氯添加对燃煤过程中汞析出规律的影响

首先利用管式炉对燃煤及燃煤加氯后煤中汞排放进行研究,结果表明,对于神混煤而言,原煤燃烧后烟气中单质Hg⁰和氧化态汞Hg²⁺的比例分别为74.3%、25.7%。添加Cl后,烟气中Hg²⁺的比例有所上升,当加氯量为0.015%、0.030%和0.045%时,烟气中Hg²⁺的比例分别上升为32.7%、36.1%和40%,随加氯量的增加,其对汞的氧化作用也随之增强。在现场工程示范试验中,利用脱硫废水中的氯氧化烟气中的汞,以达到脱硫废水与烟气中的汞协同脱除的目的。结果表明,随着脱硫废水喷洒煤的量越大,进入SCR烟气中Hg²⁺比例增大,经过SCR后Hg²⁺的比例随之增大。由于飞灰对Hg²⁺的吸附能力较Hg⁰强,电除尘系统的脱汞效率提高,但脱硫废水喷洒煤对湿电除尘系统的脱汞效率影响不大。总之,脱硫废水喷洒量越大,燃煤机组烟气净化设备对汞协同去除效率也随之提高。     

Impacts of acid gases on mercury oxidation across SCR catalyst

A series of bench-scale experiments were completed to evaluate acid gases of HCl, SO₂, and SO₃ on mercury oxidation across a commercial selective catalytic reduction (SCR) catalyst. The SCR catalyst was placed in a simulated flue gas stream containing O₂, CO₂, H₂O, NO, NO₂, and NH₃, and N₂. HCl, SO₂, and SO₃ were added to the gas stream either separately or in combination to investigate their interactions with mercury over the SCR catalyst. The compositions of the simulated flue gas represent a medium-sulfur and low- to medium-chlorine coal that could represent either bituminous or subbituminous. The experimental data indicated that 5–50 ppm HCl in flue gas enhanced mercury oxidation within the SCR catalyst, possibly because of the reactive chlorine species formed through catalytic reactions. An addition of 5 ppm HCl in the simulated flue gas resulted in mercury oxidation of 45% across the SCR compared to only 4% mercury oxidation when 1 ppm HCl is in the flue gas. As HCl concentration increased to 50 ppm, 63% of Hg oxidation was reached. SO₂ and SO₃ showed a mitigating effect on mercury chlorination to some degree, depending on the concentrations of SO₂ and SO₃, by competing against HCl for SCR adsorption sites. High levels of acid gases of HCl (50 ppm), SO₂ (2000 ppm), and SO₃ (50 ppm) in the flue gas deteriorate mercury adsorption on the SCR catalyst.     

The PCO process for photochemical removal of mercury from flue gas

A promising technology has been developed to capture and remove elemental mercury species from coal-fired power plants. Powerspan Corp. has licensed the technology and initiated a bench and pilot test program to develop the Photochemical Oxidation, or PCO™, process for commercial application with subbituminous and lignite fuels.The process has the potential to serve as a low cost mercury oxidation technology that will facilitate elemental mercury removal in a downstream SO₂ scrubber, wet electrostatic precipitator (WESP), or baghouse. It uses 254-nm (nanometer) ultraviolet light from a mercury lamp to produce an excited state mercury species in the flue gas, leading to oxidation of elemental mercury. This paper presents results of Powerspan's initial bench-scale testing on a simulated flue gas stream. Preliminary testing conducted in Powerspan's bench-scale facility showed greater than 90% oxidation and removal of elemental mercury. The process also has potential to serve as a low cost method for the removal of mercury from waste incinerator flue gases.     

The PCO process for photochemical removal of mercury from flue gas

A promising technology has been developed to capture and remove elemental mercury species from coal-fired power plants. Powerspan Corp. has licensed the technology and initiated a bench and pilot test program to develop the Photochemical Oxidation, or PCO™, process for commercial application with subbituminous and lignite fuels.The process has the potential to serve as a low cost mercury oxidation technology that will facilitate elemental mercury removal in a downstream SO₂ scrubber, wet electrostatic precipitator (WESP), or baghouse. It uses 254-nm (nanometer) ultraviolet light from a mercury lamp to produce an excited state mercury species in the flue gas, leading to oxidation of elemental mercury. This paper presents results of Powerspan's initial bench-scale testing on a simulated flue gas stream. Preliminary testing conducted in Powerspan's bench-scale facility showed greater than 90% oxidation and removal of elemental mercury. The process also has potential to serve as a low cost method for the removal of mercury from waste incinerator flue gases.     

