COMPARISON AND VALIDATION OF OHM AND SCEM MEASUREMENTS FOR A FULL-SCALE COAL-FIRED POWER PLANT

Mercury emission measurements were performed at a 250 MW coal-fired power plant using the Ontario Hydro method (OHM) and semi-continuous emission monitors (SCEM). Flue gas sampling was performed at the inlet of the air preheater and at the outlet of the electrostatic precipitator. The results indicated that there is some agreement between the OHM and SCEM measurements on the total mercury species. However, the SCEM results were not always in good agreement with the OHM measurements on the elemental mercury species. These discrepancies in elemental mercury concentrations are probably the result of the differences in the location of the SCEM and OHM probes, the temperature difference between the SCEM sampling probe and the flue gas, and the nonuniformities in mercury concentration over the flue gas duct cross section. The other factor that contributed to the deviation between the SCEM and OHM measurement results is the sampling method: the SCEM measurements were performed at a single point while the OHM probe was traversed over multiple points over the duct cross section and the results were averaged. The effect of the SCEM sampling probe temperature was investigated by designing a sampling probe that could be heated to the sampled flue gas temperatures. This resulted in improvements in the accuracy of the elemental mercury measurements by the SCEM system.     

Multi-method mercury specification from lignite-fired power plants

Mercury concentration and speciation partitioning, including total mercury, elemental mercury and oxidized mercury from a lignite-fired power plant under different operating conditions, was studied by Ontario hydro method (OHM), two kinds of continuous mercury monitors (semi-continuous emission monitor (SCEM) and continuous mercury monitor (CMM)), and the sorbent trap method. The effects of boiler load, fuel blending ratio, electrostatic precipitator, flue gas desulphurization, flue gas bypassing the FGD ratio, and mercury measuring methods on mercury emission were analyzed. The results indicated that mercury data from OHM, SCEM and CMM presented a good consistency throughout the entire testing period within ±20% acceptable range; however, the results from Appendix K provided bigger discrepancies than the results of OHM and SCEM due to the interferences of higher selenium content in the flue gas. The particulate-bound mercury removal efficiencies of ESP were determined to be 16–35%. The percentages of elemental mercury emitted from two lignite-fired power plants were in the higher ranges of 43.9–74.2%. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Kinetic mechanism studies on reactions of mercury and oxidizing species in coal combustion

The emission of mercury by coal-fired power plants has become a recent concern on the part of the electric utility industry. Knowledge of mercury kinetic mechanisms is imperative for the research of predicting mercury transformation and finding its effective control methods in coal combustion flue gas. Near the end of the flue gas path, mercury exists as a combination of elemental vapor and HgCl₂ vapor. HgCl₂ is more likely to be removed from the flue gas. Thus, the degree of oxidation is considered to be a critical factor that tends to reduce emission. In the present work, the microcosmic kinetic mechanisms of reactions between mercury and oxidizing species were investigated by ab initio calculations of quantum chemistry. The geometry optimizations of reactants, transition states, intermediates and products were made by the quantum chemistry MP2 method at SDD basis function level. All molecule energies were calculated at QCISD(T)/SDD level and corrected with zero point energy. The activation energies and heat of reactions were calculated. The reaction rate constants were calculated from transition state theory (TST). The performance of the ab initio calculations of quantum chemistry was assessed through comparisons with the literature data. The comparisons showed that the ab initio calculations of quantum chemistry were in agreement with the literature data. The results showed that quantum chemistry was an effective means for investigating kinetic mechanism of mercury interaction with combustion-generated flue gas.     

