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.     

Removal of Hg from flue gases in wet FGD by catalytic oxidation with air - An experimental study

About 46% of global mercury emissions are due to fossil fuel combustion for electrical and thermal energy production. Since more stringent emission standards are expected, important research efforts are being focused on the development of mercury removal technologies, mainly directed to two alternative approaches: (i) the enhancement of homogeneous oxidation in the flue gases of Hg⁰ to water soluble Hg²⁺ by the addition of chlorides or bromides to the boiler or; (ii) the adsorption of Hg²⁺ and Hg⁰ on impregnated activated carbon (AC). The latter may require the treatment of the entire gas volume of the thermal power plant and constantly consumes relatively large quantities of AC.A third option gaining more attention lately is based on the oxidation and retention of dissolved Hg⁰ in the wet flue gas desulphurisation (FGD) system. A series of chemical oxidants, such as halogens, hydrogen peroxide, sulphur and oxygen, are theoretically able to oxidize Hg⁰ in the wet FGD system. Most chemical oxidants when applied in the FGD, however, are non-selective and are largely consumed by SO₂ absorbed from the flue gas. The less expensive oxidant, non-selective as well, is oxygen (as air) which is already being dispersed into FGD absorbing suspension for the conversion of into .The experimental evidence of the present work showed that Hg⁰ present in the gaseous phase can be dissolved and oxidized to a high degree (70-90%) by air together with in wet FGD solutions. Transition metals such as Fe²⁺ and Mn²⁺ act as catalysts, chloride enhances the reaction, while some oxosulphur compounds, e.g. tetrathionate, inhibit the oxidation. A combination of several catalysts at a concentration of sulphite () below 100 mg L⁻¹ and an adequate redox potential of the solution can assure reasonable mercury removal even in the presence of oxidation inhibiting compounds.The main competitive reactions that govern final Hg⁰ removal in the FGD are as follows: (1) oxidation of Hg⁰ together with SO₂ with air, enhanced by catalysts; (2) removal of catalysts by precipitation in the form of Fe(OH)₃ and eventually as MnO₂ (to overcome this problem continuous addition of catalysts to the solution is required); (3) reduction of Fe³⁺ by tetrathionate to Fe²⁺ which (4) may reduce Hg²⁺ to Hg⁰ and probably (5) the complexation of Hg²⁺ by anions present which may play an important role in the mechanism by complexing the product(s) of the Hg⁰ oxidation reaction.     

Fabrication of a novel natural cellulose-based paper chemodosimeter via grafting-to of Rhodamine B moieties for detection of Hg2+

A cellulose-based paper chemodosimeter was designed and prepared by reactions of Rhodamine B with natural cellulose paper. Its sensing property to Hg²⁺ was investigated by fluorescence spectroscopies. While the Hg²⁺-indicating paper was immersed into the Hg²⁺ solution, the ring of the rhodamine spirolactam opened and the thiosemicarbazide moiety would undergo an irreversible desulfurization reaction to form its corresponding oxadiazole structure, a colorful and fluorescent product. The color change can be discerned by a naked eye under the irradiation of 365 nm UV light. The Hg²⁺-indicating paper displayed excellent selective toward Hg²⁺ over other commonly metal ions and the sensitive detection of Hg²⁺ was not interfered by other heavy metal ions. The results suggested that the Hg²⁺-indicating paper would serve as a practical fluorescent chemodosimeter for rapid and convenience detection of Hg²⁺.     

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.     

Unconventional ion exchange resins and their retention properties for Hg2+ ions

Synthesis of two unconventional ion exchange resins and their behaviour on the mercury sorption experiments were investigated.The ion exchange resins were obtained by the quaternization reaction of 4-vinylpyridine:divinylbenzene copolymer, gel-type, by two ways namely, the nucleophilic substitution of the pyridine matrix with 2-chloroacetamide and the nucleophilic addition of protonated copolymer to acrylamide.Comparative sorptions of Hg²⁺ ions on the synthesized pyridine resins by batch experiments in mono- and binary system were analyzed. Mercury retention experiments aimed to study the influence of the solution concentration, contact time and solution pH. The removal of Hg²⁺ ions from aqueous solutions depends on the pH values, the amount of the retained mercury increased with the pH value.The studied strong base pyridine anion exchange resins presented a good selectivity for the Hg²⁺ ions during the competitive sorption of Hg²⁺/Cu²⁺, Hg²⁺/Zn²⁺ and Hg²⁺/Fe³⁺ at metal cations ratio of 1:1.     

