Ultra-high adsorption of Hg0 using impregnated activated carbon by selenium

Activated carbon was one of the main adsorptions utilized in elemental mercury (Hg⁰) removal from coal combustion flue gas. However, the high cost and low physical adsorption efficiency of activated carbon injection (ACI) limited its application. In this study, an ultra-high efficiency (nearly 100%) catalyst sorbent-Se_x/Activated carbon (Se_x/AC) was synthesized and applied to remove Hg⁰ in the simulated flue gas, which exhibited 120 times outstanding adsorption performance versus the conventional activated carbon. The Se_x/AC reached 17.98 mg/g Hg⁰ adsorption capacity at 160 °C under the pure nitrogen atmosphere. Moreover, it maintained an excellent mercury adsorption tolerance, reaching the efficiency of Hg⁰ removal above 85% at the NO and SO₂ conditions in a bench-scale fixed-bed reactor. Characterized by the multiple methods, including BET, XRD, XPS, kinetic and thermodynamic analysis, and the DFT calculation, we demonstrated that the ultrahigh mercury removal performance originated from the activated Se species in Se_x/AC. Chemical adsorption plays a dominant role in Hg⁰ removal: Selenium anchored on the surface of AC would capture Hg⁰ in the flue gas to form an extremely stable substance-HgSe, avoiding subsequent Hg⁰ released. Additionally, the oxygen-containing functional groups in AC and the higher BET areas promote the conversion of Hg⁰ to HgO. This work provided a novel and highly efficient carbon-based sorbent -Se_x/AC to capture the mercury in coal combustion flue gas.

Selenium-modified porous activated carbon and the interface functional group promotes the synergistic effect of physical adsorption and chemical adsorption to promote the adsorption capacity of Hg⁰.

     

湿式烟气脱硫系统同时脱汞研究

研究表明,湿法烟气脱硫装置(WFGD)可去除烟气中绝大部分Hg²⁺,但对单质汞的吸收效果不明显,因此研究提高湿法烟气脱硫系统中单质汞的氧化率的方法对控制汞的排放具有重要意义。综述了WFGD及在此系统中各种添加剂的脱汞性能,认为在添加剂中,气态的臭氧、液态的次氯酸和氯化钠稀溶液、 黄磷乳浊液、氢硫化钠溶液及EDTA的汞去除效果较好,且不会被SO₂大量消耗,可在WFGD系统实现同时脱硫脱汞;而气态的氯气,液态的K₂S₂O₈溶液虽然也有较好的汞去除效果,但因易被SO₂或亚硫酸盐溶液消耗,当在WFGD系统中用其氧化单质汞时,需要对脱硫塔进行分层或其他改造,使烟气中的SO₂被吸收后再控制汞,提高经济性。     

Gas-phase elemental mercury removal in a simulated combustion flue gas using TiO2 with fluorescent light

A previously proposed technology incorporating TiO₂ into common household fluorescent lighting was further tested for its Hg⁰ removal capability in a simulated flue-gas system. The flue gas is simulated by the addition of O₂, SO₂, HCl, NO, H₂O, and Hg⁰, which are frequently found in combustion facilities such as waste incinerators and coal-fired power plants. In the O₂ + N₂ + Hg⁰ environment, a Hg⁰ removal efficiency (η_Hg) greater than 95% was achieved. Despite the tendency for η_Hg to decrease with increasing SO₂ and HCl, no significant drop was observed at the tested level (SO₂: 5–300 ppm_v, HCl: 30–120 ppm_v). In terms of NO and moisture, a significant negative effect on η_Hg was observed for both factors. NO eliminated the OH radical on the TiO₂ surface, whereas water vapor caused either the occupation of active sites available to Hg⁰ or the reduction of Hg₀ by free electron. However, the negative effect of NO was minimized (η_Hg > 90%) by increasing the residence time in the photochemical reactor. The moisture effect can be avoided by installing a water trap before the flue gas enters the Hg⁰ removal system.

