A mechanism study of chloride and sulfate effects on Hg reduction in sulfite solution

This paper studied the effects of sulfate and chloride ions on bivalent mercury (Hg²⁺) absorption and reduction behaviors in a simulated WFGD system. The aqueous mercuric ion-sulfite system reduction behaviors were monitored and investigated using a UV-visible spectrum. Thereafter, the mechanism of Hg²⁺ reduction in the presence of sulfate and chloride ions was proposed. Experimental results revealed that both sulfate and chloride ions had inhibition effects on aqueous Hg²⁺ reduction to Hg⁰. The inhibition was assumed due to the formation of (in the presence of ) and / (in the presence of Cl⁻). And it was found that complex was more stable than in excess of Cl⁻. The formation of the above-mentioned complexes in the presence of and Cl⁻ would damp the formation of HgSO₃, whose decomposition was assumed to be the key step of Hg²⁺ reduction.     

Effect of oxidizing agents on selenate formation in a wet FGD

In a coal combustion process, a considerable amount of selenium is captured in the wet FGD, where it is oxidized from selenite to selenate , which is difficult to remove. Diethyl-p-phenylene-diammonium (DPD) absorptiometric analysis and ion chromatography identified peroxodisulfate ion as the dominant oxidizing agent in the FGD liquor. Selenite was easily oxidized to selenate in the presence of and the oxidation was accelerated as the temperature increased. Addition of Mn²⁺ ion was found to be effective in controlling selenate formation. When Mn²⁺ ion was added, oxidized not selenite to selenate but rather Mn²⁺ to MnO₂, which captured some dissolved selenite.     

Oxidation of FGD-CaSO3 and effect on soil chemical properties when applied to the soil surface

Use of high-sulfur coal for power generation in the United States requires the removal of sulfur dioxide (SO₂) produced during burning in order to meet clean air regulations. If SO₂ is removed from the flue gas using a wet scrubber without forced air oxidation, much of the S product created will be sulfite (). Plants take up S in the form of sulfate (). Sulfite may cause damage to plant roots, especially in acid soils. For agricultural uses, it is thought that in flue gas desulfurization (FGD) products must first oxidize to in soils before crops are planted. However, there is little information about the oxidation of in FGD product to under field conditions. An FGD-CaSO₃ was applied at rates of 0, 1.12, and 3.36 Mg ha⁻¹ to the surface of an agricultural soil (Wooster silt loam, Oxyaquic Fragiudalf). The in the surface soil (0-10 cm) was analyzed on days 3, 7, 17, 45, and 61. The distribution of and Ca in the 0-90 cm soil layer was also determined on day 61. Results indicated that in the FGD-CaSO₃ rapidly oxidized to on the field surface during the first week and much of the and Ca moved downward into the 0-50 cm soil layer during the experimental period of two months. It is safe to grow plants in soil treated with FGD-CaSO₃ if the application is made at least three days to several weeks before planting.     

A comparative study of PtCo, PtCr, and PtCoCr catalysts for oxygen electro-reduction reaction

A comparative study of carbon supported Pt₃₀Co₇₀, Pt₃₀Cr₇₀, and Pt₃₀Co₃₀Cr₄₀ catalysts for oxygen electro-reduction reaction (ORR) activity was performed. In alloy catalysts synthesized via NaBH₄ reduction, more than a 3-fold improvement was observed in ORR specific activity compared with that of Pt/C catalyst, while mass activities did not show significant improvement. After annealing at 900 °C under reducing conditions, the ORR specific activities of the alloy catalysts increased to give a relative ORR catalytic activity ordering of PtCo/C-900 (2800 μA ) > PtCoCr/C-900 (1770 μA ) > PtCr/C-900 (871 μA ) > Pt/C-900 (393 μA ) > Pt/C (334 μA ). On the other hand, the ORR mass activity followed an order of PtCr/C-900 (140 mA ) > PtCoCr/C-900 (111 mA ) > PtCo/C-900 (84.1 mA ). Cyclic voltammetry results suggest that incorporation of Cr resulted in a large electrochemically active surface area producing higher mass activity in the PtCr/C-900 catalyst although it showed the lowest specific activity among the alloy catalysts. The intermediate EAS and ORR activity values of the PtCoCr/C-900 catalyst suggest that the characteristics of the PtCo/C-900 (low mass and high specific activities) and PtCr/C-900 (high mass and low specific activities) are combined by alloying of Pt with both Co and Cr.     

