用于气态零价汞转化的催化剂研究

零价汞的高效去除是燃煤烟气汞污染控制过程中的关键环节。为了促进烟气中的零价汞转化为易于去除的氧化态汞,分别考察了在有HCl存在时,几种过渡金属氧化物(Cu、Fe、Mn、Co和Zr)对零价汞氧化的催化作用,以筛选出性能较好的催化组分;为提高催化剂的抗SO2性能,分别尝试了利用几种金属元素(Sr、Ce、W和Mo)对催化剂进行掺杂改性的方法。结果表明,锰氧化物的催化作用最好,其最佳使用温度在573 K左右;SO2对零价汞的催化氧化有明显抑制作用,在无SO2及1 400 mg/m3SO2时锰催化剂对零价汞催化氧化效率分别为93%和78%。而Mo改性的锰氧化物催化剂的抗硫性能大幅提高,在1 400 mg/m3SO2存在的情况下其对零价汞的催化氧化效率可达到90%以上,较其他改性元素高。     

高温载硫活性炭的制备及脱汞能力研究

研究了载硫温度、硫炭比(简称S/C),吸附温度等因素对载硫活性炭的硫含量、脱汞能力以及硫损失的影响,探讨载硫活性炭制备的工艺条件优化。结果表明,不同载硫温度下制备的载硫活性炭的气态Hg0吸附能力远强于原料活性炭;载硫温度不同时,负载到活性炭孔隙或表面上的硫的形态不同,导致了脱汞能力的差异,较合适的载硫温度为350℃;S/C为5%(质量分数,下同)时,随着吸附温度的升高,载硫活性炭的气态Hg0吸附量降低;在一定的载硫温度下,原料中S/C越高时,制备的载硫活性炭的硫含量越高、气态Hg0吸附能力越强,但其硫损失率也越高,从实际的使用效果来看,较合适的S/C为10%。     

Influence of HCl on oxidation of gaseous elemental mercury by dielectric barrier discharge process

The influence of HCl on the oxidation of gaseous elemental mercury (Hg0) has been investigated using a dielectric barrier discharge (DBD) plasma process, where the temperature of the plasma reactor and the composition of gas mixtures of HCl, H2O, NO, and O2 in N2 balance have been varied. We observe that Cl atoms and Cl2 molecules, created by the DBD process, play important roles in the oxidation of Hg0 to HgCl2. The addition of H2O to the gas mixture of HCl in N2 accelerates the oxidation of Hg0, although no appreciable effect of H2O alone on the oxidation of Hg0 has been observed. The increase of the reaction temperature in the presence of HCl results in the reduction of Hg0 oxidation efficiency probably due to the deterioration of the heterogeneous chemical reaction of Hg0 with chlorinated species on the reactor wall. The presence of NO shows an inhibitory effect on the oxidation of Hg0 under DBD of 16% O2 in N2, indicating that NO acts as an O and O3 scavenger. At the composition of Hg0 (280 microg m(-3)), HCl (25 ppm), NO (204 ppm), O2 (16%) and N2 (balance) and temperature 90 degrees C, we obtain the nearly complete oxidation of Hg0 at a specific energy density of 8 J l(-1). These results lead us to suggest that the DBD process can be viable for the treatment of mercury released from coal-fired power plants.     

Removal of gaseous elemental mercury by dielectric barrier discharge

The removal of elemental mercury (Hg(0)) with the reactive species produced from dielectric barrier discharge (DBD) was studied. The effects of the operating parameters, such as the applied voltage, residence time, initial concentration and co-existence of other pollutants, were investigated. The removal of Hg(0) was significantly promoted by an increase in the applied voltage of the DBD reactor system. The presence of NO gas decreased the Hg(0) removal efficiency within the range of input powers tested compared to the case of Hg(0)-only due to the competition for ozone between Hg(0) and NO gas in the DBD reactor.     

高压脉冲电晕法治理有机废气实验研究

介绍了采用高压脉冲电晕法去除乙醇,甲醛,二氧甲灶模拟废气的情况。实验在线一板式电晕反应器内进行,考察了电压峰值,气体浓度,停留时间和含湿量等不同因素对去除率的影响。实验结果表明能达到较好的去除效果。     

Dynamic exchange of gaseous elemental mercury during polar night and day

From February 29 until June 15 2008 gaseous elemental mercury (GEM) fluxes above a snow covered surface was measured in Ny-Ålesund, Svalbard using a GEM flux gradient method. A clear seasonal pattern in the meteorological variables associated with the GEM flux was observed. For the first time in Ny-Ålesund a net deposition of GEM was recorded during polar night, despite the lack of Atmospheric Mercury Depletion Events (AMDE). 7500 ng m⁻² GEM was emitted from the surface snow to the air during the entire study. The depositions of GEM and reactive gaseous mercury (RGM) were calculated to be 1500 and 1000 ng m⁻², respectively, during the same time period. The GEM fluxes reported in this study were found to be comparable to GEM fluxes measured at other Arctic locations (i.e. Alert and Barrow), suggesting that GEM acts in a similar way throughout the Arctic. An assessment of the GEM flux gradient method used discovered a non-linear GEM concentration profile. The nonlinearity was explained by a non-stationary turbulence regime. The GEM flux calculated was not found to be representative for the entire surface boundary layer.     