Implications: This paper reports a novel technology for a removal of gas-phase elemental mercury (Hg⁰) from a simulated flue gas using TiO₂-coated glass beads under a low-cost, easily maintainable household fluorescent light instead of ultraviolet (UV) light. In this study, the effects of individual chemical species (O₂, SO₂, HCl, NO, and water vapor) on the performance of the proposed technology for Hg⁰ removal are investigated. The result suggests that the proposed technology can be highly effective, even in real combustion environments such as waste incinerators and coal-fired power plants.     

Recycling of iron and silicon from drinking water treatment sludge for synthesis of magnetic iron oxide@SiO<Subscript>2</Subscript> composites

More attention has been paid to the deterioration of water bodies polluted by drinking water treatment sludge (DWTS) in recent years. It is important to develop methods to effectively treat DWTS by avoiding secondary pollution. We report herein a novel investigation for recovery of Si and Fe from DWTS, which are used for the synthesis of two iron oxide@SiO₂ composites for adsorption of reactive red X-3B (RRX-3B) and NaNO₂. The results show that Fe³⁺ (acid-leaching) and Si⁴⁺ (basic-leaching) can be successfully recovered from roasted DWTS. Whether to dissolve Fe(OH)₃ precipitation is the key point for obtaining Fe₃O₄ or γ-Fe₂O₃ particles using the solvothermal method. The magnetic characteristics of Fe₃O₄@SiO₂ (390.0 m² g^?1) or Fe₂O₃@SiO₂ (220.9 m² g^?1) are slightly influenced by the coated porous SiO₂ layer. Peaks of Fe–O stretching vibration (580 cm^?1) and asymmetric Si–O–Si stretching vibrations (1080 cm^?1) of Fe₃O₄@SiO₂ indicate the successful coating of a thin silica layer (20–150 nm). The adsorption capacity of RRX-3B and NaNO₂ by Fe₃O₄@SiO₂ is better than that of Fe₂O₃@SiO₂, and both composites can be recycled through an external magnetic field. This method is an efficient and environmentally friendly method for recycling DWTS.     

Synthesis of Fe-doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocatalyst and its sonophotocatalytic activity on synthetic dye and real textile wastewater

The catalysts such as Fe, Bi₂O₃, and Fe-doped Bi₂O₃ were synthesized for the sonophotocatalytic treatment of synthetic dye and real textile wastewater. The resultant catalysts were characterized for its size and uniform shape using x-ray diffractogram (XRD) and scanning electron microscopy (SEM) which signified the nanorod shape formed Bi₂O₃. The higher ultraviolet light absorbance capacity of the catalysts was also evident using diffuse reflectance spectroscopy (DRS). Initially, the effect of conventional parameters such as initial pH, gas bubbling (argon, oxygen, air and nitrogen) and oxidant addition (H₂O₂ and peroxymonosulfate) in the presence of sonolysis (22 and 37 kHz frequency) and photolysis (UV-C light) on 10 ppm Basic Brown 1 dye was studied. The results showed that highest decolorization of 62 % was attained for 3 g/L peroxymonosulfate under 37 kHz frequency sonolysis treatment. Secondly, with the catalyst study, highest of 46 % dye color removal was obtained with 4 g/L Fe under 37 kHz frequency sonolysis treatment. The sonophotocatalytic treatment of dye with Fe-doped Bi₂O₃ catalyst in combination with peroxymonosulfate showed highest color removal of 99 %. Finally, the sonophotocatalytic treatment of real textile wastewater in the presence of 3 g/L Fe-doped Bi₂O₃ and 6 g/L peroxymonosulfate reduced the total organic carbon (TOC) and chemical oxygen demand (COD) level to 77 and 91 %, respectively, in 180 min. The reported treatment process was found to treat the synthetic dye and real textile wastewater effectively.     

