Mass transfer within electrostatic precipitators: in-flight adsorption of mercury by charged suspended particulates

Electrostatic precipitation is the dominant method of particulate control used for coal combustion, and varying degrees of mercury capture and transformation have been reported across ESPs. Nevertheless, the fate of gas-phase mercury within an ESP remains poorly understood. The present analysis focuses on the gas-particle mass transfer that occurs within a charged aerosol in an ESP. As a necessary step in gas-phase mercury adsorption or transformation, gas-particle mass transfer-particularly in configurations other than fixed beds-has received far less attention than studies of adsorption kinetics. Our previous analysis showed that only a small fraction of gas-phase mercury entering an ESP is likelyto be adsorbed by collected particulate matter on the plate electrodes. The present simplified analysis provides insight into gas-particle mass transfer within an ESP under two limiting conditions: laminar and turbulent fluid flows. The analysis reveals that during the process of particulate collection, gas-particle mass transfer can be quite high, easily exceeding the mass transfer to ESP plate electrodes in most cases. Decreasing particle size, increasing particle mass loading, and increasing temperature all result in increased gas-particle mass transfer. The analysis predicts significantly greater gas-particle mass transfer in the laminar limitthan in the turbulent limit; however, the differences become negligible under conditions where other factors, such as total mass of suspended particulates, are the controlling mass transfer parameters. Results are compared to selected pilot- and full-scale sorbent injection data.     

Estimates of increased black carbon emissions from electrostatic precipitators during powdered activated carbon injection for mercury emissions control

The behavior of mercury sorbents within electrostatic precipitators (ESPs) is not well-understood, despite a decade or more of full-scale testing. Recent laboratory results suggest that powdered activated carbon exhibits somewhat different collection behavior than fly ash in an ESP and particulate filters located at the outlet of ESPs have shown evidence of powdered activated carbon penetration during full-scale tests of sorbent injection for mercury emissions control. The present analysis considers a range of assumed differential ESP collection efficiencies for powdered activated carbon as compared to fly ash. Estimated emission rates of submicrometer powdered activated carbon are compared to estimated emission rates of particulate carbon on submicrometer fly ash, each corresponding to its respective collection efficiency. To the extent that any emitted powdered activated carbon exhibits size and optical characteristics similar to black carbon, such emissions could effectively constitute an increase in black carbon emissions from coal-based stationary power generation. The results reveal that even for the low injection rates associated with chemically impregnated carbons, submicrometer particulate carbon emissions can easily double if the submicrometer fraction of the native fly ash has a low carbon content. Increasing sorbent injection rates, larger collection efficiency differentials as compared to fly ash, and decreasing sorbent particle size all lead to increases in the estimated submicrometer particulate carbon emissions.     

Ultrafine aerosol penetration through electrostatic precipitators

This work measures the penetration of ultrafine particles through a single-stage and a two-stage ESP as a function of particle size. Also studied herein are how parameters including particle size, rate of airflow through the ESP, and voltage of the discharging electrode affect aerosol penetration through the ESP. Monodisperse particles with sizes between 10 and 60 nm were generated as the challenge aerosols to investigate the particle charges given by an ESP. A comparison of experimental and theoretical results confirms that a partial charging regime exists when the particle diameter is several tens of nanometers. Experimental results indicated that aerosol penetration through the single- and two-stage ESPs increased significantly for particles below 20 and 50 nm, respectively. However, the exact regime depends on the parameters including airflow rate, applied voltage, and configuration of the ESP. Phenomena such as ionic flow, particle space charge, and flow turbulence may significantly affect the collection efficiency of an ESP for ultrafine particles. To achieve the same collection efficiency, it is more economical to use single-stage ESPs to collect particles less than 16 nm from the standpoint of energy consumption. However, it is more economical to use two-stage ESPs to collect particles larger than 16 nm.     

