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.     

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.     

Characteristics of mercury desorption from sorbents at elevated temperatures

This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4 mm ID quartz bed enclosed in an electric furnace. Elemental mercury and mercuric chloride were tested with activated carbon and bauxite. The experimental results indicated that mercury desoption from sorbents was strongly affected by the desorption temperature and the mercury–sorbent pair. Elemental mercury was observed to desorb faster than mercuric chloride and activated carbon appeared to have higher desorption limits than bauxite at low temperatures. A kinetic model considering the mechanisms of surface equilibrium, pore diffusion and external mass transfer was proposed to simulate the observed desorption profiles. The model was found to describe reasonably well the experimental results.     

Mercury leaching characteristics of waste treatment residues generated from various sources in Korea

In this study, mercury (Hg) leaching characteristics of the waste treatment residues (fly ash, bottom ash, sludge, and phosphor powder) generated from various sources (municipal, industrial, medical waste incinerators, sewage sludge incinerator, oil refinery, coal-fired power plant, steel manufacturing plant, fluorescent lamp recycler, and cement kiln) in Korea were investigated. First, both Hg content analysis and toxicity characteristic leaching procedure (TCLP) testing was conducted for 31 collected residue samples. The Hg content analysis showed that fly ash from waste incinerators contained more Hg than the other residue samples. However, the TCLP values of fly ash samples with similar Hg content varied widely based on the residue type. Fly ash samples with low and high Hg leaching ratios (R_L) were further analyzed to identify the major factors that influence the Hg leaching potential. Buffering capacity of the low-R_L fly ash was higher than that of the high-R_L fly ash. The Hg speciation results suggest that the low-R_L fly ashes consisted primarily of low-solubility Hg compounds (Hg₂Cl₂, Hg⁰ or HgS), whereas the high-R_L fly ashes contain more than 20% high-solubility Hg compounds (HgCl₂ or HgSO₄).     

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.     

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。     

Preparation,Characterization, and Rapid Adsorption of Hg<Superscript>2+</Superscript> on Nanoscale Aramid-based Adsorbent

A series of nanaoscale aramid-based adsorbents were prepared by the functionalization of poly (p-phenylene terephthalamide) (PPTA) with different content of ethylenediamine (EDA). Their structures were characterized by field emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and elemental analysis. Metal ions, including Hg²⁺, Pb²⁺, Ag⁺, Cu²⁺, Cd²⁺, and Ni²⁺ were chosen as the models to explore the binding behaviors of PPTA–ECH–EDA in aqueous medium. Results showed that PPTA–ECH–EDA exhibited higher adsorption capacity for Hg²⁺ due to their nanoscale structures. In particular, the adsorption rate was so high that equilibrium was achieved within 15 min for Hg²⁺. The adsorption of Hg²⁺ on PPTA–ECH–EDA followed the pseudo second-order model well. Langmuir and Freundlich models were employed to fit the isothermal adsorption, and the results revealed that Freundlich isotherm was a better model to predict the experimental data. The adsorption mechanism was revealed by X-ray photoelectron spectroscopy. It is preconceived that PPTA–ECH–EDA could be used as an effective adsorbent for fast removal of heavy ions from wastewater.     

Preparation and characterization of sorbents prepared from ash (waste material) for sulfur dioxide (SO2) removal

Sorbents synthesized from various types of ash (coal fly ash, coal bottom ash, oil palm ash, and incinerator ash) for flue gas desulfurization were investigated. The sorbents were prepared by mixing the ashes with calcium oxide and calcium sulfate using the water hydration method. The effects of various sorbent preparation variables, such as the hydration period, the ratio of calcium oxide to ash, and the amount of calcium sulfate, on the Brunauer-Emmett-Teller (BET)-specific surface area of the resulting sorbent were studied using a two-level full factorial design. The surface area of the sorbents obtained range from 15.4 to 122.1m²/g. Regression models were developed to correlate the significant variables to the surface area of the sorbents. An analysis of variance (ANOVA) showed that the model was significant at a confidence level of 95%. It was found that apart from all the individual variables studied, interactions between variables also exerted a significant influence on the surface area of the sorbent. From the activity test results, it was found that sorbents prepared from coal fly ash and oil palm ash have the highest SO₂ absorption capacity. Scanning electron microscope (SEM) analysis showed that the sorbent was composed of a compound with a high structural porosity, while an X-ray diffraction spectrum showed that calcium aluminum silicate hydrate compounds are the main products of the hydration reaction.     

