Simulation of the Radiation-Chemical Conversion of Mercury Vapor in Power-Plant Flue Gases in the Presence of Hydrogen Chloride

The effect of HCl on the conversion of mercury vapor in the electron-beam treatment of power-plant flue gases for removing nitrogen and sulfur oxides was investigated. A kinetic scheme for the process consists of the liquid-phase oxidation of Hg by O₃molecules and OH radicals followed by the adsorption of liquid-phase oxidation products on soot particles, which are removed from the gas flow using filters. It was found that almost complete removal of mercury vapor is attained at typical radiation doses and process temperatures at soot concentrations higher than 100 g/m³(STP). At a soot concentration lower than 100 g/m³(STP) and an HCl concentration higher than 50 mg/m³(STP) in the gas phase, biologically active HgCl₂is formed in considerable amounts.     

Degradation of Dioxins in Electron-Beam Gas Cleaning of Sulfur and Nitrogen Oxides

The efficiency of the electron-beam treatment of power-plant flue gases for the removal of sulfur and nitrogen oxides was examined as applied to the removal of dioxins from the gases. A kinetic scheme of the process was proposed. It involves gas-phase and liquid-phase degradation of dioxin molecules by OH radicals formed under the action of ionizing radiation on gas macrocomponents. It was found that gas toxicity due to dioxins decreased by an order of magnitude at radiation doses typical of the method.     

High efficiency of Mn–Ce‐modified TiO2 catalysts for the low‐temperature oxidation of Hg0 under a reducing atmosphere

Manganese‐ and cerium oxide‐modified titania catalysts were prepared by the deposition precipitation for the removal of elemental mercury (Hg⁰) from simulated yellow phosphorus off‐gas at low temperature. In addition, these catalysts were characterized by X‐ray diffraction, Brunauer–Emmett–Teller measurements, X‐ray photoelectron spectroscopy and field‐emission scanning electron microscope to determine the surface morphology of the obtained compounds and explore their formation mechanism. The results revealed that a Mn–Ce loading and reaction temperature of 10% and 150 °C, respectively, as well as a Mn/Ce molar ratio of 2:1, led to an optimal efficiency for the oxidation of elemental mercury. Furthermore, the effects of flue gas components were investigated. The presence of O₂ clearly promoted the oxidation of Hg⁰. A CO atmosphere did not affect the Hg⁰ oxidation, when compared with N₂, whereas the presence of H₂S and water vapor inhibited the oxidation process. Furthermore, the X‐ray photoelectron spectroscopy spectra of Hg 4f revealed that the elemental mercury adsorbed by the catalyst is present as HgO. Finally, the Hg⁰ catalytic oxidation mechanism was discussed on the basis of the experimental results and characterization analysis.     

Photochemical Removal of Gaseous Elemental Mercury in a Dielectric Barrier Discharge Plasma Reactor

The plasma process has the potential to serve as a low cost mercury oxidation technology that will facilitate elemental mercury removal in a downstream of Flue Gas Desulfurization system. The performance of the main gas constituents, such as H₂O, O₂ and HCl on elemental mercury oxidation under plasma atmosphere was investigated in simulated flue gas. Experiments were carried out in a dielectric barrier discharge reactor operated at 140?°C. Photochemical effects of nanocrystalline titania on oxidation of elemental mercury were also tested. The results indicated that both H₂O and O₂ promote the oxidation of elemental mercury significantly. Active radicals generated by ionization, such as O, O₂ and OH, play the crucial roles in oxidation process. The presence of HCl in N2/O2 stream in plasma system is a very effective way of oxidizing elemental mercury, the nearly complete oxidation of elemental mercury was observed by 4?kV of applied voltage only. The best photocatalytic activity of anatase TiO₂ which was calcined at 600?°C was found in our tests. Compared with the plasma process alone, the oxidation efficiency increased 18.7?C26.3?% with the addition of photocatalyst.     

