湿法烟气脱硫系统的脱汞性能现场实验

分析湿法烟气脱硫系统的脱汞性能,对控制燃煤电厂的汞污染具有重要意义。利用安大略水法和吸附管法分别对某600 MW电厂湿法脱硫系统的进出口的烟气进行了采样,测量了烟气中各形态汞浓度,并分析了该系统对烟气总汞、气态氧化态汞的脱除效果以及对气态单质汞的影响。研究结果表明,安大略水法和吸附管法均能较为准确地测定湿法脱硫系统进出口烟气中的汞含量,测得入口和出口的氧化汞与平均值的相对误差的绝对值分别为3.5%和1.3%;入口和出口的单质汞与平均值相对误差的绝对值分别为16.6%和3.3%。其中吸附管法操作相对简单。通过湿法烟气脱硫系统后,烟气中氧化态汞的浓度可下降87.5%,其中约67.5%的氧化态汞被湿法脱硫系统脱除,约20%的氧化态汞在脱硫浆液的还原作用下被还原为单质汞,导致脱硫系统出口的单质汞浓度高于入口。     

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%。     

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。     

直接红染料的臭氧脱色与中间产物研究

以直接红B模拟染料废水为研究对象，考察了臭氧化过程中染料溶液的吸光度和TOC的变化，同时利用离子色谱仪和GC/MS对染料的降解过程进行了分析，最后用发光细菌法检测了染料溶液急性毒性的变化。结果表明，臭氧对染料的降解符合一级反应动力学，20 min时对染料的脱色率达到99.2%；反应40 min后TOC减少32.55%，染料分子有97.8%的S被氧化为SO^2-₄，偶氮键被臭氧化为N₂，分子中的仲胺基小部分转化成游离NH⁺₄和NO^-₃；在臭氧化过程前期新生成的醛类和酰胺类物质使溶液急性毒性迅速上升，25 min后溶液毒性开始逐渐下降。     

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。     

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。     

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。     

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%。     

容积负荷对ANAMMOX生物滤池脱氮效能的影响及其基质动力学

采用2套启动成功的上向流厌氧氨氧化（ANAMMOX）生物滤柱，通过调节进水NaNO₂和（NH₄）₂SO₄ 的浓度负荷及水力负荷，改变进水容积负荷，探讨容积负荷对ANAMMOX生物滤柱脱氮效能的影响及其动力学模型。结果表明，滤速恒定条件下，通过提高进水基质浓度来提高进水TN容积负荷，其容积负荷去除动力学过程符合Monod-Haldane基质抑制模型。进水NH₄⁺-N与NO₂^--N浓度分别低于100 mg/L和133 mg/L时，反应器脱氮效果不受明显影响，TN容积去除负荷可达4.21 kg/（m³·d），TN去除率可达80%以上。进水基质浓度恒定条件下，通过提高滤速来提高进水TN容积负荷，其容积负荷去除动力学过程符合零级动力学方程。不受基质浓度抑制的条件下，滤速为3.0 m/h、进水容积负荷为8.82 kg/（m³·d）时，反应器总氮容积负荷去除量可达7.15 kg/（m³·d），总氮去除率可达81.1%。     

300 MW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.     

Study on the removal of elemental mercury from simulated flue gas by Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>/AC at low temperature

Fe₂O₃ and CeO₂ modified activated coke (AC) synthesized by the equivalent-volume impregnation were employed to remove elemental mercury (Hg⁰) from simulated flue gas at a low temperature. Effects of the mass ratio of Fe₂O₃ and CeO₂, reaction temperature, and individual flue gas components including O₂, NO, SO₂, and H₂O (g) on Hg⁰ removal efficiency of impregnated AC were investigated. The samples were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Results showed that with optimal mass percentage of 3 % Fe₂O₃ and 3 % CeO₂ on Fe3Ce3/AC, the Hg⁰ removal efficiency could reach an average of 88.29 % at 110 °C. Besides, it was observed that O₂ and NO exhibited a promotional effect on Hg⁰ removal, H₂O (g) exerted a suppressive effect, and SO₂ showed an insignificant inhibition without O₂ to some extent. The analysis of XPS indicated that the main species of mercury on used Fe3Ce3/AC was HgO, which implied that adsorption and catalytic oxidation were both included in Hg⁰ removal. Furthermore, the lattice oxygen, chemisorbed oxygen, and/or weakly bonded oxygen species made a contribution to Hg⁰ oxidation.     