An investigation of mercury distribution and speciation during coal combustion

A multi-field electrostatic precipitator (ESP) and a two-stage condensing heat exchanger (CHX^®) have been added to the pilot scale Vertical Combustion Research Facility (VCRF) in CETC-O to further research into integrated emissions control for coal fired power plants. A series of combustion trials were conducted on the VCRF with three different coals (bituminous, sub-bituminous and lignite) to study mercury distribution and speciation at various VCRF locations. Results showed that, with the bituminous coal, as the flue gas cools down from 700 to 200 °C, 80% of total mercury in the gas phase existed in oxidized form and 20% in elemental form. For sub-bituminous and lignite coals, elemental mercury was the dominant form throughout the system. Analysis of deposited ash samples showed that oxidized mercury can be absorbed on carbon-rich ash deposits, although overall only a very small percentage of total mercury was absorbed on the ash. The potential of the CHX^® at removing mercury from the flue gas was also explored. Results indicated that, using wet scrubbing, the CHX^® was able to remove 98% of oxidized mercury. Though elemental mercury went through the system unabated, it is suggested that, with appropriate agent to oxidize elemental mercury in the CHX^®, it is conceivable to use CHX^® to remove both oxidized and elemental mercury. Finally, mercury balance was performed and good mercury balance was obtained across the VCRF, validating our sampling procedures and analysis methods.     

New developments in the theory and modeling of mercury oxidation and binding on activated carbons in flue gas

Recent advances in the mechanistic understanding of mercury oxidation on a carbon surface in flue gas are reviewed in this paper. Theoretical calculations were performed to determine whether the energetics are feasible for a proposed detailed model for oxidative addition of elemental mercury on a carbon edge structure. The results of the calculation show that mercury complexation with a carbenium ion formed at a zigzag edge carbon has a small positive ΔG, but attack of chloride on the complex will proceed with negative ΔG. The energetics rule out a direct covalent bond formation between mercury and the carbenium ion. Alternative concerted reaction models and double-charged models for the mechanism are also feasible but have not yet been computed.     

Effect of selective catalytic reactor on oxidation and enhanced removal of mercury in coal-fired power plants

The present study investigated the variation of mercury (Hg) speciation within the air pollution control devices (APCDs) in bituminous coal-fired power plants. The effect of selective catalytic reduction (SCR) system, which is mainly installed for NOx removal, on elemental Hg (Hg⁰) oxidation and enhancement of Hg removal within APCDs, was studied. Hg speciations in flue gas at the inlet and outlet of each APCDs, such as SCR, cold-side electrostatic precipitator (CS-ESP) and flue gas desulphurization (FGD), were analyzed. Sampling and analysis were carried out according to Ontario Hydro Method (OHM). Overall Hg removal efficiency of APCDs, on average, was about 61% and 47% with and without SCR system, respectively. In the flue gas, Hg was mainly distributed in gaseous (elemental and oxidized) form. The oxidized to elemental Hg partitioning coefficient increased due to oxidation of Hg⁰ across the SCR system and decreased due to the removal of oxidized Hg (Hg²⁺) across a wet FGD system. Hg⁰ oxidation across the SCR system varied from 74% to 7% in tested coal-fired power plants. The comparative study shows that the installation of an SCR system increased Hg removal efficiency and suppressed the reemission of captured Hg⁰ within a wet FGD system.     

Simulation of mercury emission control by activated carbon under confined-bed operations

Mercury emissions from coal-fired power plants have been a great environmental and regulatory concern due to the toxic nature of mercury and the significant amount of emissions from these plants. An effective method for controlling mercury emission is to employ activated carbon to adsorb mercury from the combustion flue gas. In this study, an activated carbon mercury sorption model was applied to simulate a confined-bed mercury emission control process. Model simulations were performed to generate dynamic mercury concentration profiles and the corresponding profiles of mercury uptake by activated carbon at various bed locations under various process conditions. The simulation parameters included flue gas flow rate, inlet mercury concentration, and adsorption bed temperature. The study has demonstrated the applicability of the model for simulating the process and provided insights into the mercury control process especially the effects of flue gas flow rate, inlet mercury concentration, and activated carbon bed temperature on the process. Such information is critically needed in the design and operation of a mercury emission control process involving activated carbon adsorption.     

