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.     

Nitrogen Oxides Emission Control Options for Coal-Fired Electric Utility Boilers

Abstract

Recent regulations have required reductions in emissions of nitrogen oxides (NO_x) from electric utility boilers. To comply with these regulatory requirements, it is increasingly important to implement state-of-the-art NO_x control technologies on coal-fired utility boilers. This paper reviews NO_x control options for these boilers. It discusses the established commercial primary and secondary control technologies and examines what is being done to use them more effectively. Furthermore, the paper discusses recent developments in NO_x controls. The popular primary control technologies in use in the United States are low-NO_x burners and overfire air. Data reflect that average NO_x reductions for specific primary controls have ranged from 35% to 63% from 1995 emissions levels. The secondary NO_x control technologies applied on U.S. coal-fired utility boilers include reburning, selective noncatalytic reduction (SNCR), and selective catalytic reduction (SCR). Thirty-six U.S. coal-fired utility boilers have installed SNCR, and reported NO_x reductions achieved at these applications ranged from 15% to 66%. Recently, SCR has been installed at >150 U.S. coal-fired utility boilers. Data on the performance of 20 SCR systems operating in the United States with low-NO_x emissions reflect that in 2003, these units achieved NO_x emission rates between 0.04 and 0.07 lb/10⁶ Btu.     

Application of ameliorated wood pulp to recover Cd(II), Pb(II), and Ni(II) from e-waste

In this study, dl-malic acid and hydrogen peroxide were used as leaching agents to remove metals from e-waste (printed-circuit boards) and itaconic acid-grafted poly(vinyl alcohol)-encapsulated wood pulp (IA-g-PVA-en-WP) to uptake metals from leachate with high proficiency [11.63 mg g^?1; 93.03 % for Cd(II), 11.90 mg g^?1; 95.18 % for Pb(II), and 12.14 mg g^?1; 97.08 % for Ni(II)]. Metals were recovered from the loaded biosorbent by desorption studies. The standard analytical techniques, such as elemental analysis, Fourier-transform-infrared spectroscopy, scanning electron microscopy, atomic force microscopy, and thermogravimetric analysis, were used to characterize the recovering agent (biosorbent). At equilibrium, the metal uptake data were fitted to Langmuir and D–R isotherms (R ² > 0.99) significantly, revealing, the homogeneous distribution of active sites on biosorbent’s backbone. The possible mechanism appeared to be ion exchanges of metal ions with H⁺ together with binding over functionalities (COO^?). Dimensionless equilibrium parameter (R _L) showed the favourability of metal uptake at lower concentration, while mean adsorption energy (E) certified the physical binding of metal on functionalities which was further confirmed by sticking probability and activation energy parameters. Reusability studies were also conducted to state the performance of biosorbent.     

The effect of triethylene tetramine upon the selective removal of nickel (II), iron (II), manganese (II) and tin (II) in rats

The distribution of Nickel-63, Iron-59, Manganese-54 and Tin-113 in plasma was studied in rats which received single intravenous (i.v.) injection of aqueous solutions of their salts alone, and in rats which also received single intramuscular (im) injection of triethylene tetramine (TETA). TETA was extremely effective in reducing the plasma concentration of Nickel-63 followed by that of Iron-59, Manganese-54 and Tin-113.     

Accumulation, speciation and cellular localization of copper in Sesbania drummondii