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.     

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.     

Waste plastics recycling by an entrained-flow gasifier

We studied an entrained-flow gasification process which efficiently converts waste plastics to energy at a high energy recovery rate. Waste plastics, after being shredded to <8 mm or <14 mm, were fed into an entrained-flow gasifier with air and oxygen. In the gasifier, organic substances were pyrolyzed, partially combusted, and then converted into synthetic gas (CO, H₂) at a high temperature (over 1600 K). The clarified gasification characteristics were that the lower heat value (LHV) of the product gas was over 4.2 MJ/Nm³ and the cold gas efficiency was approximately 60%. Other inert substances in the wastes such as ashes and metals were melted into slag and condensed on bag filters. The bag filters and a water scrubber removed impurities such as dusts, heavy metals, and hydrogen halides from the product gases. Solid hydrocarbons, which include char and soot, were removed at a hot cyclone and on the bag filters. Received: July 19, 2000 / Accepted: October 3, 2000     

Effect of liquid-to-solid ratio on semi-solid Fenton process in hazardous solid waste detoxication

The liquid-to-solid ratio (L/S) of semi-solid Fenton process (SSFP) designated for hazardous solid waste detoxication was investigated. The removal and minimization effects of o-nitroaniline (ONA) in simulate solid waste residue (SSWR) from organic arsenic industry was evaluated by total organic carbon (TOC) and ONA removal efficiency, respectively. Initially, Box-Behnken design (BBD) and response surface methodology (RSM) were used to optimize the key factors of SSFP. Results showed that the removal rates of TOC and ONA decreased as L/S increased. Subsequently, four target initial ONA concentrations including 100 mg kg⁻¹, 1 g kg⁻¹, 10 g kg⁻¹, and 100 g kg⁻¹ on a dry basis were evaluated for the effect of L/S. A significant cubic empirical model between the initial ONA concentration and L/S was successfully developed to predict the optimal L/S for given initial ONA concentration for SSFP. Moreover, an optimized operation strategy of multi-SSFP for different cases was determined based on the residual target pollutant concentration and the corresponding environmental conditions. It showed that the total L/S of multi-SSFP in all tested scenarios was no greater than 3.8, which is lower than the conventional slurry systems (L/S ? 5). The multi-SSFP is environment-friendly when it used for detoxication of hazardous solid waste contaminated by ONA and provides a potential method for the detoxication of hazardous solid waste contaminated by organics.     

Biodegradability and biodegradation rate of poly(caprolactone)-starch blend and poly(butylene succinate) biodegradable polymer under aerobic and anaerobic environment

The biodegradability and the biodegradation rate of two kinds biodegradable polymers; poly(caprolactone) (PCL)-starch blend and poly(butylene succinate) (PBS), were investigated under both aerobic and anaerobic conditions. PCL-starch blend was easily degraded, with 88% biodegradability in 44 days under aerobic conditions, and showed a biodegradation rate of 0.07 day⁻¹, whereas the biodegradability of PBS was only 31% in 80 days under the same conditions, with a biodegradation rate of 0.01 day⁻¹. Anaerobic bacteria degraded well PCL-starch blend (i.e., 83% biodegradability for 139 days); however, its biodegradation rate was relatively slow (6.1 mL CH₄/g-VS day) compared to that of cellulose (13.5 mL CH₄/g-VS day), which was used as a reference material. The PBS was barely degraded under anaerobic conditions, with only 2% biodegradability in 100 days. These results were consistent with the visual changes and FE-SEM images of the two biodegradable polymers after the landfill burial test, showing that only PCL-starch blend had various sized pinholes on the surface due to attack by microorganisms. This result may be use in deciding suitable final disposal approaches of different types of biodegradable polymers in the future.     