Electrostatic precipitator performance and trace element emissions from two Kraft recovery boilers

Fine particle emissions from combustion sources have gained attention recently due to their adverse effects on human health. The emission depends on the combustion process, fuel, and particulate removal technology. Particle concentrations at Kraft recovery boiler exits are very high, and the boilers are typically equipped with electrostatic precipitators (ESP). However, little data are available on the ESP performance in recovery boilers. Particle concentrations and size distributions were determined at two modern, operating recovery boilers. In addition, we determined the fractional collection efficiency of the ESPs by simultaneous measurements at the ESP inlet and outlet and the particulate emissions of trace metals. The particle mass concentration atthe ESP inlet was 11-24 g/Nm3 at the two boilers. Particle emissions were 30-40 mg/ Nm3 at boiler A and 12-15 mg/Nm3 at boiler B. The particle size distributions had a major particle mode at around 1 microm. These fume particles contained most of the particle mass. The main components in the particles were sodium and sulfate with minor amounts of chloride, potassium, and presumably some carbonate. The ESP collection efficiency was 99.6-99.8% at boiler A and 99.9% at boiler B. The particle penetration through the ESP was below 0.6% in the entire fume particle size range of 0.3-3 microm. Trace element emissions from both boilers were well below the limit values set by EU directive for waste incineration.     

Novel regenerable sorbent for mercury capture from flue gases of coal-fired power plant

A natural chabazite-based silver nanocomposite (AgMC) was synthesized to capture mercury from flue gases of coal-fired power plants. Silver nanoparticles were engineered on zeolite through ion-exchange of sodium ions with silver ions, followed by thermal annealing. Mercury sorption test using AgMC was performed at various temperatures by exposing it to either pulse injection of mercury or continuous mercury flow. A complete capture of mercury by AgMC was achieved up to a capture temperature of 250 degrees C. Nano silver particles were shown to be the main active component for mercury capture by amalgamation mechanism. Compared with activated carbon-based sorbents, the sorbent prepared in this study showed a much higher mercury capture capacity and upper temperature limit for mercury capture. More importantly, the mercury captured by the spent AgMC could be easily released for safe disposal and the sorbent regenerated by simple heating at 400 degrees C. Mercury capture tests performed in real flue gas environment showed a much higher level of mercury capture by AgMC than by other potential mercury sorbents tested. In our mercury capture tests, the AgMC exposed to real flue gases showed an increased mercury capture efficiency than the fresh AgMC.     

SO2 retention by reactivated CaO-based sorbent from multiple CO2 capture cycles

This paper examines the reactivation of spent sorbent, produced from multiple CO2 capture cycles, for use in SO2 capture. CaO-based sorbent samples were obtained from Kelly Rock limestone using three particle size ranges, each containing different impurities levels. Using a thermogravimetric analyzer (TGA), the sulfation behavior of partially sulfated and unsulfated samples obtained after multiple calcination-carbonation cycles in a tube furnace (TF), following steam reactivation in a pressurized reactor, is examined. In addition, samples calcined/sintered under different conditions after hydration are also examined. The results show that suitably treated spent sorbent has better sulfation characteristics than that of the original sorbent. Thus for example, after 2 h sulfation, > 80% of the CaO was sulfated. In addition, the sorbent showed significant activity even after 4 h when > 95% CaO was sulfated. The results were confirmed by X-ray diffraction (XRD) analysis, which showed that, by the end of the sulfation process, samples contained CaSO4 with only traces of unreacted CaO. The superior behavior of spent reactivated sorbent appears to be due to swelling of the sorbent particles during steam hydration. This enables the development of a more suitable pore surface area and pore volume distribution for sulfation, and this has been confirmed by N2 adsorption-desorption isotherms and the Barrett-Joyner-Halenda (BJH) method. The surface area morphology of sorbent after reactivation was examined by scanning electron microscopy (SEM). Ca(OH)2 crystals were seen, which displayed their regular shape, and their elemental composition was confirmed by energy-dispersive X-ray (EDX) analysis. The improved characteristics of spent reactivated sorbent in comparison to the original and to the sorbent calcined under different conditions and hydrated indicate the beneficial effect of CO2 cycles on sorbent reactivation and subsequent sulfation. These results allow us to propose a new process for the use of CaO-based sorbent in fluidized bed combustion (FBC) systems, which incorporates CO2 capture, sorbent reactivation, and SO2 retention.     