Removal of Elemental Mercury from Simulated Flue Gas by Combining Non-thermal Plasma with Calcium Oxide

Mercury emission from coal combustion has been the fourth biggest pollutant in China, following the dusts, SO₂ and NO_X. The technology of non-thermal plasma has been widely studied for oxidizing gaseous elemental mercury at low temperature. In this paper, a new method of combining non-thermal plasma with calcium oxide was proposed to remove elemental mercury from simulated flue gas. The effects of non-thermal plasma, input energy, combination mode of plasma and calcium oxide on Hg⁰ removal were investigated in a wire-cylinder non-thermal plasma reactor, whose energy was supplied by a high voltage alternating current power. The peak voltage and energy of the non-thermal plasma were measured by an oscilloscope and a high voltage probe (1000:1). The results showed that most of Hg⁰ was converted to oxidized mercury in simulated flue gas by non-thermal plasma treatment. The Hg⁰ removal efficiency of CaO was improved remarkably strengthened by the non-thermal plasma, which was closely related to input energy, and the maximum mercury removal efficiency was about 80 % at an optimal input energy. Through temperature-programmed decomposition and desorption and energy dispersive spectroscopy analysis, the majority of mercury species on CaO surface were Hg₂O and HgO₃ rather than HgO. Therefore, it can be concluded that O₃ plays an important role in Hg⁰ oxidation under the condition of non-thermal plasma.     

Role of Ceria in the Design of Composite Materials for Elemental Mercury Removal

The necessity to drastically act against mercury pollution has been emphatically addressed by the United Nations. Coal‐fired power plants contribute a great deal to the anthropogenic emissions; therefore, numerous sorbents/catalysts have been developed to remove elemental mercury (Hg⁰) from flue gases. Among them, ceria (CeO₂) has attracted significant interest, due to its reversible Ce³⁺/Ce⁴⁺ redox pair, surface‐bound defects and acid‐base properties. The removal efficiency of Hg⁰ vapor depends among others, on the flue gas composition and temperature. CeO₂ can be incorporated into known materials in such a way that the abatement process can be effective at different operating conditions. Hence, the scope of this account is to discuss the role of CeO₂ as a promoter, active phase and support in the design of composite Hg⁰ sorbents/catalysts. The elucidation of each of these roles would allow the integration of CeO₂ advantageous characteristics to such degree, that tailor‐made environmental solution to complex issues can be provided within a broader application scope. Besides, it would offer invaluable input to theoretical calculations that could enable the materials screening and engineering at a low cost and with high accuracy.     

The influence of the active component and support nature, gas mixture composition on physicochemical and catalytic properties of catalysts for soot oxidation

Physicochemical and catalytic properties of compositions Fe(Ce)–Mn–O/support (gamma-, theta-, alpha-Al₂O₃, SiO₂ as the support) and Pt/CeO₂/theta-Al₂O₃ for oxidation of soot were characterized. It was established that the phase composition of the initial catalysts depended mainly on the nature of the active component and preparation conditions. Non-isothermal treatment of the soot–catalyst compositions at the temperature up to 1000 °C resulted in a change in the phase composition depending mainly on the final treatment temperature. The catalyst surface area was determined by the support nature. It was established that catalyst activities for oxidation of soot are determined by both catalyst nature and composition of gas mixture. The process of the soot oxidation is thought to involve oxygen from the catalyst surface. The higher proportion of weakly bound surface oxygen, the higher was the catalyst activity. An increase in the oxygen concentration from 5% O₂/N₂ to 15% O₂/N₂ is shown to lead to a decrease of the temperature of the soot oxidation. The influence of the oxygen concentration on the process of soot oxidation becomes weaker in the presence of water vapor. Results showed that the presence of NO in the gas mixture favors a decrease in the oxidation temperature of the soot, the higher being the nitrogen oxide concentration, the more pronounced effect. Introduction of SO₂ in amount of 50 ppm in the gas mixture has no noticeable effect on the process of the soot oxidation. Among the catalysts under study, Fe–Mn–K–O/gamma-Al₂O₃ is most effective to oxidation of the soot at otherwise identical conditions.     