氯化铜改性石墨相氮化碳吸附剂的脱汞性能

针对燃煤电厂汞污染物排放控制的问题, 以尿素为前驱体, 通过直接热聚合法制得绒毛状石墨相氮化碳(g-C₃N₄), 并用于低温条件下吸附脱除单质汞(Hg⁰)。利用透射电子显微镜(TEM)、X射线衍射(XRD)、氮气吸附-脱附、X射线光电子能谱(XPS)等手段对吸附剂进行表征。结果表明:未改性g-C₃N₄具有良好的低温脱汞活性, 在120 ℃时其脱汞效率可达84.7%;CuCl₂改性可以有效提高g-C₃N₄的脱汞性能, 其脱汞效率在40~200 ℃范围内均可达到97%以上; 温度对吸附剂脱汞效率的影响较小。XPS表征测试结果表明, 铜离子和共价态氯原子均参与了单质汞的吸附脱除反应, Hg⁰被Cu²⁺离子和共价态Cl原子氧化成了Hg²⁺离子, 再吸附于g-C₃N₄表面而脱除。CO₂、SO₂和水蒸气对吸附剂脱汞效率影响较小, 但水蒸气可提高汞吸附量。     

椰壳碳基吸附剂的脱汞特性

为研究来源于生物质的椰壳活性炭对单质汞的脱除性能, 采用化学浸渍法对椰壳活性炭进行化学改性处理,并在小型实验台架上考察了椰壳碳基吸附剂的脱汞性能.并对改性前后的样品进行了BET和SEM表征分析以研究改性前后椰壳活性炭的变化规律.结果表明,改性后椰壳活性炭具有较强的脱汞能力,特别是在140℃、180℃时的脱汞效率仍保持在95%以上.改性后椰壳活性炭具有更多的利于脱汞的官能团,其主要靠化学吸附脱汞.烟气中低浓度的SO2与NO对汞的脱除有一定的抑制作用,而HCl有一定的促进作用.     

300MW燃煤机组烟气控制装置对气态汞去除效果

利用美国EPA OH法对烟气中不同形态汞的气态汞进行测试,研究300 MW锅炉的袋式除尘、静电除尘和湿法烟气脱硫对气态汞的去除效果。研究结果表明,静电除尘器对气态汞的去除效率仅为32.50%,对颗粒态汞的去除效率达76.88%,而使用袋式除尘器对气态汞的去除效率可达44.33%,可脱除99.92%以上的颗粒态汞;应用湿法烟气脱硫对二价汞的去除率可达49.03%。通过对粉煤灰、炉渣和脱硫石膏等燃煤副产物汞含量分析发现,脱硫石膏中汞的含量最高达0.77 mg/kg,汞及其环境毒性是燃煤副产物安全利用时需要注意一个主要问题。     

电晕放电等离子体对水中邻苯二甲酸二甲酯的降解

采用电晕放电等离子体降解水中的邻苯二甲酸二甲酯,研究了放电输出功率、溶液初始浓度、空气流量、初始pH、Fe2+和羟基自由基清除剂对邻苯二甲酸二甲酯去除效率的影响,并对其降解动力学进行了初步模拟。结果表明,电晕放电等离子体对水中邻苯二甲酸二甲酯有较好的去除效果。在放电功率45 W、初始浓度50 mg·L-1、空气流速2 L·h-1、初始pH 6.31、初始电导率4.05 μS·cm-1的条件下,反应30 min,邻苯二甲酸二甲酯的去除率可达到95%。酸性条件下有利于邻苯二甲酸二甲酯的降解。添加Fe2+,在反应初期可显著提高邻苯二甲酸二甲酯的降解率。羟基自由基清除剂的加入在一定程度上抑制了邻苯二甲酸二甲酯的降解。电晕放电等离子体降解邻苯二甲酸二甲酯的过程基本符合一级反应动力学。     