Chemical forms of ash-forming elements in woody biomass fuels

Advanced fuel characterization helps to predict ash fouling and slagging. Chemical fractionation analysis, i.e. sequential leaching in H₂O, NH₄Ac(aq), and HCl(aq), was applied to the biomass of spruce, pine, birch, and aspen. All of the Cl in the samples and most of the K, Na, and P were water-soluble; most of the Mg and Mn, and some of the Ca were leached in NH₄Ac; most of the Ca was leached in HCl; and most of the Si and S remained insoluble in the biomass. Ion Chromatography found the water-soluble Cl, P, and S present as Cl⁻, , and , respectively, and equimolar concentrations of as leached Ca in the acid fraction. The biomass solids were determined for anionic groups by methylene blue sorption. The contents were lowest in the wood samples (22-118 mmol/kg_D.S.) and highest in the bark samples (130-453 mmol/kg_D.S.). The closing of the ion charge balance led to a quantitative model for the ash-forming matter: water-soluble salts (KCl, K₂HPO₄, and K₂SO₄), acid-soluble minerals (CaC₂O₄), non-soluble minerals (SiO₂), and organically associated ash-forming elements (ionically bonded Ca²⁺, Mg²⁺, Mn²⁺, and K⁺, and covalently bonded P and S).     

Quantifying desorption and rearrangement rates of carbon monoxide on a PEM fuel cell electrode

A simple procedure to quantify the rates of carbon monoxide (CO) desorption from, and simultaneous rearrangement on, supported platinum fuel cell electrode (Pt on Vulcan XC-72R) is reported. The surface coverage of CO on Pt electrode in equilibrium with bulk CO was measured from the anodic peaks in the CO stripping voltammogram. The decline in these surface coverages due to desorption and rearrangement, once CO was replaced by N₂ in the gas phase was recorded and used in conjunction with a kinetic model to quantify the respective rates. Two distinct CO oxidation peaks observed in the voltammogram due to the oxidation of two distinct ad-species, namely weakly and strongly adsorbed CO ( and ), were baseline corrected and deconvoluted using a bimodal Gaussian distribution. Saturation surface coverage of decreased with increasing temperature, while the opposite was true for . Rearrangement from to was faster than the desorption rate of either CO species. The desorption rate of was at least an order of magnitude lower than that of molecules at all temperatures studied. The activation energies for desorption of and were estimated to be 24.08 and 27.99 kJ/mol, respectively. The activation energy for rearrangement from to was 35.23 kJ/mol and that from to was 27.55 kJ/mol.     

Electrochemical detection of in situ DNA damage with layer-by-layer films containing DNA and glucose oxidase and protection effect of catalase layers against DNA damage

Natural double-stranded DNA and the enzyme glucose oxidase (GOD) were assembled into layer-by-layer films on electrode surface. In the presence of glucose and Fe²⁺ in incubation solutions, GOD in the films could catalyze the reaction of glucose and O₂, and the produced H₂O₂ would further react with Fe²⁺, generating hydroxyl radical (OH) as in the Fenton reaction, which could severely damage DNA in the films. The electrocatalytic oxidation of DNA guanines by (bpy = 2,2′-bipyridine) produced by electrooxidation of at the electrodes was used to detect DNA damage induced by the in situ Fenton reaction. The additional catalase (Cat) layers assembled into the films could effectively protect the DNA from damage by decomposing the H₂O₂ produced in situ, and only when the Cat layers were located in close proximity to the GOD layers, the protection of DNA in the inner layers was most effective. The present work provides an in vitro model system to mimic the real bioprocess in DNA damage and protection through a simple electrochemical approach combined with layer-by-layer assembly.     

