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.     

A combined plasma photolysis (CPP) method for removal of CS2 from gas streams at atmospheric pressure

A combined plasma photolysis (CPP) reactor that utilizes a dielectric barrier discharge (DBD) plasma and 207 nm UV radiation from discharge-driven KrBr^* excimers was designed and constructed. Gas streams containing CS₂ were treated with stand-alone DBD and CPP at atmospheric pressure. In comparison to DBD, CPP greatly enhanced the removal efficiency at the same applied voltage, waste gas concentration and gas residence time. Thus the applied voltage could be reduced to a certain extent in the plasma processing of industrial wastes. Influences of the KrBr^* radiation, inlet CS₂ concentration and gas residence time on CS₂ removal by CPP were also studied. In addition, the likely reaction mechanisms for the removal of CS₂ by CPP are suggested based on the byproducts analysis. The enhanced removal efficiency and reaction mechanisms implied that the CPP process would probably be suitable for the removal of a large number of gaseous pollutants.     

单介质和双介质阻挡放电低温等离子体降解甲苯的比较

为研究介质阻挡放电(DBD)反应器结构对低温等离子体降解甲苯的影响,设计了具有单层介质和双层介质的DBD反应器。对2种反应器的放电特征、甲苯去除率、矿化率、CO₂选择性和能量效率进行了比较,并对施加电压和初始浓度对甲苯降解效果的影响进行了分析。结果表明：在相同电压下,双介质反应器(DDBD)具有更高的电场强度,而单介质反应器(SDBD)的输入功率更高;当甲苯浓度和电压分别为616、1 027、1 848 mg·m⁻³和14~24 kV时,双介质中的甲苯去除率为9.4%~100%、7.4%~99%、5.1%~64%,单介质为67%~98%、46%~90%、26%~59%。这说明低电压下单介质反应器的甲苯去除率更高,而高电压下则相反,并且,浓度降低、电压升高有利于甲苯的降解。单介质反应器的能量效率随电压升高而降低,双介质反应器则先升高后下降,且双介质反应器的能量效率高于单介质反应器(16~24 kV)。以上研究可为介质阻挡放电在VOCs去除方面的应用提供参考。     

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。     

SO2、NO对汞在湿法电除尘器中脱除的影响

湿法电除尘器(WESP)作为一种控制烟气中超细颗粒物的有效手段被应用于燃煤电厂的超低排放改造中,然而烟气中的Hg0受电场、水膜、烟气组分等因素的影响在WESP中的协同脱除机理尚不明确。为了深入了解该机理,探讨了WESP电场和水膜对Hg0的控制机理,并进一步研究了烟气中SO2、NO对Hg0在WESP中脱除的影响。结果表明：电场静电作用对烟气中Hg0脱除贡献较小,O2电离产物?O对Hg0的氧化作用是O2促进Hg0脱除的主要途径,水蒸气通过电离产生?OH促进Hg0氧化以及通过黏附作用促进Hg0脱除;水膜的裹挟作用对WESP系统Hg0的脱除贡献较小,溶于水中的汞不稳定且容易再释放;SO2、NO均通过在电场中电离产生?O促进Hg0氧化脱除,其中,SO2及其电离产物溶于水膜后可以与Hg2+形成稳定配合物抑制汞的再释放,而NO的电离产物在水膜中对汞再释放的抑制作用较小。     

DBD反应器电极结构对放电特征及甲苯降解效果的影响

为研究DBD反应器电极结构对放电特征和甲苯降解效果的影响,设计了具有3种不同结构高压电极(棒、螺纹棒、线圈)和接地电极(铜网、铜带、铜丝)的反应器。通过放电图像、发射光谱、电压-电流波形、李萨如图、放电功率和放电间隙气体温度分析了不同电极结构反应器的放电特性;以甲苯去除率、矿化率、能量效率为评价指标,考察了电极结构对甲苯降解效果的影响。结果表明：3种不同结构高压电极反应器的放电强度顺序为线圈>棒>螺纹棒;当甲苯质量浓度为678 mg·m⁻³、电压为12~20 kV、且以线圈为高压电极时,反应器的放电功率、放电间隙气体温度低,分别为0.4~10.3 W、28~64 ℃,而对甲苯的去除率、矿化率、能量效率均最高,分别为77.71%~100%、21.03%~35.96%、4.96~8.81 g·kWh⁻¹;3种不同结构接地电极反应器中以铜带为接地电极时放电强度最强,对甲苯的去除率、矿化率和能量效率最高,分别为25.3%~100%、3.41%~35.96%、4.96~23.17 g·kWh⁻¹。本研究可为DBD反应器在降解甲苯应用中的结构优化和材料选择提供参考。     

