Elemental Mercury Control by Novel Oxidant and Sorbent in an Entrained-Flow System

An entrained-flow system has been designed and constructed to simulate in-flight mercury capture by sorbents in ducts of coal-fired utility plants. The test conditions of 1.5 s residence time, 140°C temperature, 4.5 ppbv inlet Hg⁰ concentration, and 0–20 lb/MMacf sorbent injection rates were chosen to simulate conditions in the ducts. Novel oxidants developed in previous fixed-bed tests and novel sorbents derived from the novel oxidants were tested for their Hg⁰ capture in the entrained-flow system to examine the possibility of using those sorbents in a full-scale system. Darco-FGD and Darco Hg-LH served as benchmark sorbents with which mercury control capability of the novel oxidants and novel sorbents could be compared. The test results showed that the novel oxidants have remarkable Hg⁰ oxidation capability, and the novel sorbents showed a better performance in Hg⁰ removal than Darco Hg-LH.     

Gaseous mercury oxidation behavior in homogeneous reaction with chlorine compounds

Homogeneous oxidation reactions of gaseous elemental mercury were experimentally tested to study the behavior of mercury compounds that contribute to toxic emissions in combustion flue gas. Chemical equilibrium calculations and reaction kinetics analysis were also carried out to help explain the experimental results. In particular, the chemical forms of oxidized mercury and their reaction paths were verified in detail. Among the experimental results, molecular chlorine was confirmed to have a higher oxidizing ability toward elemental mercury than hydrogen chloride does. From the chemical equilibrium calculation, the final product of mercury compounds oxidized by chlorine was confirmed to be mercury chloride (HgCl₂). Numerical analyses of reaction kinetics were mostly consistent with the experimental results and the chemical equilibrium calculations. The ratio of mercury oxidization by chlorine increases with temperature from 473 K to 873 K, although it decreases at temperatures higher than 1000 K. Sensitivity analysis revealed the dominant reaction path of the mercury oxidation by chlorine. First, elemental mercury reacts with Cl radicals to form HgCl. Then, the HgCl reacts with Cl₂ to produce HgCl₂.     

Treatment of mercury‐contaminated soils with activated carbon: A laboratory,field, and modeling study

A series of laboratory batch leaching tests was conducted to evaluate the performance of different activated carbons in stabilizing mercury in soils. Based on the results of these experiments, an amendment application rate of 5 percent powdered activated carbon (PAC) was selected for in situ field application at a former industrial facility. A geochemical model was also developed to simulate the interactions between mercury and activated carbon in vadose‐zone soils. Modeling was used to (1) better understand possible mercury sequestration mechanisms and (2) predict the in situ performance of PAC. Model results indicate dissolved mercury concentrations observed in batch tests are consistent with equilibrium partitioning of mercury between dissolved organic matter, soil organic matter, and PAC. Activated carbon is predicted to reduce dissolved mercury concentrations via two mechanisms: (1) the formation of stable mercury complexes on PAC surfaces and (2) the direct adsorption of dissolved organic matter that would otherwise be available for mercury dissolution. Study results demonstrate PAC effectiveness for site soils with mercury concentrations below 200 mg/kg. © 2010 Wiley Periodicals, Inc.     

Experimental study on flue gas purifying of MSW incineration using in-pipe jet adsorption techniques

This paper presents the experimental research process and results about flue gas purifying of municipal solid wastes (MSW) incineration using in-pipe jet adsorption techniques. MSW incineration was carried out in a fluidized bed test rig, and the flue gas purifying was carried out in an in-pipe jet adsorption test rig. The experimental results are as follows: when the feedstock of activated carbon is 1.6g/Nm(3), the desulfurization efficiency is 83%, the denitrification efficiency is 41%, and the dechlorination efficiency is 27%. The order of purifying effect of the three kinds of adsorbents on acidic gases from MSW incineration is activated carbon>activated bauxite>kaolin. Comparison of adsorption capabilities of the three kinds of adsorbents to heavy metals shows that activated carbon is the best additive to remove Cd, Pb and Cu, kaolin is inferior, and activated bauxite is the worst one. However, activated bauxite is the best additive to remove Hg, and it can remove Cd effectively. PAHs in fly ash are dominated by three-, four-, and five-ringed PAHs, and PAHs in the flue gas mainly include three- and four-ringed PAHs. When the injected quantity of additive is constant, the order of cleaning effect on PAHs is kaolin>activated carbon>activated bauxite. These three kinds of adsorbents have different purifying effects on acidic gases, heavy metals and PAHs in the flue gas from MSW incineration. In general, activated carbon has a better adsorption capability.     