Mercury species, mass flows and processes in a cement plant

The aim of the study was to evaluate the behaviour of mercury in the cement clinker production process. Simultaneous measurements of mercury in all important materials and gas streams were performed in three sampling periods on about 300 solid samples and about 80 samples taken from gas streams. Mercury species in flue gases at characteristic parts of the process were measured as total Hg(t), particulate Hg(p), elemental Hg⁰(g) and reactive Hg²⁺(g) mercury. Based on the results of measurements, mercury mass flows and mass balances of the whole and in certain parts of the process were evaluated. It was shown that the process comprises many mercury cycles which are strongly dependent on the operating conditions and technological specifics. Cycling of mercury causes a significant enrichment of mercury inside the process. In the annual mercury input of about 27 kg, raw materials accounted near by 60% and fuels about 40% (i.e. petrol coke 31%, waste tyres 10% and waste oil 0.4%). The annual emission of mercury represented 40-70% of the inputs, while cement clinker only contained about 10%. The difference between inputs and outputs (11-45%) obtained in the annual mass balance could be assigned to mercury recycling and significant enrichment inside the process, as well as variability between spot measurements. The parts of the process with the highest mercury mass flows and the lowest material/gas flows were identified. Such points represent an opportunity to remove a significant amount of mercury from the process at low material flows and to improve mercury control. Mercury was mainly emitted in gaseous form with 92% (direct mode) or 89% (combined mode) as Hg(g) on average, of which about 2/3 was as Hg²⁺(g), and about 1/3 as Hg⁰(g). Only a small part (the rest) was emitted as particulate Hg(p). Shares of individual mercury species in the last sampling period were 65.7% Hg²⁺(g), 34.0% Hg⁰(g) and 0.3% Hg(p) on average. Ratios between individual mercury forms were found to be related to operating modes. The quantities of Hg(t), Hg(g) and Hg²⁺(g) emitted were higher when operating with the raw mills off (direct mode). It was seen that the efficiency of Hg removal was strongly related to the dust removal efficiency. Bag filters very efficiently removed all mercury species.     

Experimental study on mercury transformation and removal in coal-fired boiler flue gases

This paper reported mercury speciation and emissions from five coal-fired power stations in China. The standard Ontario Hydro Method (OHM) was used into the flue gas mercury sampling before and after fabric filter (FF)/electrostatic precipitator (ESP) locations in these coal-fired power stations, and then various mercury speciation such as Hg⁰, Hg²⁺ and Hg^P in flue gas, was analyzed by using EPA method. The solid samples such as coal, bottom ash and ESP ash, were analyzed by DMA 80 based on EPA Method 7473. Through analysis the mercury speciation varied greatly when flue gas went through FF/ESP. Of the total mercury in flue gas, the concentration of Hg²⁺ is in the range of 0.11–14.76 μg/N m³ before FF/ESP and 0.02–21.20 μg/N m³ after FF/ESP; the concentration of Hg⁰ ranges in 1.18–33.63 μg/N m³ before FF/ESP and 0.77–13.57 μg/N m³ after FF/ESP, and that of Hg^P is in the scope of 0–12.11 μg/N m³ before FF/ESP and 0–0.54 μg/N m³ after FF/ESP. The proportion of Hg²⁺ ranges from 4.87%–50.93% before FF/ESP and 2.02%–75.55% after FF/ESP, while that of Hg⁰ is between 13.81% – 94.79% before FF/ESP and 15.69%–98% after FF/ESP, with that of Hg^P is in the range of 0%–45.13% before FF/ESP and 0%–11.03% after FF/ESP. The mercury in flue gas mainly existed in the forms of Hg⁰ and Hg²⁺. The concentrations of chlorine and sulfur in coal and flue gas influence the species of Hg that are formed in the flue gas entering air pollution control devices. The concentrations of chlorine, sulfur and mercury in coal and the compositions of fly ash had significant effects on mercury emissions.     