Oxidation of elemental mercury using atmospheric pressure non-thermal plasma

The oxidation of gas phase elemental mercury (Hg0) by atmospheric pressure non-thermal plasma has been investigated at room temperature, employing both dielectric barrier discharge (DBD) of the gas mixture of Hg0 and injection of ozone (O3) into the gas mixture of Hg0. Results have shown that the oxidative efficiencies of Hg0 by DBD and the injection of O3 are 59% and 93%, respectively, with energy consumption of 23.7 J L(-1). This combined approach has indicated that O3 plays a decisive role in the oxidation of gas phase Hg0. Also the oxidation of Hg0 by injecting O3 into the gas mixture of Hg0 proceeds with better efficiency than DBD of the gas mixture of Hg0. These results have been explained by the incorporation of the competitive reaction pathways between the formation of HgO by O3 and the decomposition of HgO back to Hg0 in the plasma environment.     

介质阻挡放电氧化降解木质素磺酸钠的动力学研究

为了有效地处理难生物降解的造纸废水,采用气相介质阻挡放电产生氧化性物质,对木质素磺酸钠进行了氧化降解研究。在不同操作条件下,对其降解动力学及矿化程度进行了研究。结果表明,介质阻挡放电能有效地降解木质素磺酸钠,其氧化降解反应遵循准一级动力学反应。当峰值电压为20 kV,被水蒸气饱和的空气为气源,流量为7 L/min时,氧化处理60 min后,木质素磺酸钠降解率达到70％。其速率常数K随峰值电压、气源、气体流量和木质素磺酸钠的初始浓度的变化而不同。气体流量越大,木质素磺酸钠的初始浓度越低,速率常数K越大,降解效果越好。随着处理时间的增加,氧化性物质能将部分木质素磺酸钠矿化使溶液TOC降低,当被水蒸气饱和的空气作为气源时,氧化处理120min,21.38%的TOC被去除。     

Effect of solution pH on SO2, NO(x), and Hg removal from simulated coal combustion flue gas in an oxidant-enhanced wet scrubber

This paper presents a study on the simultaneous removal of SO2, NO(x) and Hg (both Hg0 and Hg2+) from a simulated flue gas by oxidant injection in a bench-simulated wet limestone scrubber for a wide range of slurry pH. The slurry pH strongly influenced the chemical mechanism in the scrubber and, therefore, affected pollutant removal. This paper also examines the potential ClO2(gas) reemission from a developed multipollutant scrubber at different slurry pHs. To better understand the chemical mechanisms at each slurry pH and to apply a mass balance to the process, detailed product ion analyses were performed for all experiments. Ion analysis covered three different chlorine species (chlorite, chloride, chlorate), sulfate, nitrite and nitrate. Different NO(x) removal efficiencies and mechanisms were found in acidic and alkaline pHs in the multipollutant scrubber. The acidic solution was favorable for NO and Hg0 oxidation, but increasing the slurry pH above 7.0 was disadvantageous for NO and Hg oxidation/removal. However the rate of NO(x) absorption (by percentage) was higher for the alkaline solution.     

The importance of the location of sodium chlorite application in a multipollutant flue gas cleaning system