Removal of mercury from flue gas using sewage sludge-based adsorbents

Mercury from coal-fired utility boilers, as the largest atmospheric mercury emission source, imposes serious environmental risks and health concerns. In order to explore the possibility of reducing costs of activated carbon injection, we investigated the most promising mercury control technology, Hg⁰ removal using ZnCl₂-impregnated adsorbents derived from sewage sludge. The results demonstrated that sludge-based adsorbents (SBAs) had fairly high mercury adsorption capacity over a wide range of temperatures (80–170 °C). Oxidizing atmosphere could improve the adsorption of Hg⁰ and weaken the inhibition of SO₂ on mercury adsorption to some extent. NO exhibited no obvious impact on mercury removal performance. In addition, to clarify whether oxygen- or chlorine-containing functional groups attributed to good mercury adsorption capacity of SBAs, the oxygen-containing functional groups were removed using Boehm’s method, and a temperature-programmed decomposition desorption experiment was conducted. The results suggest that chlorine-containing functional groups played a significant role in the removal process of mercury from flue gas using SBAs.     

Thermogravimetric and XRD study of the effects of chloride salts on the thermal decomposition of mercury compounds

In this paper, the effects of chloride salt (MgCl₂, CaCl₂ or NaCl) addition on the thermal decomposition of five inorganic mercury compounds (HgCl₂, HgS, Hg(NO₃)₂·H₂O, HgO, and HgSO₄) were investigated by thermogravimetric analysis. Mercury-contaminated soil samples collected from Inner Mongolia were used to verify the results. The desorption temperatures of the mercury compounds increased in the following order: HgCl = HgCl₂ < HgS < Hg(NO₃)₂·H₂O < HgO < HgSO₄. Among the chloride salts, MgCl₂ had the greatest effect on thermal desorption of the mercury compounds, with the greatest reduction in the initial temperature of thermal desorption. After MgCl₂ treatment, the mercury removal rates for the soil were 65.67–81.35 % (sample A), 70.74–84.91 % (sample B), and 69.08 % (sample C). The increase in the mercury removal rate for sample C with addition of MgCl₂ was particularly large (34.96–69.08 %). X-Ray diffraction analysis of white crystals from the thermal desorption with MgCl₂ indicated that MgCl₂ promoted conversion of the mercury compounds in the soil to mercury(II) chloride and dimercury dichloride. This transformation is beneficial for applying thermal desorption to remedy mercury-contaminated soils and treat of mercury containing waste.     

Pyrrolidinium Imides: Promising Ionic Liquids for Direct Capture of Elemental Mercury from Flue Gas

A new approach to vapor phase elemental mercury capture has been explored; this approach exploits an ionic liquid coating layer to oxidize elemental mercury for subsequent immobilization by chelating ligands. The room temperature ionic liquid 1-butyl-1-methyl pyrrolidinium bis(trifluoromethane sulfonyl)imide (P₁₄) was selected for study based on its oxidation potential window, thermal stability, and low vapor pressure. Tests were also completed in which KMnO₄ was added to P₁₄ to form a new ionic liquid, P₁₄–KMnO₄, with a higher oxidation potential. In room-temperature bulk liquid phase capture experiments, 59% of the elemental mercury in the inlet gas was captured using P₁₄ alone; mercury capture using P₁₄–KMnO₄ was quantitative. P₁₄ and P₁₄–KMnO₄ coatings were successfully applied to mesoporous silica substrates and to silica substrates functionalized with mercury chelating ligands. The coating layers were found to be thermally stable up to 300°C. Fixed-bed tests of nonfunctionalized silica coated with P₁₄ showed an elemental mercury uptake of 2.7 mg/g adsorbent at 160°C; at the same temperature, functionalized silica coated with P₁₄–KMnO₄ showed an elemental mercury capacity of at least 7.2 mg/g adsorbent, several times higher than that of activated carbon. The empty bed gas residence time in these tests was 0.04 s. A chelating adsorbent incorporating P₁₄ in the coating layer, may be capable of simultaneous removal of elemental and oxidized mercury from coal combustion flue gases.     