Enhancement of fast CO2 capture by a nano-SiO2/CaO composite at Ca-looping conditions

In this paper we show the performance of a new CO(2) sorbent consisting of a dry physical mixture of a Ca-based sorbent and a SiO(2) nanostructured powder. Thermo-gravimetric analysis (TGA) performed at conditions close to the Ca-looping process demonstrate that the rate of CO(2) capture by the mixture is enhanced during the fast carbonation stage of practical interest in applications. Moreover, the residual capture capacity of the mixture is increased. SEM/EDX, physisorption, and XRD analyses indicate that there is a relevant interaction between the nanostructured SiO(2) skeleton and CaO at high temperatures, which serves to improve the efficiency of the transfer of CO(2) to small reactive pores as well as the stability of the sorbent pore structure.     

Adsorption enhancement mechanisms of silica-titania nanocomposites for elemental mercury vapor removal

A novel nanocomposite that combines high-surface area silica with the photocatalytic properties of titania has been developed that allows for effective capture of elemental mercury vapor. The adsorption capability of the developed material has been found to improve after periods of photocatalytic oxidation. In this study, the mechanisms for adsorption enhancement were identified. BET nitrogen adsorption and mercury porosimetry were used to evaluate pore structure, and the results suggest that a decrease in contact angle was likely to be responsible for improved mercury capture over time. Contact angle measurements showed a significant change of more than 10 degrees, indicating greater attraction to mercury for the used pellets due to deposited mercuric oxide. ICP and TGA analyses showed that mercury was captured as both elemental mercury (Hg0) and mercuric oxide (HgO). In addition, it was shown that pellets used for nearly 500 h still showed greater than 90% removal efficiency and had an average capacity of 10 mg of Hg/g based on mass balance calculations, while some pellets had a capacity over 30 mg of Hg/g according to ICP and TGA analyses. Mercuric oxide doped pellets removed 100% of elemental mercury without pretreatment. The superior mercury removal efficiency combined with various advantages of the novel composite demonstrates its use as an effective alternative to conventional activated carbon injection technology.     

Collection of ultrafine diesel particulate matter (DPM) in cylindrical single-stage wet electrostatic precipitators

Long-term exposures to diesel particulate matter (DPM) emissions are linked to increasing adverse human health effects due to the potential association of DPM with carcinogenicity. Current diesel vehicular particulate emission regulations are based solely upon total mass concentration, albeit it is the submicrometer particles that are highly respirable and the most detrimental to human health. In this study, experiments were performed with a tubular single-stage wet electrostatic precipitator (wESP) to evaluate its performance for the removal of number-based DPM emissions. A nonroad diesel generator utilizing a low sulfur diesel fuel (500 ppmw) operating under varying load conditions was used as a stationary DPM emission source. An electrical low-pressure impactor (ELPI) was used to quantify the number concentration distributions of diesel particles in the diluted exhaust gas at each tested condition. The wESP was evaluated with respect to different operational control parameters such as applied voltage, gas residence time, etc., to determine their effect on overall collection efficiency, as well as particle size dependent collection efficiency. The results show that the total DPM number concentrations in the untreated diesel exhaust are in the magnitude of approximately108/cm(3) at all engine loads with the particle diameter modes between 20 and 40 nm. The measured collection efficiency of the wESP operating at 70 kV based on total particle numbers was 86% at 0 kW engine load and the efficiency decreased to 67% at 75 kW due to a decrease in gas residence time and an increase in particle concentrations. At a constant wESP voltage of 70 kV and at 75 kW engine load, the variation of gas residence time within the wESP from approximately 0.1 to approximately 0.4 s led to a substantial increase in the collection efficiency from 67% to 96%. In addition, collection efficiency was found to be directly related to the applied voltage, with increasing collection efficiency measured for increases in applied voltage. The collection efficiency based on particle size had a minimum for sizes between 20 and 50 nm, but at optimal wESP operating conditions it was possible to remove over 90% of all particle sizes. A comparison of measured and calculated collection efficiencies reveals that the measured values are significantly higher than the predicted values based on the well-known Deutsch equation.     