Treatment of waste containing EDTA by chemical oxidation

Ethylenediaminetetraacetic acid (EDTA) is a chelating agent that has been extensively used to enhance the solubilization of heavy metal cations and release of EDTA contributes to environmental problems. EDTA is recalcitrant to microbial metabolism and chemical oxidation is considered a possible method of remedial treatment. The use of the commercially available process of MIOX Corporation generates mixed oxidants on site and this solution is markedly effective in the destruction of the chelating characteristic and the decarboxylation of EDTA. When measuring the release of C-14 from carboxyl labeled EDTA, the mixed oxidant solution was comparable to the Fenton's reaction over a broad pH range. The presence of Mn²⁺, Cr³⁺, or Fe³⁺ at levels equal to that of EDTA stimulated the rate of EDTA decomposition; however, the rate of EDTA breakdown was inhibited when the concentration of Cr³⁺ or Mn²⁺ exceeded the concentration of EDTA. The treatment of Co²⁺–EDTA or Cu²⁺–EDTA with mixed oxidants in the presence of ultra violet light resulted in the loss of chelation ability of EDTA. In the absence of chelated metals, over 75% of the chelation property of a 70 mM EDTA solution was destroyed in 45 min. The reaction products resulting from the use of mixed oxidants added to EDTA were non-toxic to bacteria and should not contribute to additional environmental problems.     

水合改性对钙基吸收剂循环捕集CO2的影响

在钙基吸收剂捕集CO2的过程中，吸收剂转化率会随着循环次数的增加而迅速降低。钙基吸收剂的水合改性作为改善吸收剂循环转化率的主要方法之一受到了国内外学者的广泛关注。总结了目前国内外研究者对不同的吸收剂、循环捕集条件下的水合改性方法的研究成果。结果表明，在循环过程中的不同阶段对吸收剂进行水合处理后得到的效果不同。其中，在碳酸化阶段、煅烧阶段、循环捕集前预处理以及煅烧后对吸收剂水合改性．吸收剂捕集CO2的能力均得到了改善；碳酸化反应后对吸收剂进行水合处理是否对循环吸收有利还存在争议。目前，利用水合改性的方法提高钙基吸收剂循环捕集CO2能力的机理还存在争议，且水合改性后的吸收剂机械性能差以及此方法能耗高的问题尚待解决。     

Experimental and life cycle assessment analysis of gas emission from mechanically–biologically pretreated waste in a landfill with energy recovery

The global gaseous emissions produced by landfilling the Mechanically Sorted Organic Fraction (MSOF) with different weeks of Mechanical Biological Treatment (MBT) was evaluated for an existing waste management system. One MBT facility and a landfill with internal combustion engines fuelled by the landfill gas for electrical energy production operate in the waste management system considered. An experimental apparatus was used to simulate 0, 4, 8 and 16 weeks of aerobic stabilization and the consequent biogas potential (Nl/kg) of a large sample of MSOF withdrawn from the full-scale MBT. Stabilization achieved by the waste was evaluated by dynamic oxygen uptake and fermentation tests. Good correlation coefficients (R²), ranging from 0.7668 to 0.9772, were found between oxygen uptake, fermentation and anaerobic test values. On the basis of the results of several anaerobic tests, the methane production rate k (year^?1) was evaluated. k ranged from 0.436 to 0.308 year^?1 and the bio-methane potential from 37 to 12 N m³/tonne, respectively, for the MSOF with 0 and 16 weeks of treatment. Energy recovery from landfill gas ranged from about 11 to 90 kW h per tonne of disposed MSOF depending on the different scenario investigated. Life cycle analysis showed that the scenario with 0 weeks of pre-treatment has the highest weighted global impact even if opposite results were obtained with respect to the single impact criteria. MSOF pre-treatment periods longer than 4 weeks showed rather negligible variation in the global impact of system emissions.     

