An assessment of inorganic components in condensable particulate matter as a function of surface aggregation, spatial suspension state and particle size.

Experimental studies assessed the removal efficiency and fine-size distribution of CPM coupled with compositional analysis across air pollution control device systems (APCDs) at an ultra-low emission (ULE) power plant. The findings indicated total CPM emissions were reduced to a minimum of 0.418 mg/m3 at the Wet Electrostatic Precipitator (WESP). The Wet Flue Gas Desulfurization (WFGD) showed the highest removal efficiency (98%) across all particle sizes, notably in the ultra-micron range. Selective Catalytic Reduction (SCR) demonstrated a mere 34% overall efficiency, with a negative removal rate in the ultra-fine particle range. The WESP effectively removed CPM only in sub-micron and ultra-micron sizes, but significantly increased water-soluble ions formation in ultra-fine spatially suspended CPM (CPMspa), leading to overall negative efficiency. Thus, the removal efficiency of the ultra-fine particle range was most affected among the three particle size ranges when the flue gas went through the APCDs. Major metal elements and water-soluble ions were more readily removed by APCDs due to their surface aggregation, while the removal of trace elements like Hg and Se was limited. Reducing SO42-/NH4+ formation in SCR, and optimizing WESP spray system operations based on flue gas components are essential steps in controlling CPM concentration in ULE power plants.

Hierarchically porous biochar templated by in situ formed ZnO for rapid Pb2+ and Cd2+ adsorption in wastewater: Experiment and molecular dynamics study.

3D hierarchical porous biochar (HPBC) was synthesized by a thermally removable template without post-activation. Zn(NO3)2 decomposition produced gases and ZnO in situ to activate and expand the three-dimensional micro-and mesopores. Compared with pristine biochar (BC), the specific surface area and pore volume of HPBC were increased by 223 and 75 times, respectively. The abundant pore structure of HPBC significantly enhanced the diffusion rate of heavy metals. For example, compared to BC, the time required for HPBC to adsorb Pb2+ reach adsorption equilibrium was reduced by 87.5% (40 min vs 5min). Such an adsorption performance of HPBC was also insensitive to different background ions (K+, Na+, Ca2+, and Mg2+) with a much higher concentration than that of heavy metals. When applied to treat desulfurization wastewater from power plants, HPBC yielded 100% removal of Pb2+ and Cd2+, much higher than that by using commercial activated carbon (28%). Molecular dynamics simulation revealed different locations preferred by the adsorption of Pb2+ (micropores) and Cd2+ (mesopores) in the hierarchical pore structures. The adsorption of Pb2+ and Cd2+ on HPBC was mainly achieved by diffusion, oxygen functional group complexation, and precipitation. These results provided better knowledge to understand the microscopic adsorption mechanisms of heavy metals in hierarchical pores and a facile yet robust strategy to design such structures in biochar for efficient wastewater treatment.

Enrichment and occurrence form of rare earth elements during coal and coal gangue combustion.

Coal ash has emerged as an important alternative source for rare earth elements (REEs). The enrichment and occurrence form of REEs among coal combustion products are of great significance for both technical design and economic evaluation of recovering REEs from the coal ash. Here, the enrichment and occurrence form of REEs in the ash were investigated. Compared with ashes from muffle furnace, coal fly ash (CFA) from power plants involved higher enrichment ratio of REEs, which was explained by the fractionation of coal ashes to concentrate REEs in finer CFA, higher combustion temperature to vaporize more volatile elements, and longer residence time of fly ash to absorb REEs in the gas. In addition, CFA samples were analyzed by sequence chemical extraction procedure (SCEP) and scanning electron microscope with an energy dispersive spectrometer (SEM-EDX), which revealed the important role of aluminum in the occurrence form of REEs compared with Si in aluminosilicates of CFA. This conclusion was further confirmed by thermodynamic equilibrium calculation, which also agreed qualitatively with the observation that REEs mainly existed in the solid phase. Both experimental and computational results of this work provided insights to understand the distribution of REEs in CFA and optimize their extraction processes.