An electrochemical system for removing and recovering elemental mercury from a gas stream

The impending EPA regulations on the control of mercury emissions from the flue stacks of coal-burning electric utilities has resulted in the development of numerous advanced mercury control technologies such as sorbent injection and in-situ mercury oxidation. Although these technologies can effectively remove mercury from a flue stack they share, along with many other technologies, the common shortcoming of intermedia pollution transfer i.e. the traffic of mercury from the air phase to the solid phase and the subsequent generation of residue for landfill. This work addresses the need for an integrated system of mercury removal and recovery from flue stack gases and from the environment. The research explored the capture of elemental mercury from the gas phase at ambient temperature on an electrically conductive porous sorbent. The mercury loaded sorbent was regenerated at the anode in an electrochemical cell and the oxidized mercury recovered at the cathode as solid elemental mercury. Activated carbon cloth was selected as the most suitable sorbent as it had the highest mercury adsorption capacity of the sorbents tested and was electrically conductive. Direct and indirect electro-oxidation were shown to remove 95% and 100%, respectively, of the elemental mercury from the carbon cloth. After regeneration the carbon cloth was reused without any loss in mercury adsorption capacity. More than 99% of the mercury stripped from the cloth during regeneration was recovered at the cathode.     

Mercury vapor release from broken compact fluorescent lamps and in situ capture by new nanomaterial sorbents

The projected increase in the use of compact fluorescent lamps (CFLs) motivates the development of methods to manage consumer exposure to mercury and its environmental release at the end of lamp life. This work characterizes the time-resolved release of mercury vapor from broken CFLs and from underlying substrates after removal of glass fragments to simulate cleanup. In new lamps, mercury vapor is released gradually in amounts that reach 1.3 mg or 30% of the total lamp inventory after four days. Similar time profiles but smaller amounts are released from spent lamps or from underlying substrates. Nanoscale formulations of S, Se, Cu, Ni, Zn, Ag, and WS2 are evaluated for capture of Hg vapor under these conditions and compared to conventional microscale formulations. Adsorption capacities range over 7 orders of magnitude, from 0.005 (Zn micropowder) to 188 000 microg/g (unstabilized nano-Se), depending on sorbent chemistry and particle size. Nanosynthesis offers clear advantages for most sorbent chemistries. Unstabilized nano-selenium in two forms (dry powder and impregnated cloth) was successfully used in a proof-of-principle test for the in situ, real-time suppression of Hg vapor escape following CFL fracture.     

Nanostructured sorbents for capture of cadmium species in combustion environments

The pathways of cadmium species to form a submicrometer-sized aerosol in a combustion system exhaust were established. Cadmium oxide was the predominant species formed in the experiments and resulted in particles of a mean size of 26-63 nm with number concentrations in the range of 2-8 x 10(6) cm(-3). Two different nanostructured sorbents, a solid montmorillonite (MMT) and an in situ generated agglomerated silica, were used for capture of the cadmium species. The MMT sorbent was not stable at 1000 degrees C, and structural changes resulted. MMT did not suppress nucleation of cadmium species and partially captured it by weak physisorption as established by the leachability tests. In contrast, the in situ generated silica nanostructured agglomerates had a high surface area, suppressed nucleation of cadmium species vapors, and chemisorbed them effectively resulting in a firm binding, as compared to the MMT sorbent. There is an optimal temperature-time relationship at which the capture process is expected to be most effective. The leaching efficiency under these conditions was less than 3.2%. The nanostructured silica agglomerate size can be tuned for effective capture in existing particle control devices.     

Effect of solids concentration distribution on the flue gas desulfurization process

A dry flue gas desulfurization (FGD) process at 600-800 degrees C was studied in a pilot-scale circulating fluidized bed (CFB) experimental facility. Various fresh sorbent distribution types and internal structures were modeled numerically to investigate their effect on the gas-solid flow and sulfate reaction characteristics. Experimental results show that, after the fresh sorbent supply was stopped, the desulfurization efficiency declined rapidly even though the sorbent recirculation was maintained. Therefore, the fresh sorbent is the main contributor to the desulfurization process and the primary effect of the recirculated sorbent was to evenly distribute the fresh sorbent and to prolong the sorbent particle residence time. The numerical results demonstrate thatthe desulfurization efficiency varied greatly for the various fresh sorbent bottom injection methods. The desulfurization efficiency of the bottom-even injection method was 1.5 times that of the bottom two-sided injection method. Internal structures effectively improved the fresh sorbent solids concentration distribution and the desulfurization efficiency. Optimized internal structures increased the desulfurization efficiency of the bottom two-sided injection method by 46%, so that it was very close to that of the bottom-even injection method with only a 4.6% difference.     