负载Mn的Fe基MOFs脱汞剂烟气脱汞研究

基于Fe基金属有机骨架（MOFS）作为载体,采用浸渍法制备了负载6% Mn的Mn/MIL-100（Fe）脱汞剂。在模拟烟气中,搭建固定床研究了Mn/MIF-100（Fe）脱除单质汞（Hg⁰）性能。采用X射线衍射分析（XRD）、X射线电子能谱（XPS）、N₂吸附-脱附（BET）和热重分析（TGA）对材料进行表征。研究表明,Mn/MIF-100（Fe）脱除单质汞（Hg⁰）效率较高,在250℃,空速（GHSV）为180000h^-1时,脱汞（Hg⁰）效率达82%以上。Mn/MIF-100（Fe）主要的脱汞机理是催化氧化,Mn的负载促进了汞的吸附,并随着烟气温度的提高,单质汞的氧化效率逐渐提高。O₂和NO促进汞的脱除,SO₂和NH₃抑制汞的脱除。Mn/MIL-100（Fe）整体上对复杂烟气的适应能力强。     

Cu?Ti?O catalyst for complex purification of gases

Cu–Ti–O catalysts activity in the reactions of complete oxidation of CO and C₄H₁₀, selective catalytic reduction of NO by ammonia, SO₂ oxidation to SO₃, as well as the catalyst resistance to sulfur poisoning were studied. We suggest these catalysts for the combined removal of NO, CO and toxic organics from flue gases.     

Simultaneous Removal of Polycyclic Aromatic Hydrocarbons and Soot Particles from flue Gas by Gliding arc Discharge Treatment

The removal of Polycyclic aromatic hydrocarbons (PAH’s) and soot particles from flue gas was studied using a gliding arc discharge reactor, and the flue gas was emitted from the polyethylene (PE) or polyvinyl chloride (PVC) combustion in a laboratory-scale drop tube furnace. The removal efficiencies have ranged from 70.3% up to 74.4%. The maximum removal efficiency of soot particles was up to 89.3%. Experimental results show that the technique can successfully remove PAH’s and soot particles from flue gas, a possible mechanism is proposed to explain the experimental observations.     

Fundamentals and Environmental Applications of Non-thermal Plasmas: Multi-pollutants Emission Control from Coal-Fired Flue Gas

Simultaneous control of multi-pollutants emission from coal-fired flue gas is essential for environmental quality. Non-thermal plasma (NTP) technologies have made numerous successful applications of combined removal for sulfur dioxide (SO₂), nitrous oxide, particulate matter and mercury. Nitric oxide, elemental mercury can be oxidized in the gas phase, while fine particle gets agglomeration in the same NTP device. SO₂ gets absorbed after heterogeneous oxidation by discharge. All the gaseous pollutants and aerosols generated will be further oxidized and captured in wet NTP device. Applications of NTP and typical configurations are also summarized.     

水蒸气和α-Fe_2O_3对铈改性半焦脱除单质汞的影响研究

采用浸渍法制备了铈改性半焦吸附剂(Ce/SC),在小型固定床反应器上考察了水蒸气和α-Fe_2O_3对Ce/SC脱除Hg~0性能的影响,并利用X射线衍射、H2程序升温还原、X射线光电子能谱等分析手段对其机理进行了探究。结果表明,水蒸气会明显抑制Ce/SC对单质汞的脱除效率,原因是H_2O分子在活性组分CeO_2表面发生解离,部分晶格氧转化成Ce-OH官能团,从而导致其氧化活性的降低;α-Fe_2O_3的加入对Ce/SC的脱汞性能无显著影响;当水蒸气和α-Fe_2O_3同时存在时,Ce/SC的脱汞效率虽然有所降低,但是其降低幅度明显低于水蒸气单独作用时的情况,这主要是因为水蒸气与α-Fe_2O_3作用增加了其表面化学吸附氧的含量,提高了α-Fe_2O_3的氧化活性,促进单质汞的氧化和脱除。     

Experimental Study on Demercurization Performance of Wet Flue Gas Desulfurization System