Mercury speciation and size-specific distribution in filterable and condensable particulate matter from coal combustion.

Particle-bound mercury discharged with fine particulate matter from coal-fired power plants causes atmospheric pollution that impacts human health. In this study, the speciation and size-specific distribution of particle-bound mercury in filterable particulate matter (FPM) from an ultra-low emission power plant and condensable particulate matter (CPM) from an entrained flow reactor were analyzed. Most importantly, particle-bound mercury was enriched in fine particles smaller than 0.02 µm, whose mass fraction was several orders of magnitude higher than that in large particles. Particularly, HgBr2, HgCl2, and HgO were major mercury species in FPM, whereas CPM involves mostly HgCl2 with a small portion of HgBr2. The occurrence of these species was also confirmed by a thermodynamic equilibrium calculation. The results further revealed the effects of air pollution control devices (APCDs) on the speciation of particle-bound mercury. Specifically, an electrostatic precipitator (ESP) removed most particle-bound mercury. Similarly, wet flue gas desulfurization (WFGD) dramatically reduced particle-bound mercury for most particles, except those between 0.1 and 1 µm. At the outlet of WFGD, mercury bound with FPM10 (smaller than 10 µm) is only 0.15% of the total mercury at the inlet of selective catalytic reduction (SCR). This knowledge provides insights that can be used to design and optimize the control strategy for mercury emission in power plants.

A novel modified method for the efficient removal of Pb and Cd from wastewater by biochar: Enhanced the ion exchange and precipitation capacity.

The purpose of this research was to improve the sorption ability of Pb and Cd by promoting the ion exchange and precipitation capacity of biochar. The adsorption performance and mechanisms of Pb and Cd in wastewater using coconut shell biochar modified with magnesium were investigated. After modification, the total adsorption capacity (Qt) of Pb and Cd on Mg-coated biochar (MgBC400) increased by 20 and 30 times compared with the unmodified biochar (BC400), respectively. The removal of Pb and Cd to biochar was attributed to ion exchange (Qe), mineral precipitation (Qp), interaction with oxygen functional groups (OFGs) [(Qf)], and metal-π electron coordination (Qπ). Compared with the BC400, the adsorption capacity of the four fractions of MgBC400 increased especially the ion exchange and precipitation. The Qe values of MgBC400 were almost 49 and 59 times that of BC400 in the adsorption of Pb and Cd, respectively. The Qp values of MgBC400 increased by 214.4 and 81.7 mg/g, respectively. Ion exchange and mineral precipitation dominated the adsorption of Pb and Cd by MgBC400.

High performance aqueous supercapacitor based on nitrogen-doped coal-based activated carbon electrode materials.

The performance of a supercapacitor (SCs) fabricated from coal-based activated carbon was studied in terms of its specific capacitance (C), life cycle and rate performance. In this work, a low cost modified nitrogen-doped coal-based activated carbon (MACN) was prepared by KOH/H2O co-activation from lignite. Experimental results and density functional theory (DFT) calculations showed that introducing nitrogen atoms into the coal-based activated carbon leads to a rearrangement of the carbon skeleton structure and changes the surface chemical environment. Leading to the MACN internal disorder increases (ID/IG is up to 0.99), structural stability improves (TGA curves shift right), and various nitrogen functional groups (N-5, N-6, N-Q) are formed on the carbon surface. In addition, the MACN possesses high specific surface area (SBET: 2129 m2/g), abundant micropores (Vmic: 0.62 cm3/g), appropriate mesopores (Vmes: 0.39 cm3/g, Vmes ratio: 38.6%), low impurity content, and highly N-doping (9.59 wt%). These characteristics of the MACN provide for a high C of 323 F/g at a current density of 0.5 A/g. The enhanced MACN is 64.8% higher than the undoped MAC. Furthermore, a high energy density of 10 Wh/kg can be achieved with a MACN-assembled symmetrical cell when the power density of 250 W/kg in 6 M KOH.

Catalytic conversion of mercury over Ce doped Mn/SAPO-34 catalyst: Sulphur tolerance and SO2/SO3 conversion.