Evaluation of mercury sorbents in a lab-scale multiphase flow reactor, a pilot-scale slipstream reactor and full-scale power plant

Due to its adverse effects on human health and ecosystem, mercury emission from the coal-fired utility boiler has been generating more and more concern. Sorbent injection upstream of the electrostatic precipitator (ESP) or bag-house has been deemed one of the recommended mature technologies to reduce mercury emission. Before a sorbent is used in practice, its mercury capture ability needs to be evaluated, but has until recently only been demonstrated in bench-, pilot- or full-scale experiments separately. In this paper, a lab-scale multiphase flow reactor and a pilot-scale slipstream reactor were set up and conducted such evaluation on the two scales. After that, some kinds of sorbents were injected at a full-scale power station. The experimental results show that the lab- and pilot-scale reactor systems in this paper can provide accurate information of sorbent evaluation under flue gas atmosphere. There was significant difference between the mercury removal efficiency of tested sorbents, varying from 98.3% down to 23%. SO₂ in the flue gas was shown to inhibit mercury oxidization and capture. The sorbents have higher mercury capturing efficiency with higher injection rate and longer residence time when other conditions were held constant. In the pilot-scale, four injection ports vertical to the flue gas flow direction could help improve mixture of sorbent and flue gas so that the mercury removal efficiency became higher. The pilot-scale data can be used to predict the full-scale results. Some of the chemical and physical mechanisms responsible for the mercury removal of the sorbents were identified.     

Mercury speciation and its emissions from a 220 MW pulverized coal-fired boiler power plant in flue gas

Distributions of mercury speciation of Hg⁰, Hg²⁺ and Hg ^P in flue gas and fly ash were sampled by using the Ontario Hydro Method in a 220 MW pulverized coal-fired boiler power plant in China. The mercury speciation was varied greatly when flue gas going through the electrostatic precipitator (ESP). The mercury adsorbed on fly ashes was found strongly dependent on unburnt carbon content in fly ash and slightly on the particle sizes, which implies that the physical and chemical features of some elemental substances enriched to fly ash surface also have a non-ignored effect on the mercury adsorption. The concentration of chlorine in coal, oxyge nand NO _x in flue gas has a positive correlation with the formation of the oxidized mercury, but the sulfur in coal has a positive influence on the formation of elemental mercury. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Impact of calcium chloride addition on mercury transformations and control in coal flue gas

Pilot-scale experiments were conducted to investigate mercury transformations in coal flue gas when firing subbituminous coal with a CaCl₂ additive. Cofiring the CaCl₂ additive with the subbituminous coal resulted in approximately 50% oxidized mercury, as a result of reactive chlorine species formed in coal flue gas, compared to the dominance of elemental mercury in the baseline flue gas. The mercury data indicate that mercury-flue gas chemistry reactions may occur at fairly high temperatures (>400 °C) in chlorine-enriched flue gas. Field tests were conducted to further demonstrate the impact of cofiring CaCl₂ on the eventual fate of mercury. These tests were completed on a 650-MW subbituminous coal-fired power plant equipped with selective catalytic reduction (SCR), a fabric filter (FF), and a wet scrubber. Overall mercury removals across the SCR-FF-wet scrubber system ranged from 75% to 96% with 200-800 ppm (coal basis) chlorine addition compared to 18-32% during baseline operations. Field data indicate that the SCR enhanced mercury oxidation, possibly as a result of the supplemental formation of reactive chlorine species and the aid of the SCR catalyst. As a result, most of the mercury in the flue gas was in an oxidized state and was removed in the downstream wet scrubber, indicating that cofiring CaCl₂ is an effective mercury control approach for a subbituminous coal-fired plant equipped with an SCR and wet scrubber.     