Novel sorbents for mercury emissions control from coal-fired power plants

The authors have successfully developed novel efficient and cost-effective sorbents for mercury removal from coal combustion flue gases. These sorbents were evaluated in a fixed-bed system with a typical PRB subbituminous/lignite simulated flue gas, and in an entrained-flow system with air simulating in-flight mercury capture by sorbent injection in the ductwork of coal-fired utility plants. In both systems, one of the novel sorbents showed promising results for Hg⁰ removal. In particular, this sorbent demonstrated slightly higher efficiencies in Hg⁰ removal than Darco Hg-LH (commercially available brominated activated carbon) at the similar injection rates in the entrained-flow system. The other novel sorbent showed excellent Hg⁰ oxidation capability, and may enable coal-fired power plants equipped with wet scrubbers to simultaneously control their mercury and sulfur oxides emissions. In addition, fixed-bed results for this sorbent showed that co-injection of a very small amount (∼10%) of raw activated carbon could eliminate almost all of the mercury generated by reactions of Hg⁰ with the sorbent.     

Study of elemental mercury re-emission in a simulated wet scrubber

Mercury is a toxic pollutant that has motivated environmental regulations for emissions reduction from coal-fired power plants. Acid gas wet scrubbers are known to provide the co-benefit of SO₂ control and mercury removal, when mercury is found in the flue gas in the oxidized form. The aqueous ionic chemistry in the scrubbing solution can lead to transformation of the absorbed ionic mercury to the insoluble elemental mercury form, resulting in mercury re-emission and a reduction of the scrubber mercury capture efficiency. Laboratory-scale experiments were performed in a simulated batch scrubber. The experiments were carried out to simulate a forced oxidation limestone reactor. The effect of scrubber temperature and pH, ionic mercury concentration in the liquor, total sulfite, and chloride and bromide ion concentration in solution, and O₂ and CO₂ concentration in the gas on mercury re-emission was investigated. Of particular interest was the investigation of the impact of slurry temperature and CO₂ concentration in the gas, under conditions typical of oxy-fuel combustion condition, on mercury re-emission. The results confirm that oxidized mercury is reduced by aqueous S(IV). Higher concentrations of sulfites, chloride and bromide ions inhibit oxidized mercury transformation to elemental mercury. Higher concentrations of ionic mercury in the liquor and increased scrubber temperature and pH value results in higher re-emission levels of elemental mercury. Additionally, on the impact of oxy-fuel conditions on mercury, it was found that high availability of excess oxygen in the flue gas in contact with the scrubbing solution was found to result in lower conversion of oxidized to elemental mercury. No impact from CO₂ in the flue gas was found on elemental mercury re-emission. However, higher slurry temperatures under oxy-fuel combustion conditions would lead to increased elemental mercury re-emission. For completeness, the effectiveness of sulfide-based additives for abatement of elemental mercury re-emission was also demonstrated in this study. The suppression effectiveness of sodium hydrogen sulfide, sodium sulfide, TMT15® and the Nalco-8034 reagent was found at 99%, 97%, 93% and 99%, respectively. These additives promote precipitation of ionic mercury as mercury sulfide.     

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.     

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.     

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.     

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.     

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 %.     

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.     

燃煤烟气中SO3迁移转化特性及其控制的研究现状及展望

SO₃排放导致的烟羽浊度增大、蓝烟/黄烟现象及其排入大气环境后转化为二次气溶胶等问题,已引起广泛关注。燃煤电厂SO₃的排放主要由煤燃烧以及SCR烟气脱硝中SO₂氧化形成,随着选择性催化还原（SCR）脱硝设施的推广应用及高硫煤使用量的增多,控制燃煤SO₃排放已迫在眉睫。本文分析综述了燃煤烟气SO₃在SCR脱硝过程、低低温电除尘、湿法烟气脱硫以及湿式电除尘中的生成、迁移转化及脱除特性。同时介绍了两类控制燃煤烟气系统中SO₃的技术,一是利用现有污染物控制设备的协同作用;二是喷射碱性吸收剂吸收SO₃,综合比较了各类碱性吸收剂以及不同喷射位置,提出一种将喷碱性吸收剂与脱硫废水烟道蒸发技术相结合的控制方法。最后指出探究烟气系统中SO₃迁移转化特性以及碱性吸附剂脱除SO₃的反应机理及其影响因素是未来燃煤烟气SO₃控制技术研究的发展方向。     