A series of Mn-Ce/SAPO-34 catalysts were prepared to study the catalytic oxidisation of elemental mercury (Hg0). Sulphur tolerance and SO3 formation over the catalyst were studied further. Hg0 was transported by compressed air from PSA Cavkit. NO, SO2, and NH3 are standard gases, and H2O is produced by gas carrying. Mn could incorporate into the cerium oxide lattice to form capping oxygen and well-dispersed high valance manganese ions after the addition of Ce, which was conducive to NO removal and Hg0 oxidisation. 9 Mn-9Ce showed the best performance regarding Hg0 conversion, achieving more than 92% Hg0 conversion efficiency at 50-300 °C. The sulphur resistance of the Mn-based catalyst was significantly improved after the addition of cerium due to the high affinity of Ce for SO2, and the relative content of HgSO4 was exceeded 72% on the 9 Mn-9Ce catalyst with SO2; SO3 formation over the 9 Mn-9Ce decreased by 17% compared with the 9 Mn. H2O not only reduced the available active site, but also decreased the oxidation rate of SO2. The active sites were preferentially occupied by NH3 rather than Hg0 and SO2, generated NH4+ occupied cation vacancies. Therefore, both H2O and NH3 have inhibitory effects on Hg0 conversion and SO3 formation.

Arsenic release and transformation in co-combustion of biomass and coal: Effect of mineral elements and volatile matter in biomass.

After the co-combustion of tobacco stem/black bean straw/wheat straw/millet straw/corn stalk/rice straw and coal, it was found that all tested biomass in this study could inhibit arsenic release, but only rice straw promoted arsenic release. When the acid washed biomass was mixed with coal during combustion, the release of arsenic increased. When mineral metals (Na, K, Mg, Ca, Al and Fe) and Si elements were added to the coal, the mineral metals inhibited arsenic release. However, the release of arsenic was increased when the silicon content in biomass was high. The volatiles in the biomass also promoted the release of arsenic during co-combustion. The arsenic in the ash generated from co-combustion was mainly in the sulphide-bound state. Co-combustion of biomass and coal reduced the occurrence of an exchangeable state in the ash, and also significantly reduce the possibility of leaching.

The distribution of Pb(II)/Cd(II) adsorption mechanisms on biochars from aqueous solution: Considering the increased oxygen functional groups by HCl treatment.

The adsorption mechanisms of Pb(II) and Cd(II) in aqueous solution using camellia seed husk biochars pyrolyzed at different temperatures were studied. The adsorption of Pb(II) and Cd(II) on biochars are mainly controlled by ion exchange, oxygen functional groups (OFGs) complexation, Pb(II)/Cd(II)-π interactions, and precipitation with minerals. Compared to the raw biochars, both carboxyl and phenolic hydroxyl groups increased in the biochars washed with HCl. However, the previous research ignored the effect of the increased OFGs. Thus, a revised method was proposed from this study to more accurately calculate the contribution of four different mechanisms. Precipitation with minerals was the dominant mechanism for Pb(II) and Cd(II) removal, accounting for 80.61-89.03% and 53.57-75.84%, respectively, of the total adsorption as the pyrolysis temperature increased from 300 °C to 700 °C. As for oxygen functional groups complexation, the percentage of Pb(II) and Cd(II) removal were 4.76-8.55% and 11.34-29.59%, respectively.

In-Situ Capture of Mercury in Coal-Fired Power Plants Using High Surface Energy Fly Ash.

Coal-fired power plants represent the largest source of mercury emissions worldwide. Using fly ash, a byproduct of these plants, as a sorbent to remove mercury has proven to be difficult. Here, we found that the fresh surface of modified fly ash has good adsorption performance, and it declines obviously with time because of unsaturation characteristics on surface. On the basis of this mechanism, our study provides a method to in situ capture mercury with high surface energy modified fly ash by mechanochemical and bromide treatment. Fresh modified fly ash with active sites is injected into the flue to directly adsorb mercury. A continuous system within a full-scale 300 MWe plant showed that the mercury adsorption performance of the modified fly ash is similar to that of activated carbon, which is the industry benchmark for the treatment of mercury emission in fossil power generation units. This is a breakthrough and indicates that modified fly ash can become an efficient and convenient industrial sorbent for the removal of mercury.