Ultra-high adsorption of Hg0 using impregnated activated carbon by selenium

Activated carbon was one of the main adsorptions utilized in elemental mercury (Hg⁰) removal from coal combustion flue gas. However, the high cost and low physical adsorption efficiency of activated carbon injection (ACI) limited its application. In this study, an ultra-high efficiency (nearly 100%) catalyst sorbent-Se_x/Activated carbon (Se_x/AC) was synthesized and applied to remove Hg⁰ in the simulated flue gas, which exhibited 120 times outstanding adsorption performance versus the conventional activated carbon. The Se_x/AC reached 17.98 mg/g Hg⁰ adsorption capacity at 160 °C under the pure nitrogen atmosphere. Moreover, it maintained an excellent mercury adsorption tolerance, reaching the efficiency of Hg⁰ removal above 85% at the NO and SO₂ conditions in a bench-scale fixed-bed reactor. Characterized by the multiple methods, including BET, XRD, XPS, kinetic and thermodynamic analysis, and the DFT calculation, we demonstrated that the ultrahigh mercury removal performance originated from the activated Se species in Se_x/AC. Chemical adsorption plays a dominant role in Hg⁰ removal: Selenium anchored on the surface of AC would capture Hg⁰ in the flue gas to form an extremely stable substance-HgSe, avoiding subsequent Hg⁰ released. Additionally, the oxygen-containing functional groups in AC and the higher BET areas promote the conversion of Hg⁰ to HgO. This work provided a novel and highly efficient carbon-based sorbent -Se_x/AC to capture the mercury in coal combustion flue gas.

Selenium-modified porous activated carbon and the interface functional group promotes the synergistic effect of physical adsorption and chemical adsorption to promote the adsorption capacity of Hg⁰.

     

Gas-phase elemental mercury removal in a simulated combustion flue gas using TiO2 with fluorescent light

A previously proposed technology incorporating TiO₂ into common household fluorescent lighting was further tested for its Hg⁰ removal capability in a simulated flue-gas system. The flue gas is simulated by the addition of O₂, SO₂, HCl, NO, H₂O, and Hg⁰, which are frequently found in combustion facilities such as waste incinerators and coal-fired power plants. In the O₂ + N₂ + Hg⁰ environment, a Hg⁰ removal efficiency (η_Hg) greater than 95% was achieved. Despite the tendency for η_Hg to decrease with increasing SO₂ and HCl, no significant drop was observed at the tested level (SO₂: 5–300 ppm_v, HCl: 30–120 ppm_v). In terms of NO and moisture, a significant negative effect on η_Hg was observed for both factors. NO eliminated the OH radical on the TiO₂ surface, whereas water vapor caused either the occupation of active sites available to Hg⁰ or the reduction of Hg₀ by free electron. However, the negative effect of NO was minimized (η_Hg > 90%) by increasing the residence time in the photochemical reactor. The moisture effect can be avoided by installing a water trap before the flue gas enters the Hg⁰ removal system.

Implications: This paper reports a novel technology for a removal of gas-phase elemental mercury (Hg⁰) from a simulated flue gas using TiO₂-coated glass beads under a low-cost, easily maintainable household fluorescent light instead of ultraviolet (UV) light. In this study, the effects of individual chemical species (O₂, SO₂, HCl, NO, and water vapor) on the performance of the proposed technology for Hg⁰ removal are investigated. The result suggests that the proposed technology can be highly effective, even in real combustion environments such as waste incinerators and coal-fired power plants.     

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.     

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.     

Distribution of mercury in the combustion products from coal-fired power plants in Guizhou,southwest China

Method 30B and the Ontario Hydro Method (OHM) were used to sample the mercury in the flue gas discharged from the seven power plants in Guizhou Province, southwest China. In order to investigate the mercury migration and transformation during coal combustion and pollution control process, the contents of mercury in coal samples, bottom ash, fly ash, and gypsum were measured. The mercury in the flue gas released into the atmosphere mainly existed in the form of Hg°. The precipitator shows a superior ability to remove Hg^p (particulate mercury) from flue gas. The removal efficiency of Hg²⁺ by wet flue gas desulfurization (WFGD) was significantly higher than that for the other two forms of mercury. The synergistic removal efficiency of mercury by the air pollution control devices (APCDs) installed in the studied power plants is 66.69–97.56%. The Hg mass balance for the tested seven coal-fired power plants varied from 72.87% to 109.67% during the sampling time. After flue gas flowing through APCDs, most of the mercury in coal was enriched in fly ash and gypsum, with only a small portion released into the atmosphere with the flue gas. The maximum discharge source of Hg for power plants was fly ash and gypsum instead of Hg emitted with flue gas through the chimney into the atmosphere. With the continuous upgrading of APCDs, more and more mercury will be enriched in fly ash and gypsum. Extra attention should be paid to the re-release of mercury from the reutilization of by-products from APCDs.