Priority pollutants (Hg and Cd) removal from water by ETS-4 titanosilicate

The synthetic microporous titanosilicate material ETS-4 has been used for the removal of Hg²⁺ and Cd²⁺ from water. Batch stirred experiments were carried out to study the equilibrium and the kinetics of the removal of Hg²⁺ and Cd²⁺ from water. It has been demonstrated that ETS-4 has a great affinity for both these metal cations even when their initial concentrations are low. The uptake rates for both Hg²⁺ and Cd²⁺ were well described by the pseudo-second order model which constants confirmed that the kinetics of the removal of Cd²⁺ is faster than that of Hg²⁺. However, at the equilibrium, ETS-4 has a higher capacity to remove Hg²⁺ than Cd²⁺. Adsorption isotherms for both Hg²⁺ and Cd²⁺ were well fitted to Langmuir isotherm and the corresponding monolayer capacities of ETS-4 are 0.43 and 0.24 µmol mg^- 1, respectively, which are quite consistent with those predicted by the pseudo-second order kinetic equation. Hence, the contribution of this work is to support the use of this material for the removal of Hg²⁺ and Cd²⁺ from water.     

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.     

Synthesis of Starch-Stabilized Ag Nanoparticles and Hg2+ Recognition in Aqueous Media

The starch-stabilized Ag nanoparticles were successfully synthesized via a reduction approach and characterized with SPR UV/Vis spectroscopy, TEM, and HRTEM. By utilizing the redox reaction between Ag nanoparticles and Hg²⁺, and the resulted decrease in UV/Vis signal, we develop a colorimetric method for detection of Hg²⁺ ion. A linear relationship stands between the absorbance intensity of the Ag nanoparticles and the concentration of Hg²⁺ ion over the range from 10 ppb to 1 ppm at the absorption of 390 nm. The detection limit for Hg²⁺ ions in homogeneous aqueous solutions is estimated to be ~5 ppb. This system shows excellent selectivity for Hg²⁺ over other metal ions including Na⁺, K⁺, Ba²⁺, Mg²⁺, Ca²⁺, Fe³⁺, and Cd²⁺. The results shown herein have potential implications in the development of new colorimetric sensors for easy and selective detection and monitoring of mercuric ions in aqueous solutions.     

半干法脱硫灰对Hg~0的催化氧化及吸附特性

采用新型一体化脱硫工艺和循环流化床烟气脱硫工艺的脱硫灰为吸附剂,使用固定床反应器,在模拟烟气的条件下研究了两种半干法脱硫灰对汞的吸附及催化氧化特性。研究结果表明,吸附于脱硫灰表面的汞主要以Hg2+的形态存在,多数情况下,更高的汞氧化率伴随有更高的汞吸附率,HCl、Cl2、NO2在脱硫灰的催化作用下能有效氧化Hg0,且不同组分对Hg0的氧化作用可以累积,而NO和SO2抑制了脱硫灰对汞的吸附。脱硫灰中未燃尽碳和Fe2O3对脱硫灰吸附和催化氧化气态汞具有显著促进作用。汞吸附率和氧化率在使用两种脱硫灰作为吸附剂时均随温度升高先增大后减小,这是传质过程和反应速率共同作用的结果。     

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

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

Removal of Hg2+ from aqueous solution using a novel composite carbon adsorbent

A novel composite carbon adsorbent (GCA) has been prepared by immobilizing activated carbon and genipin‐crosslinked chitosan into calcium alginate gel beads via entrapment and applied to the removal of mercury (Hg²⁺) ions from aqueous solution (e.g., drinking water). Two bead sizes and two mixing ratios of components were obtained and characterized. Batch experiments were performed to study the uptake equilibrium and kinetics of Hg²⁺ ions by the GCA. The Hg²⁺ adsorption capacity of GCA was found to be dependent of pH and independent of size of the adsorbent. The Hg²⁺ adsorption rate of GCA increases with decreasing its bead size. However, both adsorption capacity and rate of GCA for Hg²⁺ increase with increasing its chitosan content. Otherwise, it was shown that the GCA has higher Hg²⁺ adsorption capacity and rate than activated carbon, which might be caused by the incorporation of chitosan into the GCA. The maximum Hg²⁺ adsorption capacity of GCA was found to be 576 mg/g, which is over seven times higher than that of activated carbon. Our results reveal the uniform distribution of activated carbon and chitosan within the alginate gel bead and that Hg²⁺ ions can diffuse inside the bead. It also demonstrated the feasibility of using this GCA for Hg²⁺ removal at low pH values. The Hg²⁺ absorbed beads of the GCA can be effectively regenerated and reused using H₂SO₄. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Selective chromogenic and fluorogenic signalling of Hg ions using a fluorescein-coumarin conjugate