In this study, removing sulfur dioxide (SO2), nitrogen oxides (NO(x)), and mercury (Hg) from simulated flue gas was investigated in two laboratory-sized bubbling reactors that simulated an oxidizing reactor (where the NO and Hg(0) oxidation reactions are expected to occur) and a wet limestone scrubber, respectively. A sodium chlorite solution was used as the oxidizing agent. The sodium chlorite solution was an effective additive that enhanced the NO(x), Hg, and SO2 capture from the flue gas. Furthermore, it was discovered that the location of the sodium chlorite application (before, in, or after the wet scrubber) greatly influences which pollutants are removed and the amount removed. This effect is related to the chemical conditions (pH, absence/presence of particular gases) that are present at different positions throughout the flue gas cleaning system profile. The research results indicated that there is a potential to achieve nearly zero SO2, NO(x), and Hg emissions (complete SO2, NO, and Hg removals and -90% of NO(x) absorption from initial values of 1500 ppmv of SO2, 200 ppmv of NO(x), and 206 microg/m3 of Hg(0)) from the flue gas when sodium chlorite was applied before the wet limestone scrubber. However applying the oxidizer after the wet limestone scrubber was the most effective configuration for Hg and NO(x) control for extremely low chlorite concentrations (below 0.002 M) and therefore appears to be the best configuration for Hg control or as an additional step in NO(x) recleaning (after other NO(x) control facilities). The multipollutant scrubber, into which the chlorite was injected simultaneously with the calcium carbonate slurry, appeared to be the least expensive solution (when consider only capital cost), but exhibited the lowest NO(x) absorption at -50%. The bench-scale test results presented can be used to develop performance predictions for a full- or pilot-scale multipollutant flue gas cleaning system equipped with wet flue gas desulfurization scrubber.     

Simultaneous removal of nitrogen oxide/nitrogen dioxide/sulfur dioxide from gas streams by combined plasma scrubbing technology

Oxides of nitrogen (NOx) [nitrogen oxide (NO) + nitrogen dioxide (NO2)] and sulfur dioxide (SO2) are removed individually in traditional air pollution control technologies. This study proposes a combined plasma scrubbing (CPS) system for simultaneous removal of SO2 and NOx. CPS consists of a dielectric barrier discharge (DBD) and wet scrubbing in series. DBD is used to generate nonthermal plasmas for converting NO to NO2. The water-soluble NO2 then can be removed by wet scrubbing accompanied with SO2 removal. In this work, CPS was tested with simulated exhausts in the laboratory and with diesel-generator exhausts in the field. Experimental results indicate that DBD is very efficient in converting NO to NO2. More than 90% removal of NO, NOx, and SO2 can be simultaneously achieved with CPS. Both sodium sulfide (Na2S) and sodium sulfite (Na2SO3) scrubbing solutions are good for NO2 and SO2 absorption. Energy efficiencies for NOx and SO2 removal are 17 and 18 g/kWh, respectively. The technical feasibility of CPS for simultaneous removal of NO, NO2, and SO2 from gas streams is successfully demonstrated in this study. However, production of carbon monoxide as a side-product (approximately 100 ppm) is found and should be considered.     

飞灰-氢氧化钙/聚苯硫醚(PPS)滤料对烟气中单质汞的脱除

在汞固定床实验台上进行了飞灰-氢氧化钙和PPS滤料负载飞灰-氢氧化钙吸附单质汞,以及不同温度、气体成分对滤料负载吸附剂脱除汞影响的实验研究。实验结果表明,质量配比为2:1的飞灰-Ca(OH)2吸附剂对Hg0的脱除效果最好,最高可达到34.5%左右,比纯飞灰条件下的脱除效率提高了近10%。120℃条件下,PPS滤料负载飞灰-Ca(OH)2吸附剂对汞的脱除率最高达72%,远高于滤纸薄膜上吸附剂的脱除率。随着温度升高,PPS滤料负载吸附剂的脱除效率降低。HCl、SO2和NO对PPS负载吸附剂脱除汞表现出不同程度的促进作用,HCl具有很强的促进作用,少量HCl足以大幅度提高脱除效果,SO2有一定的促进作用,NO的促进效果并不明显。     

脉冲电晕低温等离子体提高一氧化氮氧化效率的实验研究

提高一氧化氮（NO）的氧化效率对于提高生物法处理该类废气的净化效率具有重要意义。实验研究了低温等离子体在脉冲电晕条件下氧化废气中NO的过程,考察了不同峰值电压、氧气含量、气体停留时间和添加有机物等因素对提高NO氧化效率的影响。结果表明：低温等离子法可有效地提高NO的氧化效率,主要产物为NO₂;室温条件下,当进气NO浓度590 mg/m³、脉冲频率50 Hz时,增大峰值电压、气体停留时间和进气中的氧气含量可提高NO的氧化效率;在最适峰值电压15 kV,气体停留时间5 s时,NO氧化效率为20%;在进气NO中添加甲苯、乙醇后,NO氧化效率可增加至30%以上,甲苯的效果要好于乙醇。     