凹土负载催化剂对模拟烟气中单质汞的吸附

采用浸渍法制备一系列Mo掺杂MnOx/凹土催化剂(Mo-Mn-ATP),并经负载Mo/MnOx后冻干-焙烧变温致孔处理。采用比表面、孔径分析仪测定催化剂的比表面积、N2吸附-脱附等温线分析和孔径分布;X射线能谱分析仪(EDS)对催化剂成分进行分析。在固定床汞吸附实验台上,进行了凹土负载催化剂脱除模拟烟气中Hg0的实验研究和理论分析。结果表明,制得的Mo/Mn摩尔比1:3的Mo-Mn-ATP催化剂,在保持凹土原有晶体结构的基础上,随着Mo/MnOx负载量的增加,材料的比表面积和孔容减小。10%负载量,反应温度120℃的条件下,含Mo催化剂对Hg0的脱除性能最佳。     

A method for removal of CO from exhaust gas using pulsed corona discharge

An experimental study of the oxidation of CO in exhaust gas from a motorcycle has been carried out using plasma chemical reactions in a pulsed corona discharge. In the process, some main parameters, such as the initial CO concentration, amplitude and frequency of pulses, residence time, reactor volume, and relative humidity (RH), as well as their effects on CO removal characteristics, were investigated. O3, which is beneficial to reducing CO, was produced during CO removal. When the exhaust gas was at ambient temperature, more than 80% CO removal efficiency was realized at an initial concentration of 288 ppm in a suitable range of the parameters.     

Atmospheric oxidation of elemental mercury by ozone in the aqueous phase

The aqueous phase oxidation of elemental mercury by ozone has been investigated in the laboratory using a quartz glass reactor with gas phase concentrations of 400–1800ng m⁻³ and 70–200 ppb for Hg(0) and O₃, respectively. The absorption of Hg in the water phase was increased by three orders of magnitude with O₃ present. If the oxidation were to proceed with the same speed in liquid water in contact with the atmosphere,conversion rales of 1–4% h⁻¹ would be implied. Experiments using ambient urban air with 2–6 ng Hg m⁻³ confirm the process at elevated O₃ concentrations. At ambient O₃ concentrations competitive reactions become important, e.g. O₃ consumption by SO₂, hydrocarbons etc., and even some reduction of Hg²⁺ could occur. The atmospheric oxidation of Hg(0) by O₃ in water is thus considered important at high O₃ levels in regionally polluted or remote areas.     

非平衡等离子体诱导催化剂吸附单质汞

采用非平衡等离子体诱导γ-Al2O3催化剂吸附单质汞,分析了等离子体与催化剂之间的相互作用。结果表明,在放电区域填充催化剂和在气流中加入单质汞均可降低放电的起始放电电压,这是因为放电区域填充催化剂使气体空间放电转变成表面的微放电。催化剂表面可以被等离子放电直接活化,使本身不能吸附单质汞的催化剂产生很强的吸附单质汞的能力。在放电能量密度约为19 J·L-1时,等离子体诱导催化剂吸附单质汞的效率可达94.1%。O2对等离子体诱导催化剂吸附Hg0有促进作用,随着O2浓度的提高,吸附效率随之提高。当气流中含有5% O2时,单质汞的吸附效率可达到98.5%,这是因为气流中存在O2时,经放电生成的等离子体中含有活性氧物种O3和O等,这些活性物质因具有氧化单质汞的能力而增强了单质汞的吸附。此外,催化剂表面O3的分解过程也是强化单质汞的吸附的原因。     

介质阻挡放电与脉冲电晕放电修复芘污染土壤的对比研究

选取芘作为多环芳烃的代表污染物,利用介质阻挡及脉冲电晕2种放电方式产生的低温等离子体对芘污染的土壤进行修复。通过污染物处理率、影响因素和能量利用效率等实验计算结果对2种放电方式下土壤的修复效果进行比较,并从放电方式的原理、特点和反应器结构等角度进行分析。结果表明：在芘初始浓度为100 mg·kg-1、电极间隙为14 mm时,介质阻挡放电对土壤中芘的处理率较高,可达60.6%,经GC-MS图谱检测分析,其多数产物分子量小、结构简单,但该放电方式受电气参数影响较大,当电极间隙增大到20 mm时,处理率则低至28.3%,其最高能量效率仅为0.321 mg·kJ-1;而脉冲电晕放电在不同条件下处理效果稳定,电极间隙为14~20 mm时,处理率均能达50%左右,且在不同实验条件下,其能量效率为2.29~3.76 mg·kJ-1,是介质阻挡放电的10余倍。脉冲电晕放电方式在处理比污染土壤时要优于介质阻挡放电。     

Laboratory and field measurements of NOx produced from corona discharge

This research consists of a laboratory study and a field study. The laboratory research reports the formation of NO_x from a point to plane corona discharge. Discharge polarity and relative humidity determined the amount of NO_x that was produced. The positive point discharge caused more NO_x to form than the negative point discharge. For both polarities NO_x production showed a nonlinear increase with current. Relative humidity enhanced the NO_x formation for both polarities. In each case, the amount of NO_x formed was comparable to the quantity of N₂O produced from corona discharge. The research also reports the results from a field study that measured the amounts of 03 and NO₂ produced by corona discharge during a thunderstorm. The study found that the ambient concentrations of 03 and NO₂ increased several fold due to corona discharge and returned to original levels after the thunderstorm.     