Flashback propensity of syngas fuels

This paper presents experimental measurements of the critical velocity gradient and flashback behavior of H₂-CO and H₂-CH₄ mixtures. Effects of H₂ concentration, external excitation, and swirl on the flashback behavior for flames of these fuel mixtures are discussed. For H₂ concentration burner and scaling studies the critical velocity gradient (g_F), defined as the ratio of the square of the laminar burning velocity to the thermal diffusivity of the mixture , was used to quantify the flashback propensity of the flames. The critical velocity gradient of both H₂-CH₄ and H₂-CO flames changed nonlinearly with the increase in H₂ contents in the mixture. The critical velocity gradient (g_F) of 5-95% and 15-85% H₂-CO mixtures somewhat agreed with the scaling relation and yielded an average c value of 0.04. Similarly, values of a 25%H₂-75%CH₄ for different burner diameters were also fitted using the scaling relation yielding an average c value of 0.044. The g_F values of 25-75% H₂-CO mixture showed non-linear variation with the ratio (especially for ), and at a lower ratios burner diameter had small effect on critical velocity gradient measurements. The opposite trend was observed for a 25-75% H₂-CH₄ mixture showing non-linear variation at a lower ratios (for ) and having less effect at higher ratios. It was also determined that the effect of external excitation on the flashback propensity of H₂-CO flames with more than 5% H₂ was not significant. Flashback through two mechanisms and their dependence on combustor parameters were also identified for swirl stabilized H₂-CO flames.     

Oxidation kinetics of Iron(II) complexes of trans-1,2-diaminocyclohexanetetraacetate (cdta) with dissolved oxygen: Reaction mechanism, parameters of activation and kinetic salt effects

The present investigation takes concern about a spiny environmental problem afflicting the pulp mill industry exploiting the Kraft sulfate-pulp process where dilute total reduced sulfur contaminants are co-mixed with oxygen in large-volume gas effluents. A potential Redox process for removing the total reduced sulfurs consists in oxidizing them by means of iron(III) organometallic complexes while the co-mixed oxygen mediates the oxidative regeneration of iron(II) into iron(III) complexes. In this work, the oxidation kinetics of iron(II) trans-1,2,-diaminocyclohexanetetraacetate (cdta) complexes with molecular oxygen (O₂) as the source oxidant was investigated for a wide pH range (1.75<pH<12) in a 3.2 dm³ single-phase stirred cell reactor within the [281-323 K] temperature range. Simultaneous measurements of iron(II)-cdta (50-) and O₂ (0.5-) were used to clarify the reaction mechanism which has been interpreted differently in previous works. The observed kinetic data in alkaline solutions could be accounted for in terms of three forward [Fe²⁺cdta^4-+O₂ (rate-limiting, k_1,app), , 2Fe²⁺cdta^4-+H₂O₂] and one reverse [ (k_-1,app,n=0 or 1)] elementary steps. Assessment of the rate-limiting apparent rate constant led to the following results ( at and , , ). Fe³⁺OH^-cdta^4-, being the dominating iron(III) product at pH>10, was found to be less reactive than Fe³⁺cdta^4- with the superoxide intermediate , thus reducing the effect of the reverse step at higher pH. A study on the effect of electrolytes on the reaction rate led to the conclusion that salts increase the rate constant k_1,app. Finally, kinetic results in acidic conditions leading to the formation of other iron(II)-cdta complexes (i.e., Fe²⁺cdta^4-H⁺) and another superoxide intermediates are reported and discussed.     

Li-ion diffusion kinetics in LiFePO4 thin film prepared by radio frequency magnetron sputtering

LiFePO₄ thin films were prepared by radio frequency (RF) magnetron sputtering and were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and atomic force microscope (AFM). Li-ion chemical diffusion coefficients, , were measured by potentiostatic intermittent titration technique (PITT), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). The effects of Ag content, film thickness, and film orientation on the electrochemical performance and Li-ion chemical diffusion coefficients of the LiFePO₄ thin films were investigated. values were measured using the liquid electrolyte and the solid electrolyte, and the obtained values were discussed. The values by PITT and EIS were in the range of 10⁻¹⁴ to 10⁻¹² and 10⁻¹⁵ to 10⁻¹² cm² s⁻¹, respectively and that by CV was in the order of 10⁻¹⁴ cm² s⁻¹.     