新型吸附材料AGS在油气回收中的应用

考查了自制疏水性硅胶吸附材料AGS在加油站模拟油气回收装置及某油库现场油气回收装置的应用效果,并与常用的柱状活性炭进行了比较。实验结果表明：与活柱状性炭相比,AGS对油气的吸附速率和吸附量较小,但是油气脱附效果更好;将二者混合得到的吸附材料同时具备二者的优点,既具有较高的油气吸附量又具有良好的脱附性能,使油气回收装置具有更大的油气吸附量和更好的回收效果。     

Sulfur polymer solidification/stabilization of elemental mercury waste

Elemental mercury, contaminated with radionuclides, presents a waste disposal problem throughout the Department of Energy complex. In this paper we describe a new process to immobilize elemental mercury wastes, including those contaminated with radionuclides, in a form that is non-dispersible, will meet EPA leaching criteria, and has low mercury vapor pressure. In this stabilization and solidification process, elemental mercury is combined with an excess of powdered sulfur polymer cement (SPC) and sulfide additives in a mixing vessel and heated to approximately 40 degrees C for several hours, until all of the mercury is converted into mercuric sulfide (HgS). Additional SPC is then added and the temperature of the mixture raised to 135 degrees C, resulting in a molten liquid which is poured into a mold where it cools and solidifies. The final treated waste was characterized by powder X-ray diffraction and found to be a mixture of the hexagonal and orthorhombic forms of mercuric sulfide. The Toxicity Characteristic Leaching Procedure was used to assess mercury releases, which for the optimized process averaged 25.8 microg/l, with some samples being well below the new EPA Universal Treatment Standard of 25 microg/l. Longer term leach tests were also conducted, indicating that the leaching process was dominated by diffusion. Values for the effective diffusion coefficient averaged 7.6x10(-18) cm2/s. Concentrations of mercury vapor from treated waste in equilibrium static headspace tests averaged 0.6 mg/m3.     

Simultaneous capture of metal, sulfur and chlorine by sorbents during fluidized bed incineration

Metal capture experiments were carried out in an atmospheric fluidized bed incinerator to investigate the effect of sulfur and chlorine on metal capture efficiency and the potential for simultaneous capture of metal, sulfur and chlorine by sorbents. In addition to experimental investigation, the effect of sulfur and chlorine on the metal capture process was also theoretically investigated through performing equilibrium calculations based on the minimization of system free energy. The observed results have indicated that, in general, the existence of sulfur and chlorine enhances the efficiency of metal capture especially at low to medium combustion temperatures. The capture mechanisms appear to include particulate scrubbing and chemisorption depending on the type of sorbents. Among the three sorbents tested, calcined limestone is capable of capturing all the three air pollutants simultaneously. The results also indicate that a mixture of the three sorbents, in general, captures more metals than a single sorbent during the process. In addition, the existence of sulfur and chlorine apparently enhances the metal capture process.     

Mercury Capture on Fly Ash and Sorbents: The Effects of Coal Properties and Combustion Conditions

The US fleet of coal-fired power plants, with generating capacity of just over 300 GW, is known to be a major source of domestic mercury (Hg) emissions. To address this, in March 2005, the Environmental Protection Agency (EPA) promulgated the Clean Air Mercury Rule (CAMR) to reduce emissions of mercury from these plants. It is generally believed that most of the initial (Phase I) mercury reductions will come as a co-benefit of existing controls used to remove particulate matter (PM), SO₂, and NO _X . Deeper reductions in emissions (as required in Phase II of CAMR) may require the installation of mercury-specific control technology. Duct injection of activated carbon sorbents is the mercury-specific control technology that has been most widely studied and has been demonstrated over a wide range of coal types and combustion conditions. The effectiveness of the mercury control options (both “co-benefit control” and “mercury-specific control”) is significantly impacted by site-specific characteristics such as the combustion conditions, the configuration of existing air pollution controls, and the type of coal burned. This paper identifies the role of coal properties and combustion conditions in the capture of mercury by fly ash and injected sorbents.     

钛铁矿造孔核桃壳基活性炭的制备及其吸附性能

以核桃壳为原料,钛铁矿为造孔剂,制备钛铁矿造孔核桃壳基活性炭。实验结果表明：在氯化锌浓度为3mol/L、碳化时间为40min、碳化温度为400℃、钛铁矿加入量为5%的条件下,制得的钛铁矿造孔核桃壳基活性炭对苯酚、碱性品红、Pb²⁺的吸附量分别达到了156.80,181.35,35.84mg/g,比核桃壳活性炭分别提高了25.84%,18.59%,19.10%;钛铁矿作为造孔剂制备活性炭,可以降低碳化温度和缩短碳化时间,且对活性炭中孔的形成起促进作用,有利于对大分子物质和重金属的吸附去除。     