Mercury adsorption characteristics of HBr-modified fly ash in an entrained-flow reactor.

In this study, the mercury adsorption characteristics of HBr-modified fly ash in an entrained-flow reactor were investigated through thermal decomposition methods. The results show that the mercury adsorption performance of the HBr-modified fly ash was enhanced significantly. The mercury species adsorbed by unmodified fly ash were HgCl2, HgS and HgO. The mercury adsorbed by HBr-modified fly ash, in the entrained-flow reactor, existed in two forms, HgBr2 and HgO, and the HBr was the dominant factor promoting oxidation of elemental mercury in the entrained-flow reactor. In the current study, the concentration of HgBr2 and HgO in ash from the fine ash vessel was 4.6 times greater than for ash from the coarse ash vessel. The fine ash had better mercury adsorption performance than coarse ash, which is most likely due to the higher specific surface area and longer residence time.

Application of fly ash as an adsorbent for Estradiol in animal waste.

The contamination of agricultural ground with estrogen compounds through application of animal wastes is a present concern. At the same time, current uses for waste fly ash having high carbon content are limited. To help mitigate these problems, we examine using waste fly ash as a useful adsorbent for Estradiol in pig waste digests. In this study, Estradiol was added to vials containing water and fly ash from several different power plants. After an extraction process, the amount of Estradiol in the water was measured. Commercial activated carbon was also used for comparison purposes. Vials containing varying concentrations of Estradiol and no trapping material were used as a control. The results from this study indicate that fly ash can be used as a trapping material for Estradiol in water, but that commercially available activated carbon can trap about an order of magnitude more Estradiol than the fly ash and that the effects of the fly ash matrix can both inhibit and promote the solvation of Estradiol into water depending possibly upon pH and cation concentration effects. In addition, preliminary extraction studies using pig waste digest indicate that fly ash can be used as adsorbent for Estradiol present in pig waste.

Co-combustion characteristics and blending optimization of tobacco stem and high-sulfur bituminous coal based on thermogravimetric and mass spectrometry analyses.

Despite much research on co-combustion of tobacco stem and high-sulfur coal, their blending optimization has not been effectively found. This study investigated the combustion profiles of tobacco stem, high-sulfur bituminous coal and their blends by thermogravimetric analysis. Ignition and burnout performances, heat release performances, and gaseous pollutant emissions were also studied by thermogravimetric and mass spectrometry analyses. The results indicated that combustion of tobacco stem was more complicated than that of high-sulfur bituminous coal, mainly shown as fixed carbon in it was divided into two portions with one early burning and the other delay burning. Ignition and burnout performances, heat release performances, and gaseous pollutant emissions of the blends present variable trends with the increase of tobacco stem content. Taking into account the above three factors, a blending ratio of 0­20% tobacco stem content is conservatively proposed as optimum amount for blending.

Mercury emission and plant uptake of trace elements during early stage of soil amendment using flue gas desulfurization materials.

A pilot-scale field study was carried out to investigate the distribution of Hg and other selected elements (i.e., As, B, and Se), i.e., emission to ambient air, uptake by surface vegetation, and/or rainfall infiltration, after flue gas desulfurization (FGD) material is applied to soil. Three FGD materials collected from two power plants were used. Our results show Hg released into the air and uptake in grass from all FGD material-treated soils were all higher (P < 0.1) than the amounts observed from untreated soil. Hg in the soil amended with the FGD material collected from a natural oxidation wet scrubber (i.e., SNO) was more readily released to air compared to the other two FGD materials collected from the synthetic gypsum dewatering vacuum belt (i.e., AFO-gypsum) and the waste water treatment plant (i.e., AFO-CPS) of a forced oxidation FGD system. No Hg was detected in the leachates collected during the only 3-hour, 1-inch rainfall event that occurred throughout the 4-week testing period. For every kilogram of FGD material applied to soil, AFO-CPS released the highest amount of Hg, B, and Se, followed by SNO, and AFO gypsum. Based on the same energy production rate, the land application of SNO FGD material from Plant S released higher amounts of Hg and B into ambient air and/or grass than the amounts released when AFO-gypsum from Plant A was used. Using FGD material with lower concentration levels of Hg and other elements of concern does not necessary post a lower environmental risk. In addition, this study demonstrates that considering only the amounts of trace elements uptake in surface vegetation may under estimate the overall release of the trace elements from FGD material-amended soils. It also shows, under the same soil amendment conditions, the mobility of trace elements varies when FGD materials produced from different processes are used.