A novel, Hg²⁺-selective chemosensor was prepared via Mannich reaction of dichlorofluorescein with piperazinyl-coumarin moiety. The dichlorofluorescein–coumarin derivative exhibited well-defined Hg²⁺-selective chromogenic behavior, indicated by a green to pink colour change in solution, as well as fluorogenic signalling. Significant changes in fluorescence of the dichlorofluorescein subunit were analyzed in reference to the rather constant coumarin emission as an internal standard yielding Hg²⁺ selectivity. The Hg²⁺ selectivity of the chemosensor was not appreciably affected by the presence of common coexisting alkali, alkaline earth, and transition metal ions. The detection limit of the dichlorofluorescein–coumarin conjugate for the determination of Hg²⁺ ions was 4.3 × 10⁻⁶ mol L⁻¹ and the conjugate dye could be used as a chemosensor for the analysis of Hg²⁺ ions in aqueous environments.     

A naphthalimide-rhodamine ratiometric fluorescent probe for Hg based on fluorescence resonance energy transfer

On the basis of fluorescent resonance energy transfer from 1,8-naphthalimide to rhodamine B, a new fluorophore dyads (4) containing rhodamine B and a naphthalimide moiety was synthesized as a ratiometric fluorescent probe for detecting Hg²⁺ with a broad pH range 5.7-11.0. The selective fluorescence response of 4 to Hg²⁺ is due to the Hg²⁺-promoted desulfurization of the thiocarbonyl moiety, leading to the ring-opening of rhodamine B moiety of 4. When 4 was employed at 0.1 μM with the slit size being 20 nm/20 nm, a low level of Hg²⁺ (up to 3 × 10⁻⁸ M) can be detected using the system.     

In situ detection and removal of metal ion by porous gold electrode

A sensing electrode for the detection of heavy metal ions in aqueous solution selectively measured the concentrations of target materials on its functionalized surface, which has affinity to target metal ions. Target ions were adsorbed simultaneously on the functionalized electrode during the sensing process. Therefore, to understand this, experiments on the amperometric response and isotherms with an initial concentration of Hg²⁺ were tested. Detection current was dependent on the concentration of Hg²⁺, and the equilibrium concentration of Hg²⁺ adsorbed to the electrode showed a Langmuirian shape. Correlation between the detection current and removal capacity for Hg²⁺ revealed that it is possible to estimate the adsorbed concentration on the electrode during the sensing step. Although the macroporous gold electrode prepared herein showed relatively low adsorption performance compared to conventional adsorbents, when we prepare nanoporous gold electrodes with a uniform nanopore structure and large surface area, in situ detection and simultaneously removal of metal ions by nanoporous gold electrode will be possible.     

Hg detection by aniline-based conjugated copolymers with high selectivity

Conjugated polymers (P1, P1L and P2-P5) constructed by alkynyl-substituted aniline and substituted arene analogs could be synthesized through Pd-catalyzed Sonogashira coupling. The responsive optical properties of poly(2-ethynyl aniline) (P1 and P1L for different molecular weights, P1L with longer chains on average) toward various metal ions (including Ni²⁺, Ag⁺, Cu²⁺, Zn²⁺, Fe³⁺, Fe²⁺, Mn²⁺, Na⁺, Ca²⁺, Pb²⁺, K⁺, Cr³⁺, Al³⁺, Cd²⁺, Pt²⁺, Au³⁺ and Tl³⁺) were investigated. Hg²⁺ exhibited the most pronounced fluorescence response of both P1 and P1L without interference from those coexistent ions due to aniline in the polymer backbone as the metal binding ligand, while other metal ions does not cause obvious change of fluorescence. Compared with P1, P1L exhibits better sensitivity toward Hg²⁺. Introducing pyridyl, thienyl or phenyl groups into the polymer backbone would weaken the quenching responses to Hg²⁺ compared with P1. The results indicated P1 and P1L could be used as a selective fluorescence sensor toward Hg²⁺.     