Observations of mercury-containing aerosols

In situ analyses with a laser ionization mass spectrometer have shown that a large fraction of aerosols in the bottom few kilometers of the stratosphere contain small amounts of mercury (1). Electron microscopy of particles collected near the tropopause has also detected mercury. The distribution of mercury onto many particles, including those less than 20 nm in diameter, indicates that the mercury is from local condensation of mercury compounds onto particles rather than transport of mercury-rich aerosols from surface sources. Although the results are only semiquantitative, they suggest that most of the mercury in the lower stratosphere is converted into the particulate phase. Mercury-containing particles were present at both middle latitudes and the tropics in two seasons. There is therefore good reason to believe that particulate mercury above the tropopause is global and could affect the atmospheric lifetime of mercury. There are indications that bromine and/ or iodine may be involved in the conversion of mercury from the gas to particle phase. Measurements at altitudes below 5 km did not find mercury in any particles despite sampling some particles that clearly originated in the stratosphere. This indicates that the particulate mercury from the lower stratosphere may be volatile enough to evaporate or decompose once particles reach warmer temperatures.     

Effect of operating parameters and reactor structure on moderate temperature dry desulfurization

A moderate temperature dry desulfurization process at 600-800 degrees C was studied in a pilot-scale circulating fluidized bed flue gas desulfurization (CFB-FGD) experimental facility. The desulfurization efficiency was investigated for various operating parameters, such as bed temperature, CO2 concentration, and solids concentration. In addition, structural improvements in key parts of the CFB-FGD system, i.e., the cyclone separator and the distributor, were made to improve the desulfurization efficiency and flow resistance. The experimental results show that the desulfurization efficiency increased rapidly with increasing temperature above 600 degrees C due to enhanced gas diffusion and the shift of the equilibrium for the carbonate reaction. The sorbent sulfated gradually after quick carbonation of the sorbent with a long particle residence time necessary to realize a high desulfurization ratio. A reduced solids concentration in the bed reduced the particle residence time and the desulfurization efficiency. A single-stage cyclone separator produced no improvement in the desulfurization efficiency compared with a two-stage cyclone separator. Compared with a wind cap distributor, a large hole distributor reduced the flow resistance which reduced the desulfurization efficiency due to the reduced bed pressure drop and worsened bed fluidization. The desulfurization efficiency can be improved by increasing the collection efficiency of fine particles to prolong their residence time and by improving the solids concentration distribution to increase the gas-solid contact surface area.     

Alpha-pinene oxidation in the presence of seed aerosol: estimates of nucleation rates, growth rates, and yield

A recently developed inverse-modeling procedure has been applied to a case study of particle nucleation and growth following alpha-pinene and SO2 oxidation in a smog chamber. With the use of only the measured aerosol size distributions as input, the condensational growth rate is obtained by regression analysis of the general dynamic equation, taking into account coagulation and wall losses. The growth rate provides an indirect measure of the concentration of the condensing species, offset by their vapor pressures. Assuming a particle density of 1.0 g cm(-3), an aerosol yield of 7 +/- 1% is obtained for an initial alpha-pinene concentration of 14 ppbv and a final organic aerosol mass of 4 microg m3. Using the estimated vapor concentration, we show that the time-dependence of the yield is at least partly due to the time needed for condensation. Such a kinetic limitation to secondary organic aerosol formation may have implications for our understanding of gas-particle partitioning. The measured size distributions are also used to determine the empirical nucleation rate; it appears to be enhanced by the presence of organics.     