Kinetic analysis on LiFePO4 thin films by CV, GITT, and EIS

LiFePO₄ thin films were deposited on Ti substrates by pulsed laser deposition (PLD). The apparent chemical diffusion coefficients of lithium in the films, , were measured by cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT), and electrochemical impedance spectroscopy (EIS). The average values calculated from CV results were in the order of 10⁻¹⁴ cm² s^–1. The values obtained by GITT, and EIS techniques were in the range of 10^–14–10^–18 cm² s^–1, 10^–14–10^–18 cm² s^–1, respectively. The values obtained by the two methods show a minimum point at x ∼ 0.5 for Li_1−xFePO₄. However, the overpotential values of the LiFePO₄ thin film electrodes obtained from the GITT results and the diffusion impedance deduced from the impedance spectra also show the minimum values at x ∼ 0.5 for Li_1–xFePO₄. This contradict could be caused by the improper use of GITT and EIS techniques for measuring the chemical diffusion coefficient of Li in Li_1–xFePO₄ which constitutes two phase, i.e., LiFePO₄ and FePO₄ in this region.     

Preparation and electrochemical studies of metal–carbon composite catalysts for small-scale electrosynthesis of H2O2

Numerous transition metal–carbon composite catalysts (M = V, Zn, Ni, Sn, Ce, Ba, Fe, Cu) have been synthesized and tested for electroreduction of O₂ to H₂O₂, The activity and selectivity of all synthesized catalysts for electrosynthesis of H₂O₂ were determined by the rotating ring-disk electrode method in acidic and neutral electrolytes. The Co-based catalysts in general showed the highest activity towards H₂O₂ formation. Experiments with different loading contents of Co showed that the activation overpotential losses of oxygen reduction to H₂O₂ reduces as loading increases to about 4 wt% Co. Addition of Co beyond this level did not seem to impact the overpotential losses. The cobalt-based catalysts, were spray-coated onto 120 μm thick Toray^® graphite substrates, and were studied in bulk electrolysis cells for up to 100 h at potentiostatic conditions (0.25 V vs. RHE) in pH 0, 3, and 7 electrolytes. At (25 °C and 1 bar) with a catalysts loading of about and using dissolved O₂ in 0.5 M H₂SO₄, typical H₂O₂ electrosynthesis rates of about were reached with current efficiencies of about 85 ± 5% at 0.25 V (vs. RHE).     

Investigation of formic acid oxidation on Ti/IrO2 electrodes

A model has been proposed according to which the voltammetric charge involved in the Ti/IrO₂ electrodes is due to two contributions: a faradaic contribution due to surface redox activities at the IrO₂ coating and a non-faradaic contribution due to the charging of electrical double layer (). The later has been proposed as a tool for the estimation of the relative surface area of the Ti/IrO₂ electrodes.Differential electrochemical mass spectrometry (DEMS) measurements using H₂¹⁸O has demonstrated that we are dealing with an active electrode in which the surface redox couple IrO₃/IrO₂ acts as mediator in the oxidation of formic acid (FA).From the voltammetric measurements using different IrO₂ loading and FA concentrations, the kinetic parameters of FA oxidation via the surface redox couple IrO₃/IrO₂ have been determined.Finally a model has been proposed considering that FA oxidation at Ti/IrO₂ anodes is controlled by mass transfer. The good agreement between the experimental results and the model indicates that the surface reaction between FA and the electrogenerated IrO₃ is a fast reaction.     