The demercurization performance of wet flue gas desulfurization (WFGD) system was investigated by measuring mercury concentrations at the inlet and outlet of WFGD system with a QM201H mercury analyzer. The selected desulfurizer included NH₃·H₂O, NaOH, Na₂CO₃, Ca(OH)₂ and CaCO₃. The influences of adding oxidant and coagulant such as KMnO₄, Fenton reagent, K₂S₂O₈/CuSO₄ and Na₂S into desulfurization solutions were also studied. The results show that elemental mercury is the main component of gaseous mercury in coal‐fired flue gas, and the proportion of oxidized mercury is less than 36%. Oxidized mercury could be removed by WFGD system efficiently, and the removal efficiency could amount to 81.1%–92.6%. However, the concentration of elemental mercury slightly increased at the outlet of WFGD as a result of its insolubility and re‐emission. Therefore, the removal efficiency of gaseous mercury is only 13.3%–18.3%. The mercury removal efficiency of WFGD system increased with increasing the liquid‐gas ratio. In addition, adding KMnO₄, Fenton reagent, K₂S₂O₈/CuSO₄ and Na₂S into desulfurization solutions could increase the mercury removal efficiency obviously. Various additives have different effects, and Na₂S is demonstrated to be the most efficient, in which a mercury removal efficiency of 67.2% can be reached.     

MnOx-TiO2吸附剂对燃煤烟气中汞的脱除

以锐钛矿型TiO_2为载体,采用浸渍法对其进行MnO_x改性制备脱汞吸附剂,探究了负载量、焙烧温度、反应温度及烟气组分等参数对吸附剂脱汞性能的影响。利用N_2吸附-脱附、TG/DTG、XRD、FT-IR、Hg-TPD、XPS等方法对吸附剂的理化性质进行了表征。结果表明,Mn的最佳负载量为12%,最佳焙烧温度和反应温度分别为450和300℃,在实验条件下MnO_x-TiO_2吸附剂可达到的最佳脱汞效率为98.46%。烟气中少量的O_2及微量的HCl对吸附剂的脱汞有较强的促进作用;SO_2对吸附剂的脱汞有较强的抑制作用,SO_2与Hg~0存在的竞争吸附作用以及脱汞反应中产生的硫酸盐覆盖活性位点表面,是导致脱汞效率下降的主要原因。烟气中的CO_2和NO也会对汞的脱除产生轻微的抑制作用。负载在吸附剂上的MnO_x存在Mn~(4+)、Mn~(3+)两种价态,其中,Mn~(4+)将Hg~0氧化为Hg~(2+),自身被还原为Mn~(3+)。结合实验和分析结果发现,Hg~0的吸附和氧化基本遵循Mars-Maessen和Langmuir-Hinshelwood机理。     

复杂烟气条件下太西活性焦脱除Hg0的实验研究

为了解复杂烟气条件下活性焦吸附剂的脱汞特性,利用汞渗透管和主要气体成分模拟复杂烟气,在实验室规模的固态吸附剂汞吸附效能测定系统上,进行了太西活性焦吸附单质汞的实验研究,并采用FT-IR对活性焦表面进行了光谱表征。结果表明,在活性焦表面存在各种含氧官能团;在CO₂/N₂/O₂/SO₂/Hg⁰烟气体系中,当SO₂加入量为400、855、1 520 mL/m³时,出口汞浓度分别为36、43、48 μg/m³,SO₂对系统吸附Hg⁰的能力有抑制作用;在CO₂/N₂/O₂/NO/Hg⁰烟气体系中,较低浓度的NO对Hg⁰脱除有抑制作用,而高浓度值的NO抑制作用减弱;在CO₂/N₂/O₂/NO/SO₂/Hg⁰烟气体系下,提高NO浓度对Hg⁰脱除有一定的促进作用,而提高SO₂浓度初期促进汞的脱除,后期则表现为抑制作用。     

Use of radiation sources with mercury isotopes for real-time highly sensitive and selective benzene determination in air and natural gas by differential absorption spectrometry with the direct Zeeman effect

A new analytical portable system is proposed for the direct determination of benzene vapor in the ambient air and natural gas, using differential absorption spectrometry with the direct Zeeman effect and innovative radiation sources: capillary mercury lamps with different isotopic compositions (¹⁹⁶Hg, ¹⁹⁸Hg, ²⁰²Hg, ²⁰⁴Hg, and natural isotopic mixture). Resonance emission of mercury at a wavelength of 254 nm is used as probing radiation. The differential cross section of benzene absorption in dependence on wavelength is determined by scanning of magnetic field. It is found that the sensitivity of benzene detection is enhanced three times using lamp with the mercury isotope ²⁰⁴Hg in comparison with lamp, filled with the natural isotopic mixture. It is experimentally demonstrated that, when benzene content is measured at the Occupational Exposure Limit (3.2 mg/m³ for benzene) level, the interference from SO₂, NO₂, O₃, H₂S and toluene can be neglected if concentration of these gases does not exceed corresponding Occupational Exposure Limits. To exclude the mercury effect, filters that absorb mercury and let benzene pass in the gas duct are proposed. Basing on the results of our study, a portable spectrometer is designed with a multipath cell of 960 cm total path length and detection limit 0.5 mg/m³ at 1 s averaging and 0.1 mg/m³ at 30 s averaging. The applications of the designed spectrometer to measuring the benzene concentration in the atmospheric air from a moving vehicle and in natural gas are exemplified.     