7种烟用添加剂对烟气气溶胶粒径分布的影响

为研究典型烟用添加剂（包括丙二醇、丙三醇、呋喃酮、香兰素、乙酰丙酸、亚麻酸和棕榈酸）对不同粒径烟气气溶胶粒相物质量分布的影响以及在气溶胶中的粒径分布,采用单通道吸烟机-电子低压撞击器（ELPI）,分12级捕集烟气气溶胶粒相物,进行重量分析研究粒相物的质量分布,并采用GC-MS和LC-MS/MS测定了7种添加剂在不同粒径气溶胶中的分布。实验结果表明,添加7种添加剂的卷烟样品,其气溶胶粒相物的质量均主要分布在中间粒径上（0.14~1.17 μm）,但添加不同添加剂对气溶胶质量粒径分布的影响不同,总体趋势如下:香兰素、乙酰丙酸、亚麻酸和呋喃酮能增加大于0.431 μm处粒相物质量,使小于0.261 μm处粒相物质量减小;丙二醇和丙三醇使0.261 μm处粒相物的质量减少;棕榈酸无明显影响。7种添加剂在不同粒径气溶胶粒相物中的释放量均随粒径增加先增加后减小,与粒相物质量分布一致,并主要分布在中等粒径0.261~0.722 μm的颗粒中,但不同添加剂在不同粒径粒相物中的浓度（释放量与粒相物质量之比）呈现不同的分布趋势:随着粒径的增加,丙二醇、乙酰丙酸、亚麻酸和棕榈酸的浓度先增加后减小,丙三醇的浓度先减小后略微增加,香兰素和呋喃酮的浓度无明显差异。添加合适的烟草添加剂可改变烟气气溶胶粒相物的分布,并在不同粒径粒相物中呈现不同的分布特征,研究结果可为卷烟配方设计及卷烟安全性研究提供理论基础和数据支持。      

Iron blast furnace slag/hydrated lime sorbents for flue gas desulfurization

Sorbents prepared from iron blast furnace slag (BFS) and hydrated lime (HL) through the hydration process have been studied with the aim to evaluate their reactivities toward SO2 under the conditions prevailing in dry or semidry flue gas desulfurization processes. The BFS/HL sorbents, having large surface areas and pore volumes due to the formation of products of hydration, were highly reactive toward SO2, as compared with hydrated lime alone (0.24 in Ca utilization). The sorbent reactivity increased as the slurrying temperature and time increased and as the particle size of BFS decreased; the effects of the liquid/solid ratio and the sorbent drying conditions were negligible. The structural properties and the reactivity of sorbent were markedly affected by the BFS/HL ratio; the sorbent with 30/70 ratio had the highest 1 h utilization of Ca, 0.70, and SO2 capture, 0.45 g SO2/g sorbent. The reactivity of a sorbent was related to its initial specific surface area (Sg0) and molar content of Ca (M(-1)); the 1 h utilization of Ca increased almost linearly with increasing Sg0/M. The results of this study are useful to the preparation of BFS/HL sorbents with high reactivity for use in the dry and semidry processes to remove SO2 from the flue gas.     

Hydrocarbon condensation in heavy-duty diesel exhaust

The semivolatile mass fraction of diesel exhaust particles was studied using size-resolved on-line techniques (DMA-ELPI; TDMA-ELPI). The average density of the semivolatile liquid on the particles was measured to be approximately 0.8 g/cm3. The measured size resolved values of mass transfer imply that condensation, or diffusion-limited mass transfer, plays a major role in driving the volatile matter to the diesel exhaust particles. The measured mass change values correspond to highly size dependent mass fractions for the semivolatile component, ranging from approximately 20-80%. Integrated over particle size distribution, the volatile mass fractions were 25 and 45% for the two load points studied. Calculation, based on the measured particle properties, indicates that only 10% volatile mass fraction could be explained by monolayer adsorption. The size resolved changes in particle effective density, fractal dimension, volatile mass fractions and mass are all in agreement with theoretical considerations of condensation.     

不同烟丝含水率卷烟主流烟气气溶胶的粒径分布特征

  目的  烟丝含水率对烟气颗粒的影响。  方法  采用DMS500快速粒径谱仪和电子低压撞击器(ELPI), 在ISO抽吸模式下, 考察不同烟丝含水率卷烟烟气气溶胶的粒数粒径分布和质量粒径分布特征。  结果  ① 不同含水率(8.1%、12.6%和17.6%)卷烟烟气气溶胶的粒数粒径均在40~400 nm呈近似对数正态分布。随着含水率增加, 全部抽吸口数的烟气粒子平均数浓度无显著变化、体积浓度明显降低、粒数中值直径(CMD)和粒子体积中值直径(VMD)呈降低趋势。②3种含水率卷烟的烟气气溶胶质量主要集中在100~1000 nm, 随着含水率增加, 质量粒径分布向小粒径位移, 抽吸口数相同条件下捕集的气溶胶颗粒总质量降低。  结论  上述规律可为卷烟加工工艺参数的优化和卷烟产品开发提供参考。