Selenium speciation in flue desulfurization residues.

Flue gas from coal combustion contains significant amounts of volatile selenium (Se). The capture of Se in the flue gas desulfurization (FGD) scrubber unit has resulted in a generation of metal-laden residues. It is important to determine Se speciation to understand the environmental impact of its disposal. A simple method has been developed for selective inorganic Se(IV), Se(VI) and organic Se determination in the liquid-phase FGD residues by hydride generation atomic fluorescence spectrometry (AFS). It has been determined that Se(IV), Se(VI) and organic Se can be accurately determined with detection limits (DL) of 0.05, 0.06 and 0.06 microg/L, respectively. The accuracy of the proposed method was evaluated by analyzing the certified reference material, NIST CRM 1632c, and also by analyzing spiked tap-water samples. Analysis indicates that the concentration of Se is high in FGD liquid residues and primarily exists in a reduced state as selenite (Se(IV)). The toxicity of Se(IV) is the strongest of all Se species. Flue gas desulfurization residues pose a serious environmental risk.

Studies of the fate of sulfur trioxide in coal-fired utility boilers based on modified selected condensation methods.

The formation of sulfur trioxide (SO(3)) in coal-fired utility boilers can have negative effects on boiler performance and operation, such as fouling and corrosion of equipment, efficiency loss in the air preheater (APH), increase in stack opacity, and the formation of PM(2.5). Sulfur trioxide can also compete with mercury when bonding with injected activated carbons. Tests in a lab-scale reactor confirmed there are major interferences between fly ash and SO(3) during SO(3) sampling. A modified SO(3) procedure to maximize the elimination of measurement biases, based on the inertial-filter-sampling and the selective-condensation-collecting of SO(3), was applied in SO(3) tests in three full-scale utility boilers. For the two units burning bituminous coal, SO(3) levels starting at 20 to 25 ppmv at the inlet to the selective catalytic reduction (SCR), increased slightly across the SCR, owing to catalytic conversion of SO(2) to SO(3,) and then declined in other air pollutant control device (APCD) modules downstream to approximately 5 ppmv and 15 ppmv at the two sites, respectively. In the unit burning sub-bituminous coal, the much lower initial concentration of SO(3) estimated to be approximately 1.5 ppmv at the inlet to the SCR was reduced to about 0.8 ppmv across the SCR and to about 0.3 ppmv at the exit of the wet flue gas desulfurization (WFGD). The SO(3) removal efficiency across the WFGD scrubbers at the three sites was generally 35% or less. Reductions in SO(3) across either the APH or the dry electrostatic precipitator (ESP) in units burning high-sulfur bituminous coal were attributed to operating temperatures being below the dew point of SO(3).

A technique for sequential leaching of coal and fly ash resulting in good recovery of trace elements.

Coal and fly ash contain many elements. These elements exist in different forms which may change throughout the coal combustion process. There are several processes, including X-ray techniques and leaching techniques by which studies have attempted to assess the form of a particular element in a sample. This work focuses on determining the leachability of selected elements sequentially leached in four extraction solutions: water, 1M ammonium acetate, 3M hydrochloric acid and 50% hydrofluoric acid. The emphasis is on evaluating the steps involved in the leaching process with the mass recovery for each element being the basis for evaluation. The total amount of each element that will leach out under the given extraction condition is presented as a fraction of the total present in the material. The materials evaluated were NIST coal and fly ash standards. The elements measured in this study include aluminum, barium, beryllium, calcium, chromium, cobalt, iron, magnesium, manganese, nickel, potassium, sodium, strontium, vanadium and zinc.