Thermodynamic possibilities and constraints of pure hydrogen production by a chromium,nickel, and manganese-based chemical looping process at lower temperatures

The reduction of chromium, nickel, and manganese oxides by hydrogen, CO, CH₄, and model syngas (mixtures of CO + H₂ or H₂ + CO + CO₂) and oxidation by water vapor has been studied from the thermodynamic and chemical equilibrium point of view. Attention was concentrated not only on the convenient conditions for reduction of the relevant oxides to metals or lower oxides at temperatures in the range 400–1000 K, but also on the possible formation of soot, carbides, and carbonates as precursors for the carbon monoxide and carbon dioxide formation in the steam oxidation step. Reduction of very stable Cr₂O₃ to metallic Cr by hydrogen or CO at temperatures of 400–1000 K is thermodynamically excluded. Reduction of nickel oxide (NiO) and manganese oxide (Mn₃O₄) by hydrogen or CO at such temperatures is feasible. The oxidation of MnO and Ni by steam and simultaneous production of hydrogen at temperatures between 400 and 1000 K is a difficult step from the thermodynamics viewpoint. Assuming the Ni—NiO system, the formation of nickel aluminum spinel could be used to increase the equilibrium hydrogen yield, thus, enabling the hydrogen production via looping redox process. The equilibrium hydrogen yield under the conditions of steam oxidation of the Ni—NiO system is, however, substantially lower than that for the Fe—Fe₃O₄ system. The system comprising nickel ferrite seems to be unsuitable for cyclic redox processes. Under strongly reducing conditions, at high CO concentrations/partial pressures, formation of nickel carbide (Ni₃C) is thermodynamically favored. Pressurized conditions during the reduction step with CO/CO₂ containing gases enhance the formation of soot and carbon-containing compounds such as carbides and/or carbonates.     

燃煤电站布袋除尘器和静电除尘器脱汞性能比较

采用国际上通用的Ontario Hydro方法（OHM）对中国五个燃煤电站布袋除尘器（FF）/静电除尘器（ESP）前、后的烟气进行采样,应用美国EPA标准方法测定了烟气中Hg0、Hg2+和HgP的浓度。应用DMA80测定固体样品（煤、底灰、ESP飞灰）中的汞浓度。由汞平衡得出各个环节中汞所占的份额。由此得到FF和ESP脱除烟气中汞的性能。安装FF的电站1和2的综合脱除效率约为80%和20%,安装ESP的电站3、4和5的综合脱除效率分别为6%、20%和4%左右。这说明FF比ESP有更加优良的脱汞性能,而且FF/ESP脱除烟气中的汞受到很多因素的影响。     

Control factors and by-products during decomposition of butane in electron beam irradiation

This research was conducted to determine the removal characteristics of butane, using an electron beam. Influential factors, such as an initial concentration, background gases (nitrogen, air, and helium), and absorbed doses (kGy) were investigated. The decomposition efficiencies of background gases showed that oxidation caused by radicals formed from gases, such as N₂ and O₂, had a greater influence on results than oxidation from primary electrons for butane removal. Removal efficiencies were 40% at 2.5 kGy and 66% at 10 kGy, when the initial concentration of butane was 60 ppmC. When the initial concentration was lower, the energy efficiency of butane removal by electron beam was higher. By-products, including CO₂, CO, acetaldehyde, and acetone, formed after electron beam irradiation. Concentrations of CO₂ and CO tended to increase when absorbed doses increased as butane was decomposed by the electron beam through an advanced oxidation.