Anion exchanged polymerized ionic liquids: High free volume single ion conductors

In this study, we investigate the isolated effect of anion type on the chemical, thermal, and conductive properties of imidazolium-based polymerized ionic liquids (PILs). PILs with various anions at constant average chain length were prepared by ion exchange with a water-soluble PIL precursor, (poly(1-[(2-methacryloyloxy)ethyl]-3-butylimidazolium bromide) (poly(MEBIm-Br)). NMR, IR, and elemental analysis confirm that anion exchange of ploy(MEBIm-Br) with bis(trifluoromethanesulfonyl) imide (TFSI), tetrafluoroborate (BF₄), trifluoromethanesulfonate (Tf), and hexafluorophosphate (PF₆) in water resulted in nearly fully exchanged PILs. As a function of anion type, the glass transition temperature plays a dominant role, but not the sole role in determining ion conductivity. Other factors affecting ionic conductivity include the size and symmetry of the anion and dissociation energy of the ion pair. Both the Vogel-Fulcher-Tammann (VFT) and Williams-Landel-Ferry (WLF) equations were employed to investigate the temperature dependent ionic conductivities. The (9.03) and (168 K) values obtained from the WLF regression of these PILs greatly deviate from the classical WLF values originally obtained from the mechanical relaxation of uncharged polymers ( = 17.44,  = 51.6 K) and the WLF values obtained from the conductive properties of other polymer electrolytes. This suggests that the fractional free volume (f (T_g) = B/(2.303)) and Vogel temperature (T₀ = T_g − ) are strong functions of ion concentration, where high free volume allows for ion mobility at temperatures farther below the glass transition temperature of the polymer.     

Aspects of the development of a copper electrowinning cell based on reactive electrodialysis

This paper reports work aimed at developing a new copper electrowinning cell based on reactive electrodialysis (RED) which uses Fe²⁺→Fe³⁺+e as anodic reaction. In this lab-scale cell, the anolyte (aqueous FeSO₄+H₂SO₄) and the catholyte (aqueous CuSO₄+H₂SO₄) are kept separate by an anion membrane which prevents cation and water transport between the electrolytes. Both solutions are agitated by recirculation. The kinetics of the anodic reaction have been studied via potentiodynamic experiments on various anode materials (lead, platinum, ruthenium oxide, iridium oxide and graphite). The highest oxidation rate was obtained on platinum and the lowest one on lead, whereas the remaining materials showed satisfactory performance. Results in the lab-scale RED cell show that, depending on experimental conditions, for a cell current density of , the cell voltage ranges from 1.81 to , the cathodic current efficiency from 97.2% to 98.3% and the specific energy consumption, from 1.53 to of deposited copper.     

Experimental investigation of a pilot-scale jet bubbling reactor for wet flue gas desulphurisation

In the present work, an experimental parameter study was conducted in a pilot-scale jet bubbling reactor for wet flue gas desulphurisation (FGD). The pilot plant is downscaled from a limestone-based, gypsum producing full-scale wet FGD plant. Important process parameters, such as slurry pH, inlet flue gas concentration of SO₂, reactor temperature, and slurry concentration of Cl⁻ have been varied. The degree of desulphurisation, residual limestone content of the gypsum, liquid phase concentrations, and solids content of the slurry were measured during the experimental series.The SO₂ removal efficiency increased from 66.1% to 71.5% when the reactor slurry pH was changed from 3.5 to 5.5. Addition of Cl⁻ (in the form of CaCl₂·2H₂O) to the slurry increased the degree of desulphurisation to above 99%, due to the onset of extensive foaming, which substantially increased the gas-liquid contact area. An increase in the inlet flue gas SO₂ concentration from 502 to led to a decrease in the SO₂ removal efficiency from 80.1% to 69.4%. A temperature increase from 296 to caused a reduction in the degree of desulphurisation from 69.4% to 68.1%, but this result is almost within the experimental uncertainty. The residual limestone level in the gypsum formed increased with increasing values of reactor slurry pH, inlet flue gas SO₂ concentration, and slurry concentration of Cl⁻.     