循环流化床中烟气飞灰汞迁移规律

在小型热态循环流化床试验台上进行褐煤、烟煤、无烟煤燃烧试验,研究3种典型煤的烟气气态汞和飞灰颗粒汞迁移规律。试验结果表明：褐煤、烟煤、无烟煤在燃烧过程中,炉膛温度、空截面风速、给煤量以及煤颗粒大小变化时,汞元素在烟气和飞灰之间的迁移规律相似;降低炉膛密相区温度和增大炉膛空截面风速可促进烟气气态总汞Hg^T（g）迁移到飞灰颗粒汞Hg（p）中,同时也促进烟气气态零价汞Hg⁰（g）向烟气气态二价汞Hg²⁺（g）和Hg（p）转化;增加给煤量,烟气气态总汞Hg^T（g）和烟气气态零价汞Hg⁰（g）减少,飞灰颗粒汞Hg（p）含量增加,并且影响Hg⁰（g）的转化;选择合适的煤颗粒粒度可以促进Hg⁰（g）的转化以及Hg^T（g）向Hg（p）迁移。随燃烧工况的变化,3种煤Hg^T（g）、Hg（p）和Hg⁰（g）含量变化趋势相似,但含量相差较大,Hg⁰（g）占Hg^T（g）的比例y值也不同,其中无烟煤的y值高于烟煤和褐煤的y值。     

Investigation on elemental mercury oxidation mechanism by non-thermal plasma treatment

Converting elemental mercury into divalent compound is one of the most important steps for mercury abatement from coal fired flue gas. The oxidation of elemental mercury was investigated in this paper using dielectric barrier discharge (DBD) non-thermal plasma (NTP) technology at room temperature. Effects of different flue gas components like oxygen, moisture, HCl, NO and SO₂ were investigated. Results indicate that active radicals including O, O₃ and OH all contribute to the oxidation of elemental mercury. Under the conditions of 5% O₂ in the simulated flue gas, about 90.2% of Hg⁰ was observed to be oxidized at 3.68 kV discharge voltage. The increase of discharge voltage, O₂ level and H₂O content can all improve the oxidation rate, individually. With O₂ and H₂O both existed, there is an optimal moisture level for the mercury oxidation during the NTP treatment. In this test, the observed optimal moisture level was around 0.74% by volume. Hydrogen chloride can promote the oxidation of mercury due to chlorine atoms produced in the plasma process. Both NO and SO₂ have inhibitory effects on mercury oxidation, which can be attributed to their competitive consumption of O₃ and O.     

Mercury emissions from six coal-fired power plants in China

Mercury emission field measurements based on the Ontario Hydro Method (OHM) were conducted for six coal-fired power plants in China. The mercury mass balances for the six power plants varied from 100.3% to 139.5% of the input coal mercury for the whole system. About 0.02%–1.2% of the mercury remained in the bottom ash. In the first five power plants equipped with pulverized coal boiler, most of the mercury was emitted from the stack to the atmosphere. The plants with Electrostatic Precipitator (ESP) system emitted more Hg⁰ than Hg²⁺, while the plants with the Fabric Filter (FF) emitted less Hg⁰ than Hg²⁺. Virtually all of the Hg^P enter the ESP or the FF was removed. The FF systems had better Hg⁰ and Hg²⁺ removal efficiencies than the ESP systems. The flue gas desulfurization (FGD) system removed up to 78.0% of Hg²⁺ and only 3.14% of Hg⁰ in the flue gas, while 8.94% of the original mercury in the coal was removed by the FGD system. The average mercury removal efficiencies of the ESP systems was 11.5%, that of the FF systems was 52.3% and that of the combined ESP + FGD system was 13.7%, much lower than the average removal efficiencies of pollution control device systems in US plants which have been used in previous studies of Chinese mercury emission inventory. Hg⁰, rather than Hg²⁺ as assumed in previous estimates, has been found to be the dominant species emitted in the atmosphere. The average emission factor was found to be 4.70 g/TJ (10.92 bl/Tbtu), which is much higher than for US plants burning bituminous coals due to the high mercury content in the Chinese coal and the low mercury removal efficiency of air pollution control devices of power plants.     