The Control of SO2 Dry Deposition on to Natural Surfaces by NH3 and its Effects on Regional Deposition

Two years of continuous measurements of SO₂deposition fluxes to moorland vegetation are reported. The mean flux of 2.8 ng SO₂ m^-2 s^-1 is regulated predominantly by surface resistance (r _c) which, even for wet surfaces, was seldom smaller than 100 s m^-1. The control of surface resistance is shown to be regulated by the ratio of NH₃SO₂ concentrations with an excess of NH₃ generating the small surface resistances for SO₂. A dynamic surface chemistry model is used to simulate the effects of NH₃ on SO₂ deposition flux and is able to capture responses to short-term changes in ambient concentrations of SO₂, NH₃ and meteorological conditions. The coupling between surface resistance and NH₃/SO₂ concentration ratios shows that the deposition velocity for SO₂ is regulated by the regional pollution climate. Recent long-term SO₂ flux measurements in a transect over Europe demonstrate the close link between NH₃/SO₂ concentrations and rc (SO₂). The deposition velocity for SO₂ is predicted to have increased with time since the 1970s and imply a 40% increase in v _d at a site at which the annual mean ambient SO₂ concentrations declined from 47 to 3 g m^-3 between 1973 and 1998.     

Biodegradation of an Epoxy-Based Thermoplastic Polyester, Poly(Hydroxy Ester Ether) in a Laboratory-Scale Compost System

An epoxy-based thermoplastic polyester, poly(hydroxy ester ether), was incubated under aerobic conditions in a laboratory-scale compost system for 168 days to evaluate its potential for biodegradation. Radiolabeled test polymer [uniformly ¹⁴C ring-labeled, poly(hydroxy ester ether)] was incorporated into a mature compost and a sludge-amended compost at a loading of 3 mg test polymer/g compost. ¹⁴C-Cellulose was used as the positive control and a biologically inhibited control reactor was used to assess abiotic degradation of the test polymer. Degradation of the test polymer was assessed by measuring the amount of ¹⁴C-CO₂ from each of the test reactors. In addition, at selected time intervals subsamples of the compost were collected and serially extracted with water, methanol, and dimethylformamide to monitor degradation of the ¹⁴C-test polymer and provide a partial characterization of the degradation intermediates. Extensive degradation of ¹⁴C-poly(hydroxy ester ether) was observed in the test reactors with degradation half-life of the parent polymer (t _1/2) of approximately 32 days. By the end of the study, only 2% of the total ¹⁴C activity in the test reactors was attributed to intact polymer, with most of the measurable ¹⁴C activity converted to either ¹⁴C-CO₂ (26% of total ¹⁴C activity) or nonextractable products (accounting for 60% of the total activity). In contrast to the test reactors, only 3% of the ¹⁴C-poly(hydroxy ester ether) added to the biologically inhibited control reactor was mineralized to ¹⁴C-CO₂. The results obtained from the microbially active and biologically inhibited compost systems indicate that the poly(hydroxy ester ether) polymer was degraded, at least in part, by a biologically mediated process.     

Observations on the methane oxidation capacity of landfill soils

The objective of this study was to determine the role of CH₄ loading to a landfill cover in the control of CH₄ oxidation rate (g CH₄ m⁻² d⁻¹) and CH₄ oxidation efficiency (% CH₄ oxidation) in a field setting. Specifically, we wanted to assess how much CH₄ a cover soil could handle. To achieve this objective we conducted synoptic measurements of landfill CH₄ emission and CH₄ oxidation in a single season at two Southeastern USA landfills. We hypothesized that percent oxidation would be greatest at sites of low CH₄ emission and would decrease as CH₄ emission rates increased. The trends in the experimental results were then compared to the predictions of two differing numerical models designed to simulate gas transport in landfill covers, one by modeling transport by diffusion only and the second allowing both advection and diffusion. In both field measurements and in modeling, we found that percent oxidation is a decreasing exponential function of the total CH₄ flux rate (CH₄ loading) into the cover. When CH₄ is supplied, a cover’s rate of CH₄ uptake (g CH₄ m⁻² d⁻²) is linear to a point, after which the system becomes saturated. Both field data and modeling results indicate that percent oxidation should not be considered as a constant value. Percent oxidation is a changing quantity and is a function of cover type, climatic conditions and CH₄ loading to the bottom of the cover. The data indicate that an effective way to increase the % oxidation of a landfill cover is to limit the amount of CH₄ delivered to it.     

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.