Implications: Method 30B and the Ontario Hydro Method (OHM) were used to test the mercury concentration in the flue gas discharged from seven power plants in Guizhou Province, China. The concentrations of mercury in coal samples, bottom ash, fly ash, and gypsum were also measured. By comparison of the mercury content of different products, we found that the maximum discharge source of Hg for power plants was fly ash and gypsum, instead of Hg emitted with flue gas through the chimney into the atmosphere. With the continuous upgrading of APCDs, more and more mercury will be enriched in fly ash and gypsum. Extra attention should be paid to the re-release of mercury from the reutilization of by-products from APCDs.     

Simultaneous removal of NOx,SO2, and Hg from flue gas in FGD absorber with oxidant injection (NaClO2)– full-scale investigation

ABSTRACT

This article presents the results of an industrial-scale study (on 400 MW_e lignite fired unit) of simultaneous NO_x, SO₂, and Hg^T removal in FGD absorber with oxidant injection (NaClO₂) into flue gas. It was confirmed that the injection of sodium chlorite upstream the FGD (Flue Gas Desulfurization) absorber oxidize NO to NO₂, Hg⁰ to Hg²⁺, and enhancing NO_x and Hg^T removal efficiency from exhaust gas in FGD absorber. Mercury removal efficiency grows with the rise of degree of oxidation NO to NO₂ and was limited by the phenomenon of re-emission. For NO_x removal the most critical parameters is slurry pH and temperature. There was no negative effect on sulfur dioxide removal efficiency caused by oxidant injection in tested FGD absorber. Based on the data provided, NO_x and Hg^T emissions can be reduced by adjusting the FGD absorber operating parameters combined with oxidant injection.     

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。     

Low Concentration Mercury Sorption Mechanisms and Control by Calcium-Based Sorbents: Application in Coal-Fired Processes

ABSTRACT

The capture of elemental mercury (Hg⁰) and mercuric chloride (HgCl₂) by three types of calcium (Ca)-based sor-bents was examined in this bench-scale study under conditions prevalent in coal-fired utilities. Ca-based sorbent performances were compared with that of an activated carbon. Hg⁰ capture of about 40% (nearly half that of the activated carbon) was achieved by two of the Ca-based sorbents. The presence of sulfur dioxide (SO₂) in the simulated coal combustion flue gas enhanced the Hg⁰ capture from about 10 to 40%. Increasing the temperature in the range of 65-100 °C also caused an increase in the Hg⁰ capture by the two Ca-based sorbents. Mercuric chloride (HgCl₂) capture exhibited a totally different pattern. The presence of SO₂ inhibited the HgCl₂ capture by Ca-based sorbents from about 25 to less than 10%. Increasing the temperature in the studied range also caused a decrease in HgCl₂ capture. Upon further pilot-scale confirmations, the results obtained in this bench-scale study can be used to design and manufacture more cost-effective mercury sorbents to replace conventional sorbents already in use in mercury control.     

Simultaneous Control of Hg0, SO2, and NOx by Novel Oxidized Calcium-Based Sorbents

Abstract

Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents leads to a significant improvement in elemental Hg vapor (Hg⁰), SO₂, and NO_x removal from simulated flue gases. In the study presented here, two classes of Ca-based sorbents (hydrated limes and silicate compounds) were investigated. A number of oxidizing additives at different concentrations were used in the Ca-based sorbent production process. The Hg⁰, SO₂, and NO_x capture capacities of these oxidant-enriched sorbents were evaluated and compared to those of a commercially available activated carbon in bench-scale, fixed-bed, and fluid-bed systems. Calcium-based sorbents prepared with two oxidants, designated C and M, exhibited Hg⁰ sorp-tion capacities (~100 μg/g) comparable to that of the activated carbon; they showed far superior SO₂ and NO_x sorption capacities. Preliminary cost estimates for the process utilizing these novel sorbents indicate potential for substantial lowering of control costs, as compared with other processes currently used or considered for control of Hg⁰, SO₂, and NO_x emissions from coal-fired boilers. The implications of these findings toward development of multipollutant control technologies and planned pilot and field evaluations of more promising multipollutant sorbents are summarily discussed.