火电厂烟气汞形态转化机理及控制方法

汞是煤中最易挥发的重金属元素之一,燃烧产物中汞的排放为火电厂锅炉汞污染的主流。烟气中的汞主要采用活性炭或者其他吸附剂、飞灰再循环、湿法烟气脱硫装置等手段来去除,但普遍存在吸附剂价格昂贵、经济效应不高,具体脱除效应不明显、仅适用中小型火电厂锅炉等实际问题。为配合脱汞市场,需要在完善测试手段和控制手段的基础上,着重解决多组分污染物联合脱除汞反应的竞争机制和活性/选择性调控规律、吸收剂固体表面物理化学、大容积/大流量反应器内超低浓度污染物的富集/反应机理等关键技术问题。在火电厂烟气零价汞形态转化机理、汞迁移转化动力学模型的研究以及高效价廉吸附剂的开发等方面取得突破,开发具有自主知识产权的新型燃煤电厂烟气中汞排放控制方法。     

Sorbents for CO2 capture from high carbon fly ashes

Fly ashes with high-unburned-carbon content, referred to as fly ash carbons, are an increasing problem for the utility industry, since they cannot be marketed as a cement extender and, therefore, have to be disposed. Previous work has explored the potential development of amine-enriched fly ash carbons for CO(2) capture. However, their performance was lower than that of commercially available sorbents, probably because the samples investigated were not activated prior to impregnation and, therefore, had a very low surface area. Accordingly, the work described here focuses on the development of activated fly ash derived sorbents for CO(2) capture. The samples were steam activated at 850 degrees C, resulting in a significant increase of the surface area (1075m(2)/g). The activated samples were impregnated with different amine compounds, and the resultant samples were tested for CO(2) capture at different temperatures. The CO(2) adsorption of the parent and activated samples is typical of a physical adsorption process. The impregnation process results in a decrease of the surface areas, indicating a blocking of the porosity. The highest adsorption capacity at 30 and 70 degrees C for the amine impregnated activated carbons was probably due to a combination of physical adsorption inherent from the parent sample and chemical adsorption of the loaded amine groups. The CO(2) adsorption capacities for the activated amine impregnated samples are higher than those previously published for fly ash carbons without activation (68.6 vs. 45mg CO(2)/g sorbent).     

Novel Mercury Oxidant and Sorbent for Mercury Emissions Control from Coal-fired Power Plants

The authors have successfully developed novel efficient and cost-effective sorbent and oxidant for removing mercury from power plant flue gases. These sorbent and oxidant offer great promise for controlling mercury emissions from coal-fired power plants burning a wide range of coals including bituminous, sub-bituminous, and lignite coals. A preliminary analysis from the bench-scale test results shows that this new sorbent will be thermally more stable and cost-effective in comparison with any promoted mercury sorbents currently available in the marketplace. In addition to the sorbent, an excellent elemental mercury (Hg(0)) oxidant has also been developed, and will enable coal-fired power plants equipped with wet scrubbers to simultaneously control their mercury emissions as well as their sulfur oxides emissions. This will work by converting all elemental mercury to an oxidized form which will be removed by the wet scrubber. This will result in significant cost savings for mercury emissions control to the atmosphere, and will help in keeping electric costs low. The sorbent and oxidant will benefit from the utilization of a waste stream from the printed circuit board (PCB) industry, and would thus be environmentally beneficial to both of the utility and electronics industries. The sorbent also demonstrated thermal stability up to 350°C, suggesting a possibility of an application in pulverized coal-fired power plants equipped with hot-side electrostatic precipitators and coal gasification plants.     

用微孔填充理论研究活性炭对有机气体的吸附性能

用微孔填充理论研究了活性炭C40／4对丙酮、甲苯、二氯甲烷有机气体的吸附性能,测试了该活性炭对3种有机气体在不同温度下（288．15,293．15,298．15K）的吸附结果。用D—R方程处理了实验数据,建立了3种有机气体在活性炭C40／4上的等温吸附模型,并将实验测试值与理论预测值进行了比较。实验结果表明：微孔填充理论及D—R方程可很好地描述活性炭C40／4对有机气体的吸附性能,理论预测值与实验测试值的平均相对误差小于3％;有机气体分压较高时,由于发生毛细凝聚,理论预测值较实验测试值偏低。     

