等离子体协同光催化去除模拟烟气中SO2的实验研究

近年来,低温等离子体技术以及纳米TiO₂光催化技术在烟气脱硫中的应用越来越引起人们的关注。利用填充床反应器将这2种技术有机地结合起来，进行了大量脱硫实验研究。研究结果表明，等离子体协同光催化去除烟气中的SO₂与单独采用等离子体技术相比，其SO₂的去除率可提高5%～20%。同时，探讨了等离子体协同TiO₂光催化剂的脱硫机理，分别研究了外加电压、气体流量和SO₂初始浓度等因素对脱硫效率的影响。实验结果表明，当SO₂初始浓度为800 mg/m³，输入电压为17.5 kV，气体流量为0.2 m³/h时，SO₂脱除率可以达到77.6%。     

H2O2溶液同时脱硫脱硝实验研究

二氧化硫和氮氧化物是电厂产生的主要大气污染物,研究焦点越来越集中在在一个反应器内实现同时脱硫脱硝。实验以H₂O₂溶液作为吸收液,在自制的鼓泡反应器内,对模拟烟气进行同时脱硫脱硝的实验研究,实验结果表明：H₂O₂浓度、反应温度、NO浓度、SO₂浓度、烟气流量对脱除率影响显著,pH、氧含量对脱硝率影响不大。在整个实验范围内脱硫效率总是保持在98.5%以上,脱硝效率最高达到67.4%。     

湿式烟气脱硫系统同时脱汞研究

研究表明,湿法烟气脱硫装置(WFGD)可去除烟气中绝大部分Hg²⁺,但对单质汞的吸收效果不明显,因此研究提高湿法烟气脱硫系统中单质汞的氧化率的方法对控制汞的排放具有重要意义。综述了WFGD及在此系统中各种添加剂的脱汞性能,认为在添加剂中,气态的臭氧、液态的次氯酸和氯化钠稀溶液、 黄磷乳浊液、氢硫化钠溶液及EDTA的汞去除效果较好,且不会被SO₂大量消耗,可在WFGD系统实现同时脱硫脱汞;而气态的氯气,液态的K₂S₂O₈溶液虽然也有较好的汞去除效果,但因易被SO₂或亚硫酸盐溶液消耗,当在WFGD系统中用其氧化单质汞时,需要对脱硫塔进行分层或其他改造,使烟气中的SO₂被吸收后再控制汞,提高经济性。     

密相半干法低温同时脱硫脱硝影响因素

针对90~160℃的低温条件下,SO₂对钙基吸收剂吸收NO_x的影响进行了实验研究,分析了烟气温度T、含氧率、含湿量等对SO₂促进钙基吸收剂吸收NO_x的影响。实验结果表明,当烟气中SO₂浓度的升高可促进钙基吸收剂对NO_x的吸收;同时,维持反应系统在9.2%的含湿量;保证烟气温度在结露点以上,使系统在90~100℃的温度区间;控制系统漏风率,防止含氧率的升高;保证前端电除尘效率的同时,将一部分电除尘捕集到的灰尘作为钙基脱硫剂的添加剂,并使之参与脱硫反应器内的钙基吸收剂循环过程中;可较多地脱除烟气中的污染物质。     

双循环多级水幕吸收塔烟气除尘脱硫性能研究

以改进后的双循环多级水幕塔对烟气进行除尘脱硫性能的研究,利用双循环不同pH值控制的优点和多级水幕的效果,增加气液接触面积和传质动力,提高SO₂吸收效果。在正交实验的最佳运行工况基础上,实验从烟气流量、上下两段pH、L/G和SO₂进气浓度等方面进行单因素研究。结果表明,除尘效率维持在98%以上,进气SO₂浓度在5 000 mg/m³以下时,脱硫率在93%以上。上段pH值为6、下段pH值为5、L/G在15左右的脱硫效率和运行工况最佳,无结垢现象发生。改进后的吸收塔具有良好的应用前景,实验结果对于现场脱硫设备的调试和运行有很好的参考价值。     