Growth, accumulation and intracellular speciation and distribution of copper (Cu) in Sesbania drummondii was studied using scanning-electron microscopy (SEM), X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). The growth of seedlings was assessed in terms of biomass accumulation. The growth of the seedling was enhanced by 73.5% at a low Cu concentration (50 mg l⁻¹) compared to the control treatment. Additionally, seedling growth was inhibited by 18% at 300 mg l⁻¹ Cu with respect to the control. Copper concentration in roots and shoots was increased with increasing Cu concentration in the growth solution. The accumulation of Cu was found to be higher in roots than in the shoots. At a concentration of 300 mg l⁻¹ Cu, the roots accumulated 27,440 mg Cu kg⁻¹ dry weight (dw) while shoots accumulated 1282 mg Cu kg⁻¹ dw. Seedlings were assessed for photosynthetic activity by measuring chlorophyll a fluorescence parameters: F_v/F_m and F_v/F₀ values. Photosynthetic integrity was not affected by any of the Cu treatments. The X-ray absorption spectroscopic (XAS) studies showed that Cu was predominantly present as Cu(II) in Sesbania tissue. In addition, from the XAS studies it was shown that the Cu exists in a mixture of different coordination states consisting of Cu bound to sugars and small organic acids with some possible precipitated copper oxide. From the EXAFS studies, the coordination of Cu was determined to have four equatorial oxygen(nitrogen) ligands at 1.96 Å and two axial oxygen ligands at 2.31 Å. Scanning-electron microscopy studies revealed the distribution of Cu within the seedlings tissues, predominantly accumulated in the cortical and vascular (xylem) regions of root tissues. In the stem, most of the Cu was found within the xylem tissue. However, the deposition of Cu within the leaf tissues was in the parenchyma. The present study demonstrates the mechanisms employed by S. drummondii for Cu uptake and its biotransformation.     

Size distribution and source identification of total suspended particulate matter and associated heavy metals in the urban atmosphere of Delhi

A study of the atmospheric particulate size distribution of total suspended particulate matter (TSPM) and associated heavy metal concentrations has been carried out for the city of Delhi. Urban particles were collected using a five-stage impactor at six sites in three different seasons, viz. winter, summer and monsoon in the year 2001. Five samples from each site in each season were collected. Each sample (filter paper) was extracted with a mixture of nitric acid, hydrochloric acid and hydrofluoric acid. The acid solutions of the samples were analysed in five-particle fractions by atomic absorption spectrometry (AAS). The impactor stage fractionation of particles shows that a major portion of TSPM concentration is in the form of PM0.7 (i.e. <0.7microm). Similarly, the most of the metal mass viz. Mn, Cr, Cd, Pb, Ni, and Fe are also concentrated in the PM0.7 mode. The only exceptions are size distributions pertaining to Cu and Ca. Though, Cu is more in PM0.7 mode, its presence in size intervals 5.4-1.6microm and 1.6-0.7microm is also significant, whilst in case of Ca there is no definite pattern in its distribution with size of particles. The average PM10.9 (i.e. <10.9microm) concentrations are approximately 90.2%+/-4.5%, 81.4%+/-1.4% and 86.4%+/-9.6% of TSPM for winter, summer and monsoon seasons, respectively. Source apportionment reveals that there are two sources of TSPM and PM10.9, while three and four sources were observed for PM1.6 (i.e. <1.6microm) and PM0.7, respectively. Results of regression analyses show definite correlations between PM10.9 and other fine size fractions, suggesting PM10.9 may adequately act as a surrogate for both PM1.6 and PM0.7, while PM1.6 may adequately act as a surrogate for PM0.7.     

A study of gas-phase mercury speciation using detailed chemical kinetics.

Mercury speciation in combustion-generated flue gas was modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for the chlorination and oxidation of key flue-gas components, including elemental mercury (Hg0). Results indicated that the performance of the model is very sensitive to temperature. Starting with pure HCl, for lower reactor temperatures (less than approximately 630 degrees C), the model produced only trace amounts of atomic and molecular chlorine (Cl and Cl2), leading to a drastic underprediction of Hg chlorination compared with experimental data. For higher reactor temperatures, model predictions were in good accord with experimental data. For conditions that produce an excess of Cl and Cl2 relative to Hg, chlorination of Hg is determined by the competing influences of the initiation step, Hg + Cl = HgCl, and the Cl recombination reaction, 2Cl = Cl2. If the Cl recombination reaction is faster, Hg chlorination will eventually be dictated by the slower pathway Hg + Cl2 = HgCl2.     

Simultaneous control of Hg0, SO2, and NOx by novel oxidized calcium-based sorbents

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 NOx 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 NOx 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 sorption capacities (approximately 100 microg/g) comparable to that of the activated carbon; they showed far superior SO2 and NOx 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 NOx 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.     

Conductive and convective heat transfer augmentation in flat plate solar collector from energy,economic and environmental perspectives — a comprehensive review

Environmental Science and Pollution Research - The primary objective of the paper is to identify the effective way to enhance the conductive and convective heat transfer of the FPSC. The...     

Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) 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 NOx 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.