A highly selective ratiometric fluorescent sensor for Hg2+ based on 1,8‐naphthalimide

A sulfur probe based on 1,8‐naphthalimide was designed and synthesised, and its sensing behaviour towards a mercury ion was investigated by fluorescence spectroscopy. The probe showed higher selective recognition towards Hg²⁺ than towards other metal ions in methanol solution. Compared with 4‐amino‐substituted naphthalimide derivatives, the probe exhibited different fluorescent characteristics for sensing Hg²⁺. The novel, reaction‐based probe is recommended for selective recognition of Hg²⁺ with significant fluorescence change.     

Polymer-based fluorescence sensor incorporating triazole moieties for Hg detection via click reaction

The polymer could be obtained by the polymerization of 1,4-dibutoxy-2,5-diethynylbenzene (M-1) with 1,4-diazidobenzene (M-2)via click reaction. The polymer show blue fluorescence. The responsive optical properties of the polymer on various transition metal ions were investigated by fluorescence spectra. Compared with other cations, such as Co²⁺, Ni²⁺, Ag⁺, Cd²⁺, Cu²⁺ and Zn²⁺, Hg²⁺ can exhibit the most pronounced fluorescence response of the polymer Hg²⁺ can exhibit the most pronounced fluorescence response of the polymer due to triazole moiety in the polymer main chain as the metal binding ligand. The results indicate this kind of conjugated polymer with triazole moiety synthesized by click reaction can be used as a selective fluorescence sensor for Hg²⁺ detection.     

Colorimetric detection of Hg2+ using a mixture of an anionic azo dye and a cationic polyelectrolyte in aqueous solution

We investigated a colorimetric chemosensor for Hg²⁺ based on a mixture of xylidyl blue I as an anionic organic dye and poly(diallyldimethylammonium chloride) as a cationic polyelectrolyte in an aqueous solution at pH 7.5. The addition of Hg²⁺ to the mixture induced a bathochromic shift in the absorption spectra with a distinct color change from red to green which was readily identifiable by the naked eye, whereas the other metal ions gave rise to insignificant color changes. By contrast, upon adding Hg²⁺ to xylidyl blue I alone, the solution underwent no significant change in color. Moreover, a stoichiometric ratio for the complex between xylidyl blue I and Hg²⁺ in the presence of poly(diallyldimethylammonium chloride) was determined to be 1:1 by the absorption titration curve and Job's plot. Thus, the mixture can be used as a selective naked‐eye colorimetric chemosensor for Hg²⁺ over other common metal ions. This study raises the possibility that the combination of an organic dye and an oppositely charged polyelectrolyte is a potential candidate for the easy construction of a new chemosensor system. © 2018 Society of Chemical Industry     

A benzothiazole-based semisquarylium dye suitable for highly selective Hg sensing in aqueous media

A novel semisquarylium dye was synthesized by the reaction between 3,4-dibutoxy-3-cyclobutene-1,2-dione and a benzothiazolium salt and its metal ion sensing properties were investigated using absorption and emission spectroscopy. These misquarylium exhibited high selectivity for Hg²⁺ ions, as compared with Ca²⁺, Pb²⁺, Al³⁺, Ce²⁺, Ba²⁺, Ni²⁺, Cd²⁺, Zn²⁺ and Mg²⁺ ions in DMSO/H₂O (9:1, v/v), which was attributed to the formation of a 2:1 BSQ:Hg²⁺ coordination complex, the formation of which was supported by the calculated geometry of the complex.     

Removal of Hg0 from flue gas using two homogeneous photo‐fenton‐like reactions

Removal of Hg⁰ using two homogeneous Photo‐Fenton‐Like reactions was first investigated in a photochemical reactor. Effects of process parameters on Hg⁰ removal were studied. Free radical and reaction products were analyzed. Removal pathways of Hg⁰ were discussed. Simultaneous removal of Hg⁰, NO, and SO₂ is also studied briefly. The results show that UV power, wavelength, H₂O₂ concentration, and solution pH have great effects on Hg⁰ removal. Hg⁰, and SO₂ concentrations, solution temperature, Fe³⁺, Cu²⁺, , and concentrations also have significant effects on Hg⁰ removal. However, concentrations of CO₂, NO, O₂, Cl^?, , , SiO₂, Al₂O₃, and Fe₂O₃ only have slight effects on Hg⁰ removal. Hg⁰/NO/SO₂ can be simultaneously removed by Photo‐Fenton‐Like reactions. ·OH was captured, and / /Hg²⁺ were also detected. Removals of Hg⁰ by photochemical oxidation and ·OH oxidation play a major role, and removal of Hg⁰ by H₂O₂ oxidation only plays a secondary role in removal of Hg⁰. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1322–1333, 2015