新型转式垃圾焚烧过程中脱氯脱硫机理的研究

为了探讨有机垃圾焚烧过程钙基添加剂对HCl,SO_x生成特性的影响,分别在自行设计的中空水冷转式垃圾焚烧炉和固定床加热炉中进行了一系列的实验,研究结果表明新型转式焚烧炉具有强化传热传质特性,能提高HCl、SO_x的脱除率,可抑制有害气体的生成;同时也研究了 HCl,SO₂气体同时存在时,钙基添加剂对脱氯脱硫效率的影响规律。     

超重力-磷酸钠法脱除低浓度SO2

为开发脱硫率高、成本低、可回收SO₂的脱硫技术,以旋转填料床为吸收设备,磷酸钠溶液为吸收剂,系统开展了液气比L/G、转速N、气体中SO₂浓度CSO₂,in、吸收剂磷酸浓度CL和初始pH等工艺参数和溶液再生循环次数对脱硫率η影响的实验研究。结果表明,η随L/G、N、CL和初始pH的增加而增大,且它们的值越低时,η增加越明显;受G和CSO₂,in影响较小。在适宜操作条件下,脱硫率达99%以上,出口SO₂浓度低于100 mg/m³。磷酸钠溶液可再生循环使用,脱硫率稳定在99%以上。表明超重力-磷酸钠法脱硫技术在小的液气比下即可达到高的脱硫率,吸收剂循环使用,可实现低成本并达标治理SO₂废气,且适用范围宽,具有良好的工业应用前景。     

改性稻草秸秆活性炭的制备及其对SO_2的吸附

以稻草秸秆为原料,在N2氛围中制备活性炭。利用TG/DTG、Boehm滴定、BET比表面积测试、活性炭的工业分析对秸秆在200、300、400、500℃下制备的活性炭形态及其表面化学性质进行了表征。分别比较了原生秸秆、炭化秸秆、乙二胺基秸秆、乙二胺基炭化秸秆用于脱除SO_2气体的吸附效果。结果表明:活性炭的炭化得率是随着温度升高而不断下降;随着炭化温度升高,活性炭的pH值、灰分也随之增加,挥发分含量则不断下降,活性炭表面的酸性官能团减少、碱性官能团增多;乙二胺基炭化秸秆的脱硫效果明显,饱和硫容达到了176.4 mg·g-1。通过研究得出将改性稻草秸秆活性炭应用于烟气脱硫是可行的。     

水体中常见无机阴离子对TiO2薄膜光催化降解甲醛的影响

选择了5种水体中常见的阴离子(Cl^-,SO^2-₄,HPO^2-₄/HPO^2-₄,HCO^-₃/CO^2-₃和NO^-₃),分别考查了其对TiO₂薄膜光催化降解模拟甲醛废水的反应速率的影响;从上述离子的光吸收,对·OH的捕获及其生成的相应的无机自由基的氧化作用以及与甲醛的竞争吸附3个方面讨论了上述离子影响TiO₂薄膜光催化降解模拟甲醛废水的反应速率的原因。结果表明,HCO^-₃/CO^2-₃对TiO₂薄膜光催化降解甲醛具有抑制作用,Cl^-和SO^2-₄的影响不大,H₂PO^-₄/HPO^2-₄和NO^-₃具有促进作用。造成上述结果的主要原因是HCO^-₃/CO^2-₃具有很强的·OH捕获作用;Cl^-,SO^2-₄对·OH捕获作用以及竞争吸附都较弱;H₂PO^-₄/HPO^2-₄在TiO₂表面具有较强的吸附能力,释放出的H⁺起到了酸催化剂的作用;NO^-₃在紫外光的照射下可以产生·OH,此外NO^-₃作为电子受体而降低了TiO₂表面光生电子和空穴的复合几率。     

几种试剂对硝酸根光催化脱色甲基橙的影响

以NO^-₃为光催化剂,在紫外灯照射下,对甲基橙溶液进行光催化脱色。结果表明,叔丁醇、甲醇和乙醇对催化脱色反应有抑制作用; KBr和Na₂SO₄对脱色反应均有促进作用;而且KBr的加入量存在最佳值; Na₂SO₄的促进作用随Na₂SO₄的量的增加逐渐增强。Na₂CO₃的存在对甲基橙的脱色反应没有影响。K₂S₃O₈和NO^-₃之间存在较强的协同作用;KIO₃和NO^-₃之间存在相加作用;KBrO₃和NO^-₃之间存在拮抗作用。     