活性炭吸附黏胶纤维生产废气中的CS2

分别采用静态吸附和柱穿透吸附研究了活性炭对黏胶纤维生产废气中CS₂的吸附性能,考察了温度、水蒸气含量和预吸附H₂S时间对活性炭吸附CS₂效果的影响。实验结果表明：活性炭静态吸附CS₂的吸附等温线可用D-R方程很好地拟合,吸附温度升高,活性炭对CS₂的吸附量降低;Y-N方程能很好地拟合CS₂在活性炭上的柱吸附穿透过程,吸附温度升高,CS₂在活性炭上的吸附穿透时间缩短;进气水蒸气含量增大,吸附穿透时间缩短;预吸附H₂S时间延长,活性炭对CS₂的吸附穿透时间缩短;脱附温度升高,CS₂脱附率和脱附速率均加快。     

活性焦烟气脱汞的试验研究与数值模拟

采用固定床吸附系统,对自制褐煤活性焦的脱汞性能进行了试验研究,研究发现自制活性焦对烟气中Hg0有一定的吸附能力,随着Hg0的入口浓度的增加,活性焦质量的增加,活性焦的吸附量也在增加。40mg时3号活性焦由10ng/min汞入1：2浓度时26．68％的最大吸附效率提高到40ng／min汞入口浓度时的53．12％。10ng/min汞入口浓度时3号活性焦在40mg时的最大吸附效率为26．68％,而在80mg时吸附效率提高到43．2％。烟气中的SO2、NO气体对活性焦吸附汞有一定的促进作用。在试验的基础上建立了固定床吸附系统的数学模型,基于Lan—mguir吸附系数,考虑吸附过程中颗粒内、外的传质控制过程,建立质量平衡方程。通过Matlab模型计算,计算结果与试验结果基本吻合,计算的活性焦脱汞效率要优于试验数值,计算的是理想情况下活性焦对汞的吸附效率,实际情况会有所降低。     

Modeling of mercury sorption by activated carbon in a confined,a semi-fluidized,and a fluidized bed

A process model was developed to simulate elemental mercury sorption by activated carbon in three distinct beds, namely a confined, a semi-fluidized, and a fluidized bed. The model involved the coupling of a kinetic model based on the mechanisms of surface equilibrium and external mass transfer, and a material balance model based on the tank-in-series approach. For surface equilibrium, three different equilibrium laws were used in the model, namely the Henry's Law, the Langmuir isotherm and the Freundlich isotherm. Literature mercury sorption data were used to determine the best-fit values of parameters for these equilibrium expressions. The parameter-fitted model was then used to simulate mercury sorption processes in the three distinct beds. The simulation parameters were mercury concentration, gas flow rate, adsorption temperature and the degree of semi-fluidization. The simulation results have indicated that the model is capable of describing the literature available mercury sorption data. All the three surface equilibrium laws appear to simulate the adsorption profiles equally well mainly because the sorption process occurs in an extremely low concentration range. The simulation results for the three distinct beds have suggested that the confined bed has the best mercury control performance; however, it generates the highest pressure-drop across the bed. A fluidized bed creates the least pressure drop; however, its sorption performance is poor. A semi-fluidized bed offers acceptable performance with affordable pressure-drops and can be a practical candidate for the process.     

The behaviour of ashes and heavy metals during the co-combustion of sewage sludges in a fluidised bed

Co-combustion tests of dry sewage sludges with coal were performed in a pilot bubbling FBC aiming at the characterization of ashes and determining the behaviour of heavy metals in the process. The tests showed compliance with the regulatory levels as far as heavy metal emissions were concerned. The bottom ashes, which accounted for about 70% of the total ash production, were obtained in a granular form, with diameters ranging from 0.5 to 4 mm. The heavy metals were distributed in ashes obtained from different locations of the installation and their concentrations were found to vary depending on the location of capture. The increase in heavy metals content in bottom ashes was not found to lead to higher leachability and ecotoxicity compared to sewage sludges, suggesting that there could be opportunities for their further use. Mercury suffered vaporisation inside the reactor, thus leaving bottom ashes free of contamination by it. However, there was observed a strong retention of mercury in cyclone ashes due to the presence of unburned carbon which probably acted as an adsorbent. The effluent mercury was also found to be mostly associated with the particulate fraction, being less than 20% emitted in gaseous forms. The results suggested that the combustion of the sewage sludge could successfully be carried out and the amount of unburned carbon leaving the combustor but captured in cyclone was large enough to ensure substantial retention of mercury at low temperatures, hence could contribute to an improvement of the mercury release which still remains an issue of great concern to resolve during combustion of waste materials.