Modeling mercury speciation in combustion flue gases using support vector machine: prediction and evaluation.

Mercury emission from coal combustion has become a global environmental problem. In order to accurately reveal the complexly nonlinear relationships between mercury emissions characteristics in flue gas and coal properties as well as operating conditions, an alternative model using support vector machine (SVM) based on dynamically optimized search technique with cross-validation, is proposed to simulate the mercury speciation (elemental, oxidized and particulate) and concentration in flue gases from coal combustion, then the configured SVM model is trained and tested by simulation results. According to predicted accuracy of indicating generalization capability, the model performance is compared and evaluated with the conventional multiple nonlinear regression (MNR) models and the artificial neural network (ANN) models. As a result, it is found that, the SVM provides better prediction performances with the mean squared error of 0.0095 and the correlation coefficient of 0.9164 for testing sample. Moreover, based on the SVM model, the correlativity between coal properties as well as operating condition and mercury chemical form is also analyzed in order to deeply understand mercury emissions characteristics. The result demonstrates that SVM can offer an alternative and powerful approach to model mercury speciation in coal combustion flue gases.

Simulation of mercury capture by sorbent injection using a simplified model.

Mercury pollution by fossil fuel combustion or solid waste incineration is becoming the worldwide environmental concern. As an effective control technology, powdered sorbent injection (PSI) has been successfully used for mercury capture from flue gas with advantages of low cost and easy operation. In order to predict the mercury capture efficiency for PSI more conveniently, a simplified model, which is based on the theory of mass transfer, isothermal adsorption and mass balance, is developed in this paper. The comparisons between theoretical results of this model and experimental results by Meserole et al. [F.B. Meserole, R. Chang, T.R. Carrey, J. Machac, C.F.J. Richardson, Modeling mercury removal by sorbent injection, J. Air Waste Manage. Assoc. 49 (1999) 694-704] demonstrate that the simplified model is able to provide good predictive accuracy. Moreover, the effects of key parameters including the mass transfer coefficient, sorbent concentration, sorbent physical property and sorbent adsorption capacity on mercury adsorption efficiency are compared and evaluated. Finally, the sensitive analysis of impact factor indicates that the injected sorbent concentration plays most important role for mercury capture efficiency.

Enhancement of mercury capture by the simultaneous addition of hydrogen bromide (HBr) and fly ashes in a slipstream facility.

Low halogen content in tested Powder River Basin (PRB) coals and low loss of ignition content (LOI) in PRB-derived fly ash were likely responsible for higher elemental mercury content (averaging about 75%) in the flue gas and also lower mercury capture efficiency by electrostatic precipitator (ESP) and wet-FGD. To develop a cost-effective approach to mercury capture in a full-scale coal-fired utility boiler burning PRB coal, experiments were conducted adding hydrogen bromide (HBr) or simultaneously adding HBr and selected fly ashes in a slipstream reactor (0.152 x 0.152 m) under real flue gas conditions. The residence time of the flue gas inside the reactorwas about 1.4 s. The average temperature of the slipstream reactor was controlled at about 155 degrees C. Tests were organized into two phases. In Phase 1, only HBr was added to the slipstream reactor, and in Phase 2, HBr and selected fly ash were added simultaneously. HBr injection was effective (>90%) for mercury oxidation at a low temperature (155 degrees C) with an HBr addition concentration of about 4 ppm in the flue gas. Additionally, injected HBr enhanced mercury capture by PRB fly ash in the low-temperature range. The mercury capture efficiency, attesting conditions of the slipstream reactor, reached about 50% at an HBr injection concentration of 4 ppm in the flue gas. Compared to only the addition of HBr, simultaneously adding bituminous-derived fly ash in a minimum amount (30 lb/MMacf), together with HBr injection at 4 ppm, could increase mercury capture efficiency by 30%. Injection of lignite-derived fly ash at 30 lb/MMacf could achieve even higher mercury removal efficiency (an additional 35% mercury capture efficiency compared to HBr addition alone).