燃煤电厂协同脱汞研究进展及强化措施

燃煤电厂是大气汞排放的重要源头,但是我国目前尚无完善的烟气汞控制方案。本文简要综述了国内外烟气脱汞技术研究现状,统计了国内污控设备（包括脱硝设备、除尘设备和脱硫设备）的装机容量。指出污控设备对烟气汞具有一定的协同脱除作用,但是受到我国煤质及运行条件等因素的制约,效果并不理想。本文结合国内某燃煤电厂的实测情况,提出了以下强化措施：①通过添加溴盐溶液,提高选择性催化还原（SCR）对烟气汞的氧化效率;②通过粉末活性炭与溴盐联合使用,强化静电除尘器（ESP）对烟气汞的协同脱除效率,脱汞效率可达90%以上;③通过精确控制脱硫浆液的pH值以及定期外排脱硫浆液,以降低其中汞的再释放率,维持湿法脱硫工艺（WFGD）稳定的烟气汞协同脱除效率;④通过优化和调整锅炉运行条件,提高现有污控设备体系的协同脱汞能力。     

烧结烟气脱硫制酸净化工序的设计与生产实践

介绍了太原钢铁（集团）有限公司炼铁厂烧结机烟气活性炭干法脱硫富集SO_2烟气的组分和工况。该富集SO_2烟气流量小、温度高、高含硫、高含尘并含有氨、氟、氯、汞等有害杂质,设计采用喷淋塔一一级泡沫柱洗涤器—气体冷却塔—二级泡沫柱洗涤器—两级电除雾器稀酸洗工艺加以处理,并对净化设备进行了设计选型。炼铁厂450m~烧结机烟气脱硫制酸装置已稳定运行1年多时间,净化工序各项指标均达到或超过设计值,较好地解决了恶劣工况烧结烟气净化除杂问题,净化收率达到99.01%,净化工序出口烟气尘（ρ）1.4mg/m~3,硫酸雾、HF、HCl、NH_3等微量。     

The effect of chlorine and oxygen concentrations on the removal of mercury at an FGD-batch reactor

A series of laboratory scale experiments were conducted in an FGD-batch reactor. A synthetic flue gas was produced and directed through a CaCO₃ suspension contained in a glass reactor vessel. The suspension temperature was set at 54 °C through a water bath. In order to observe the distribution of mercury species in the system, solid, liquid and gaseous samples were taken and analysed. For gaseous mercury determination, continuous measurements were carried out, up and downstream the reactor. Furthermore, the concentration of chlorine in the scrubber solution of the system was varied from 0 to 62 g/l under different oxidative conditions.In a first approach, a concentration drop of elemental mercury coming out of the system was observed. The latter occurs only when high concentrations of Cl⁻ are present, combined with a high O₂ availability in the scrubber. It was also observed that mercury species distribution in the different phases varies, depending on the available chemical form of chlorine and oxygen concentration.     

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.     

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.     

Laboratory study of air-water-coal combustion product (fly ash and FGD solid) mercury exchange

Recent laboratory research has indicated that coal fly ash derived from subbituminous and bituminous type coals is a sink for atmospheric mercury (Hg), however lignite-based ash was found to emit Hg to the air. Solids collected from systems with components that enhance Hg removal (i.e. activated carbon injection (ACI), flue gas desulfurization (FGD), and selective catalytic reduction (SCR) or selective non-catalytic reduction (SNCR)) may have higher Hg concentrations and therefore a higher potential for Hg release. For this study we investigated the potential for Hg release to the air and water from coal combustion products (CCPs) collected from coal-fired units with FGD equipment, SCR and SNCR equipment, and sorbent injection for Hg removal. In the laboratory study, most dry samples acted as sinks for atmospheric Hg in the dark at 25 °C. When exposed to light or increased temperature (45 °C), deposition of Hg to the fly ash substrates in most cases continued but decreased. Wet FGD samples emitted Hg. However, they became a sink for atmospheric Hg or exhibited low Hg emission rates when dried. Mercury flux in the dark at 25 °C was correlated with fly ash carbon content (LOI). Most liquid extracts derived using the synthetic precipitation leaching procedure (SPLP EPA method 1312) had very low Hg concentrations (<13 ng/l).     

Mercury speciation and emission from the coal‐fired power plant filled with flue gas desulfurization equipment

Mercury speciation and emission from two Chinese coal‐fired power stations equipped with flue gas desulfurization device were investigated. Research results reveal that Hg⁰ is the main form in the flue gas in Plant 1; Hg²⁺ is the main form in the flue gas in Plant 2. Most of mercury was emitted to the atmosphere, which was about 77–98%, and the elemental mercury released to atmosphere ranged 73–94% approximately. A pot of mercury is adsorbed by bottom ash, electrostatic precipitator (ESP) ash, and gypsum in Plant 1. However, most mercury, the scale of which is 75–83.2%, is collected by ESP ash, and only 7.0–12.2% mercury is emitted to the atmosphere in Plant 2. The mercury removal by NID semi‐desulfurization system is higher than wet flue gas desulfurization (WFGD) desulfurization system.