Cu/SAPO-34 对模拟烟气中零价汞的脱除性能

采用离子交换法将不同比例的Cu负载于SAPO-34分子筛,通过固定床反应器考察其对模拟烟气中零价汞（Hg0）的催化去除效果,并使用BET、XRD、SEM等方法对材料性能进行分析表征。结果发现：在脱汞效率测试中,1.5×10-5 HCl能显著提升Cu/SAPO-34对Hg0的去除效率。在100～250 ℃范围内,Hg0去除率均能达到80%以上,最大去除效率达到97%。在抗水抗硫实验中,H2O对Cu/SAPO-34-10%脱汞效率影响很小;通入2×10-3 SO2 450 min后,Hg0去除率仍有85%,停止通入SO2后材料的脱汞效率能够恢复。     

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.     

改性酚醛泡沫脱除SO2/NOx影响因素模型

改性酚醛泡沫具有良好的吸附性能,可用于脱除气态污染物,需深入研究其脱除效率与各影响因素间关系。首次引入支持向量机建立改性酚醛泡沫吸附反应床模型,研究在不同温度、气质比、含氧量等影响因素下改性酚醛泡沫脱除二氧化硫、氮氧化物等气态污染物的脱除效果及最优反应条件。烟气模拟脱硫脱硝实验确定RBF-ε-SVM模型为反应器内最优污染物浓度分布预测模型,惩罚系数c=100,gamma因子g=0.1。基于最优模型的各影响因素实验表明：氧气含量在6%时改性酚醛泡沫脱硫脱硝效果最佳;随着质气比的增加脱除效果增强;反应温度在80 ℃内脱除SO2和NO的效率随着烟气温度的升高而降低。该模型可用于改性酚醛泡沫吸附反应床的最优工况选择,反应器内浓度分布的在线监控,以及指导反应器的放大、中试。     

多针-板脉冲放电处理模拟尾气中的NOx

机动车尾气中NOx受到人们普遍关注。采用多针-板放电反应器,研究NOx浓度变化随电气、气体等参数的变化规律,为脉冲放电去除NOx提供一定理论支撑。结果表明：在一定条件下提高脉冲电压有利于NO转化;脉冲重复频率增大可提升NOx去除率,脉冲重复频率达到一定值时NOx去除率增幅不明显;流量增大利于NO转化,不利于NOx去除;随氧浓度的升高NO转化率呈现先降低后升高,NOx去除率逐渐降低。当氧浓度低于5%时,NOx主要是通过NO还原成N2;氧浓度高于5%时,NO主要通过氧化转化为NO2。     

电极尺寸对介质阻挡放电冷等离子体去除NO的影响

设计了一套高压电源装置以及相应的同轴圆柱 筒介质阻挡放电管 ,研究了放电管中心电极直径以及介质层管内径变化对放电冷等离子体去除NO的影响。实验结果表明 ,这 2种电极尺寸的变化对NO去除率有显著的影响。中心电极直径的增加 ,有助于增强放电 ,但同时减小了反应空间 ;介质层管内径增加 ,延长停留时间的同时放电的强度却相应减弱了。所以中心电极的直径或介质层的内径均应有一最佳值 ,使得其他条件不变的情况下NO的去除效果最佳。     

Effects of sulfur dioxide and nitric oxide on mercury oxidation and reduction under homogeneous conditions

This paper is particularly related to elemental mercury (Hg0) oxidation and divalent mercury (Hg2+) reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO2). As a powerful oxidant and chlorinating reagent, Cl2 has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO2, NO, as well as H2O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO2 and NO on Hg0 oxidation and Hg2+ reduction with the intent of unraveling unrecognized interactions among Cl species, SO2, and NO most importantly in the presence of H2O. The experimental results demonstrated that SO2 and NO had pronounced inhibitory effects on Hg0 oxidation at high temperatures when H2O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg2+ back into its elemental form. Data revealed that SO2 and NO were capable of promoting homogeneous reduction of Hg2+ to Hg0 with H2O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H2O was removed from the gas blend.