Factors influencing concentrations of dissolved gaseous mercury (DGM) and total mercury (TM) in an artificial reservoir

The effects of various factors including turbidity, pH, DOC, temperature, and solar radiation on the concentrations of total mercury (TM) and dissolved gaseous mercury (DGM) were investigated in an artificial reservoir in Korea. Episodic total mercury accumulation events occurred during the rainy season as turbidity increased, indicating that the TM concentration was not controlled by direct atmospheric deposition. The DGM concentration in surface water ranged from 3.6 to 160 pg/L, having a maximum in summer and minimum in winter. While in most previous studies DGM was controlled primarily by a photo-reduction process, DGM concentrations tracked the amount of solar radiation only in winter when the water temperature was fairly low in this study. During the other seasons microbial transformation seemed to play an important role in reducing Hg(II) to Hg(0). DGM increased as dissolved organic carbon (DOC) concentration increased (p-value < 0.01) while it increased with a decrease of pH (p-value < 0.01).     

高压脉冲电晕处理发动机尾气中的NO的实验研究

本文通过对高压脉冲电晕放电产生的等离子体活性物质对发动机尾气中的NO进行活化 ,研究其净化率与电压、频率、风速以及初始浓度的关系及其相互之间的影响 ,同时研究NO的产物NO2 随电压、频率、风速以及初始浓度的生成关系 ,实验表明 ,NO的净化率能够达到 5 0 %以上 ,在风速不大的条件下 ,NO转化的主要产物为NO2     

Relationship between the loading rate of inorganic mercury to aquatic ecosystems and dissolved gaseous mercury production and evasion

The purpose of our study was to test the hypothesis that dissolved gaseous mercury (DGM) production and evasion is directly proportional to the loading rate of inorganic mercury [Hg(II)] to aquatic ecosystems. We simulated different rates of atmospheric mercury deposition in 10-m diameter mesocosms in a boreal lake by adding multiple additions of Hg(II) enriched with a stable mercury isotope (²⁰²Hg). We measured DGM concentrations in surface waters and estimated evasion rates using the thin-film gas exchange model and mass transfer coefficients derived from sulfur hexafluoride (SF₆) additions. The additions of Hg(II) stimulated DGM production, indicating that newly added Hg(II) was highly reactive. Concentrations of DGM derived from the experimental Hg(II) additions (“spike DGM”) were directly proportional to the rate of Hg(II) loading to the mesocosms. Spike DGM concentrations averaged 0.15, 0.48 and 0.94 ng l⁻¹ in mesocosms loaded at 7.1, 14.2, and 35.5 μg Hg m⁻² yr⁻¹, respectively. The evasion rates of spike DGM from these mesocosms averaged 4.2, 17.2, and 22.3 ng m⁻² h⁻¹, respectively. The percentage of Hg(II) added to the mesocosms that was lost to the atmosphere was substantial (33–59% over 8 weeks) and was unrelated to the rate of Hg(II) loading. We conclude that changes in atmospheric mercury deposition to aquatic ecosystems will not change the relative proportion of mercury recycled to the atmosphere.     

Inactivation of MS2 bacteriophage by streamer corona discharge in water

Electrical discharge processes are emerging as water treatment technologies applicable to both the degradation of organic contaminants as well as inactivation of pathogens. Particularly as a disinfection technology, electrical discharge processes do not produce toxic byproducts, and effectively inactivate a wide spectrum of microorganisms by multiple lethal actions generated by the formation of plasma channels. This study demonstrates the inactivation of a virus using the streamer corona discharge process (SCDP) with MS2 phage as a surrogate. A rapid inactivation of MS2 phage (i.e., approximately 4 log inactivation in 5 min) was observed in all experimental runs conducted. Discharge conditions such as applied voltage and storage capacitance significantly affected the inactivation efficiency of MS2 phage, whereas the influence of water quality parameters was minor. In order to elucidate the mechanism of MS2 phage inactivation, potentially lethal factors that can be generated by the SCDP were selected, and their roles in the inactivation of MS2 phage were examined. As a result, effects of UV radiation, chemical oxidants, and pulsed electric fields were found to be insignificant. The shockwave generated upon plasma channel formation appears to be the most important factor responsible for MS2 phage inactivation.