Mercury removal from coal combustion by Fenton reactions. Paper B: Pilot-scale tests

This second paper in a series describes results of pilot-scale testing for mercury (Hg) removal from coal combustion flue gas using a scrubbing solution based on the Fenton reactions. The selected reagents contain hydrogen peroxide and iron salts. The mercury scrubbing was performed in a condensing heat exchanger (CHX) with flue gas generated by coal combustion in CANMET’s vertical combustor research facility (VCRF). Both the Ontario Hydro method and a Hg CEM were used for Hg sampling and speciation. The results, obtained with the combustion of three different pulverized coals – bituminous, sub-bituminous and lignite – showed that the CHX was very effective in removing oxidized mercury (Hg(II)). Concerning the performance of the scrubbing solutions, 30–40% of elemental mercury (Hg(0)) oxidation was achieved for the lignite coal, with the solution being preferably composed of FeCl₃ and H₂O₂ and with pH value between 1 and 3. Results also showed that better Hg removal results were achieved by combining sulphur removal and Hg removal in the same stage of the CHX. An additional test done on the pilot-scale research boiler with a conventional wet scrubber showed that the Hg removal capability using the Fenton reactions was not dependent on the configuration of the wet scrubber. Although the Hg(0) oxidation ratio was not particularly high compared to the achievements from bench-scale tests, considering the economic and non-toxic nature of the scrubbing solution and the readily available equipment, the current results are encouraging and deserve further work to develop a better understanding of the chemistry in order to determine if the method can be further optimized.     

Analysis of mercury species present during coal combustion by thermal desorption

Mercury in coal and its emissions from coal-fired boilers is a topic of primary environmental concern in the United States and Europe. The predominant forms of mercury in coal-fired flue gas are elemental (Hg⁰) and oxidized (Hg²⁺, primarily as HgCl₂). Because Hg²⁺ is more condensable and far more water soluble than Hg⁰, the wide variability in mercury speciation in coal-fired flue gases undermines the total mercury removal efficiency of most mercury emission control technologies. It is important therefore to have an understanding of the behaviour of mercury during coal combustion and the mechanisms of mercury oxidation along the flue gas path. In this study, a temperature programmed decomposition technique was applied in order to acquire an understanding of the mode of decomposition of mercury species during coal combustion. A series of mercury model compounds were used for qualitative calibration. The temperature appearance range of the main mercury species can be arranged in increasing order as HgCl₂ < HgS < HgO < HgSO₄. Different fly ashes with certified and reference values for mercury concentration were used to evaluate the method. This study has shown that the thermal decomposition test is a newly developed efficient method for identifying and quantifying mercury species from coal combustion products.     

HgCl2 sorption on lignite activated carbon: Analysis of fixed-bed results

Factors that influence kinetic reactivity and equilibrium between elemental mercury, carbon, and flue gas components have been the focus of numerous studies. This study pertains to recent bench-scale fixed-bed tests in which activated carbon was exposed to HgCl₂ in a flue gas composition typical of an unscrubbed eastern bituminous coal. Results are discussed in light of a refined binding site model based on the zigzag carbene structures recently proposed for electronic states at the edges of the carbon graphene layers.     

改性活性炭吸附单质汞的研究现状

汞污染主要来自于人为的燃煤烟气排放,而烟气汞污染控制的难点在于气态单质汞的脱除。活性炭吸附法是较为成熟且效果较好的一种方法,本文对近10年来改性活性炭吸附单质汞的研究状况进行综述。     

Mercury Speciation in Flue Gases after an Oxidative Acid Wet Scrubber

Flue gases from a hazardous waste incinerator have been sampled in three campaigns, before and after, an oxidative acid wet scrubber working with the MercOx‐process. A continuous emission monitor for mercury speciation was used before the scrubber in the first campaign. In all campaigns, impingers with KCl and KMnO₄ were used. A solid adsorption method was used in the last campaign. The mercury leaving the scrubber is oxidized at > 90 % efficiency (independent of the inlet speciation). A substantial decrease in the redox potential of the scrubber liquid caused an increased fraction of elemental gaseous mercury to be present in the clean gas. The measurements also show that the scrubber has the ability to readily absorb mercury peaks. During one extreme peak of 3,600 μg/m³ (dry gas) in the raw gas, the removal efficiency was above 99.9 %.