Simultaneous removal of sulfur dioxide and polycyclic aromatic hydrocarbons from incineration flue gas using activated carbon fibers

Incineration flue gas contains polycyclic aromatic hydrocarbons (PAHs) and sulfur dioxide (SO₂). The effects of SO₂ concentration (0, 350, 750, and 1000 ppm), reaction temperature (160, 200, and 280 °C), and the type of activated carbon fibers (ACFs) on the removal of SO₂ and PAHs by ACFs were examined in this study. A fluidized bed incinerator was used to simulate practical incineration flue gas. It was found that the presence of SO₂ in the incineration flue gas could drastically decrease removal of PAHs because of competitive adsorption. The effect of rise in the reaction temperature from 160 to 280 °C on removal of PAHs was greater than that on SO₂ removal at an SO₂ concentration of 750 ppm. Among the three ACFs studied, ACF-B, with the highest microporous volume, highest O content, and the tightest structure, was the best adsorbent for removing SO₂ and PAHs when these gases coexisted in the incineration flue gas.

ImplicationsSimultaneous adsorption of sulfur dioxide (SO₂) and polycyclic aromatic hydrocarbons (PAHs) emitted from incineration flue gas onto activated carbon fibers (ACFs) meant to devise a new technique showed that the presence of SO₂ in the incineration flue gas leads to a drastic decrease in removal of PAHs because of competitive adsorption. Reaction temperature had a greater influence on PAHs removal than on SO₂ removal. ACF-B, with the highest microporous volume, highest O content, and tightest structure among the three studied ACFs, was found to be the best adsorbent for removing SO₂ and PAHs.     

Removal of SO2 From Flue Gases Using Carbon at Elevated Temperatures

The interaction of a typical flue gas with active charcoal and bituminous coal char at temperatures between 600 and 800°C and atmospheric pressure has been studied. The SO₂ in the flue gas interacts with the carbon to form primarily H₂S, COS, and a carbon-sulfur surface complex. H₂S and COS break through the carbon bed much in advance of SO₂. At 800°C, sulfur retention on the bed exceeds at least 11% before SO₂ breakthrough occurs. The reaction of H₂S and COS with O₂ over active charcoal at 100–140°C to produce sulfur, which deposits on the carbon, has also been studied and found to be feasible. As a result of this study, a new process is outlined for the removal of SO₂ from flue gas, with the ultimate conversion     

Reaction behavior of SO2 in the sintering process with flue gas recirculation

The primary goal of this paper is to reveal the reaction behavior of SO₂ in the sinter zone, combustion zone, drying–preheating zone, and over-wet zone during flue gas recirculation (FGR) technique. The results showed that SO₂ retention in the sinter zone was associated with free-CaO in the form of CaSO₃/CaSO₄, and the SO₂ adsorption reached a maximum under 900ºC. SO₂ in the flue gas came almost from the combustion zone. One reaction behavior was the oxidation of sulfur in the sintering mix when the temperature was between 800 and 1000ºC; the other behavior was the decomposition of sulfite/sulfate when the temperature was over 1000ºC. However, the SO₂ adsorption in the sintering bed mainly occurred in the drying–preheating zone, adsorbed by CaCO₃, Ca(OH)₂, and CaO. When the SO₂ adsorption reaction in the drying–preheating zone reached equilibrium, the excess SO₂ gas continued to migrate to the over-wet zone and was then absorbed by Ca(OH)₂ and H₂O. The emission rising point of SO₂ moved forward in combustion zone, and the concentration of SO₂ emissions significantly increased in the case of flue gas recirculation (FGR) technique.

Implications: Aiming for the reuse of the sensible heat and a reduction in exhaust gas emission, the FGR technique is proposed in the iron ore sintering process. When using the FGR technique, SO₂ emission in exhaust gas gets changed. In practice, the application of the FGR technique in a sinter plant should be cooperative with the flue gas desulfurization (FGD) technique. Thus, it is necessary to study the influence of the FGR technique on SO₂ emissions because it will directly influence the demand and design of the FGD system.     

