ)效果的影响，从热力学和动力学方面对吸附过程进行了分析，并通过FT-IR和SEM探讨了其相关吸附机理。结果表明：增加吸附剂用量、延长吸附时间和降低铀初始质量浓度都能提高有机改性蛭石对铀的去除率，最佳吸附pH值为6.5左右，120 min达到吸附平衡；用絮凝剂协同吸附能提高有机改性蛭石对铀的吸附效果；有机改性蛭石对铀的吸附遵循Langmuir吸附等温线，符合准二级动力学方程。有机改性蛭石吸附铀前后的FT-IR表明，-OH、Si[CDS1]O等基团起重要作用；SEM分析表明，有机改性蛭石吸附U(Ⅵ)引起其形态结构的改变。     

Fe(OH)3胶体对铀的吸附行为

为研究地浸采铀工艺过程中Fe(OH)₃胶体对铀的吸附,利用在无水乙醇中制备的Fe(OH)₃胶体,研究了pH值、初始铀浓度及吸附时间等对Fe(OH)₃胶体吸附铀的影响。采用准一级、复合二级与Elovich动力学模型对数据进行了动力学计算与分析,结果表明Elovich 动力学方程更适合描述Fe(OH)₃胶体对铀的吸附行为。采用Freundlich与Langmuir等温吸附方程对实验数据进行了热力学分析和拟合,结果表明Freundlich模型更适合描述Fe(OH)₃胶体对铀的吸附行为。综合两种等温吸附方程,推测Fe(OH)₃胶体对铀的吸附属于不均匀表面的单层物理吸附。根据激光粒度分析与SEM分析结果推测,Fe(OH)₃胶体对铀具有较强的吸附性能,吸附主要是表面吸附。     

Fast and low-temperature elimination of organic templates from SBA-15 using dielectric barrier discharge plasma

Organic templates P-123 of mesoporous SBA-15 can be effectively removed in a few minutes (4min) by using the dielectric-barrier discharge (DBD) plasma technique at ambient pressure and low gas temperature (around 130°C). The mesoporous SBA-15 was characterized by FT-IR, ²⁹ Si solid sate NMR, TEM, XRD, TGA and N₂ adsorption/desorption isotherms. The as-made SBA-15 treated with DBD plasma exhibited a larger surface area of 790 m ²·g ⁻¹ with larger pores and microspore volume than samples prepared by using the conventional thermal calcination method (550 °C and 5h, 660 m ²·g ⁻¹ ). In addition to less shrinkage of the silica framework, the DBD-prepared SBA-15 showed significantly increased weight loss of 8.3% about 200 °C as compared with that of conventional calcination (5.5%), which is attributed mainly to the dehydroxylation by condensation of silanol groups.     

活性炭纤维在低温下对Kr的静态吸附

研究了粘胶基活性炭纤维(Viscose-based ACF,VACF)、沥青基活性炭纤维(Pitch-based ACF,PACF)和颗粒活性炭(Grain activated carbon,GAC)在201K时对Kr的静态吸附等温线和吸附速度,并与同样条件下VACF对Xe的吸附进行了比较。结果表明：在201K条件下,VACF对Kr,Xe具有基本相同的平衡吸附容量,但VACF对Kr的吸附速度要大于对Xe的吸附速度。