Estimate of solid flow rate from pressure measurement in circulating fluidized bed

A method is described to estimate solid mass flow rate based on measurement of pressure drop in horizontal section of circulating fluid bed (CFB). A theoretical model was derived based on momentum balance equation and used to predict the solids flow rate. Several approaches for formulating such models are compared and contrasted. A correlation was developed that predicts the solids flow rate as a function of pressure drop measured in the horizontal section of piping leading from the top of the riser to the cyclone, often referred to as the cross-over. Model validation data was taken from literature data and from steady state, cold flow, CFB tests results of five granular materials with various sizes and densities in which the riser was operated in core-annular and dilute flow regimes. Experimental data were taken from a 0.20 m ID cross-over piping and compared to literature data generated in a 0.10 m ID cross-over pipe. The solids mass flow rate data were taken from statistically designed experiments over a wide range of Froude number , load ratio , Euler number , density ratio , Reynolds number , and Archimedes number . Several correlations were developed and tested to predict the solids mass flux based on measuring pressure drop in the horizontal section of CFB. It was found that load ratio is a linear function of the Euler number and that each of these expressions all worked quite well (R² > 95%) for the data within the range of conditions from which the coefficients were estimated.     

Characteristics and reactivities of Ca(OH)2/silica fume sorbents for low-temperature flue gas desulfurization

Ca(OH)₂/silica fume sorbents were prepared with various Ca(OH)₂/silica fume weight ratios and slurrying times at 65°C and a water/solid ratio of 10/1. Dry sorbents prepared were characterized, and their reactivities toward SO₂ were measured in a differential fixed-bed reactor at the conditions similar to those in the bag filters in the dry and semidry flue gas desulfurization (FGD) processes. The reaction between Ca(OH)₂ and silica fume in the slurry was very fast. The formation of calcium silicate hydrates, which were mainly C-S-H(I), resulted in sorbent particles with a highly porous structure that seemed compressible under high pressures. The sorbents were mesoporous, and their specific surface areas and pore volumes were much larger than those of Ca(OH)₂ alone. The utilization of Ca of sorbent increased with increasing silica fume content mainly due to the increase in the specific surface area of sorbent. The sorbent with Ca(OH)₂ had the maximum SO₂ capture. Sorbents with Ca(OH)₂ contents less than and greater than would have a SO₂ capture greater than that of Ca(OH)₂ alone. Both the utilization of Ca and SO₂ capture per unit specific surface area of sorbent decreased in general with increasing specific surface area. At the same Ca(OH)₂ content, the utilization of Ca or SO₂ capture of the Ca(OH)₂/silica fume sorbent was greater than that of the Ca(OH)₂/fly ash sorbent; however, the amount of SO₂ captured per unit surface area of the former sorbent was smaller than that of the latter sorbent. The results of this study are useful to the preparation of silica-enhanced sorbents for use in the dry and semidry FGD processes.     

Investigation on diffusion behavior of Li in LiFePO4 by capacity intermittent titration technique (CITT)

Capacity intermittent titration technique (CITT) was used to investigate the chemical diffusion coefficient () of lithium-ion in LiFePO₄ cathode material. The values of at the galvano-charge current of 0.2 and 0.4 mA were respectively found to range from 8.8 × 10⁻¹⁶ to 8.9 × 10⁻¹⁴ cm² s⁻¹ and from 1.2 × 10⁻¹⁶ to 8.5 × 10⁻¹⁴ cm² s⁻¹ in the voltage range from 3.2 to 4 V (vs. Li⁺/Li). The transfer coefficients of cathode (0.32-0.42) and anodic (0.26-0.3), and the standard rate constant (1.58 × 10⁻⁹ to 1.30 × 10⁻⁸ cm s⁻¹) were measured from the Tafel plots of LiFePO₄ in the equilibrium potential range from 3.06 to 3.45 V. From these kinetic parameters, the finite kinetics at interface was taken into account to revise the above values of . The revised values of at the galvano-charge current of 0.2 and 0.4 mA were respectively found to range from 2.44 × 10⁻¹⁵ to 2.21 × 10⁻¹³ cm² s⁻¹ and from 5.81 × 10⁻¹⁶ to 3.22 × 10⁻¹³ cm² s⁻¹ in the voltage range from 3.2 to 4 V. Results show that the approximation of infinite charge-transfer kinetics leads to a spurious value of which is lower than the revised value, and the spurious extent depends on the galvano-charge current of CITT experiment.