Electric Utility Applications Of Fabric Filters

Encouraged by the successes attained with fly ash control by fabric filters in Pennsylvania Power & Light and Colorado Ute, other utilities are installing, planning, and/or considering baghouses as a practical and economical means for controlling emissions from the burning of low sulfur coals. Where deposits of alkaline reagents (i.e. nahcolite) are available, some power plants are also considering a process for dry scrubbing SO₂ from the flue gas. By introducing such reagents with the emission ahead of the fabric collector, both partlculates and SO₂ are removed.     

Formation of chlorinated species through reaction of SO2 with NaClO2 powder and their role in the oxidation of NO and Hg0

This study examines gaseous chlorinated species generated from the reaction of sulfur dioxide (SO₂) with sodium chlorite powder (NaClO_2(s)) to obtain insight into the propensity of this process to enhance NO and Hg⁰ oxidation. A packed bed reactor containing NaClO_2(s) was used and the reaction temperature was set to 130 °C. Initially, we determined that the presence of SO₂ enhances the oxidation of NO and Hg⁰ by reaction with NaClO_2(s). We then introduced NO₂ into the gas mixture as a radical scavenger and determined that the chlorinated species generated by the reaction of SO₂ with NaClO_2(s) are OClO, Cl, ClO, and Cl₂. Based on these results, we suggest that such gaseous chlorinated ones are responsible for the enhancement of NO and Hg⁰ oxidation.     

Opacity Reduction Using Dry Hydrated Lime Injection

Abstract

This investigation studied the effects of injecting dry hydrated lime into flue gas to reduce sulfur trioxide, (SO₃) concentrations and consequently stack opacity at the University of Missouri-Columbia power plant. The opacity was due to sulf uric acid mist forming at the stack from high SO₃ concentrations. As a result of light scattering by the mist, a visible plume leaves the stack. Therefore, reducing high concentrations of SO₃ reduces the sulfuric acid mist and consequently the opacity. To reduce SO₃ concentrations, dry hydrated lime is periodically injected into the flue gas upstream of a baghouse and downstream of an induced draft fan. The hydrated lime is transported downstream by the flue gas and deposited on the filter bags in the baghouse forming a filter cake. The reaction between the SO₃ and the hydrated lime takes place on the filter bags. The hydrated lime injection system has resulted in at least 95% reduction in the SO₃ concentration and has reduced the opacity to acceptable limits. Low capital equipment requirements, low operating cost, and increased bag life make the system very attractive to industries with similar problems.     

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。     

Investigation of Selective Catalytic Reduction Impact on Mercury Speciation under Simulated NOx Emission Control Conditions

Abstract

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NO_x) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NO_x reduction, promote the formation of oxidized mercury (Hg²⁺).

The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg⁰) oxidation. Bench-scale experiments were conducted to investigate Hg⁰ oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO₂) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO₂ in the flue gases on Hg⁰ oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg⁰ to Hg²⁺ under SCR reaction conditions. The importance of HCl for Hg⁰ oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg⁰ oxidation occurring across the SCR reactors in the field.     

Catalytic destruction of pentachlorobenzene in simulated flue gas by a V2O5-WO3/TiO2 catalyst

Pentachlorobenzene (PeCB) in simulated flue gas was destructed by a commercial V₂O₅-WO₃/TiO₂ catalyst in this study. The effects of reaction temperature, oxygen concentration, space velocity and some co-existing pollutants on PeCB conversion were investigated. Furthermore, a possible mechanism for the oxidation of PeCB over the vanadium oxide on the catalysts was proposed. Results show that the increase of gas hourly space velocity (GHSV) and the decrease of operating temperature both resulted in the decrease of PeCB removal over the catalyst, while the effect of the oxygen content in the range of 5-20% (v/v) on PeCB conversion was negligible. PeCB decomposition could be obviously affected by the denitration reactions under the conditions because of the positive effect of NO but negative effect of NH₃. The introduction of SO₂ caused the catalyst poisoning, probably due to the sulfur-containing species formed and deposited on the catalyst surface. The PeCB molecules were first adsorbed on the catalyst surface, and then oxidized into the non-aromatic acyclic intermediates, low chlorinated aromatics and maleic anhydride.     

Effects of Sulfur Dioxide and Nitric Oxide on Mercury Oxidation and Reduction under Homogeneous Conditions

Abstract

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.