Physiological characteristics of <Emphasis Type="Italic">Plantago major</Emphasis> under SO<Subscript>2</Subscript> exposure as affected by foliar iron spray

Sulfur dioxide (SO₂) is considered as a main air pollutant in industrialized areas that can damage vegetation. In the present study, we investigated how exposure to SO₂ and foliar application of iron (Fe) would affect certain physiological characteristics of Plantago major. The plant seedlings exposed or unexposed to SO₂ (3900 μg m^?3) were non-supplemented or supplemented with Fe (3 g L^?1) as foliar spray. Plants were exposed to SO₂ for 6 weeks in 100 × 70 × 70 cm chambers. Fumigation of plants with SO₂ was performed for 3 h daily for 3 days per week (alternate day). Lower leaf Fe concentration in the plants exposed to SO₂ at no added Fe treatment was accompanied with incidence of chlorosis symptoms and reduced chlorophyll concentration. No visible chlorotic symptoms were observed on the SO₂-exposed plants supplied with Fe that accumulated higher Fe in their leaves. Both at with and without added Fe treatments, catalase (CAT) and peroxidase (POD) activity was higher in the plants fumigated with SO₂ in comparison with those non-fumigated with SO₂. Foliar application of Fe was also effective in increasing activity of antioxidant enzymes CAT and POD. Exposure to SO₂ led to reduced cellulose but enhanced lignin content of plant leaf cell wall. The results obtained showed that foliar application of Fe was effective in reducing the effects of exposure to SO₂ on cell wall composition. In contrast to SO₂, application of Fe increased cellulose while decreased lignin content of the leaf cell wall. This might be due to reduced oxidative stress induced by SO₂ in plants supplied with Fe compared with those unsupplied with Fe.     

Quick vaporization of sprayed sodium hypochlorite (NaClO(aq)) for simultaneous removal of nitrogen oxides (NOx), sulfur dioxide (SO2), and mercury (Hg0)

Sodium hypochlorite (NaClO) has been widely used as a chemical additive for enhancing nitrogen oxide (NO_x; NO + NO₂), sulfur dioxide (SO₂), and mercury (Hg⁰) removals in a wet scrubber. However, they are each uniquely dependent on NaClO_(aq) pH, hence making the simultaneous control difficult. In order to overcome this weakness, we sprayed low liquid-to-gas (L/G) ratio (0.1 L/Nm³) of NaClO_(aq) to vaporize quickly at 165 °C. Results have shown that the maximized NO_x, SO₂, and Hg⁰ removals can be achieved at the pH range between 4.0 and 6.0. When NO_x and Hg⁰ coexist with SO₂, in addition, their removals are significantly enhanced by reactions with solid and gaseous by-products such as NaClO_(s), NaClO_2(s), OClO, ClO, and Cl species, originated from the reaction between SO₂ and NaClO_(aq). We have also demonstrated the feasibility of this approach in the real flue gases of a combustion plant and observed 50%, 80%, and 60% of NO_x, SO₂, and Hg⁰ removals, respectively. These findings led us to conclude that the spray of NaClO_(aq) at a relatively high temperature at which the sprayed solution can vaporize quickly makes the simultaneous control of NO_x, SO₂, and Hg⁰ possible.

Implications: The simple spray of NaClO_(aq) at temperatures above 165 °C can cause the simultaneous removal of gaseous NO_x, SO₂, and Hg⁰ by its quick vaporization. Their maximized removals are achieved at the pH range between 4.0 and 6.0. NO_x and Hg⁰ removals are also enhanced by gaseous and solid intermediate products generated from the reaction of SO₂ with NaClO_(aq). The feasibility of this approach has been demonstrated in the real flue gases of a combustion plant.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

Investigation of Selective Catalytic Reduction Impact on Mercury Speciation under Simulated NOx Emission Control Conditions

Abstract

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NO_x) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NO_x reduction, promote the formation of oxidized mercury (Hg²⁺).

The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg⁰) oxidation. Bench-scale experiments were conducted to investigate Hg⁰ oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO₂) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO₂ in the flue gases on Hg⁰ oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg⁰ to Hg²⁺ under SCR reaction conditions. The importance of HCl for Hg⁰ oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg⁰ oxidation occurring across the SCR reactors in the field.     

Effect of solution pH on aging dynamics and surface structural evolution of mZVI particles: H<Subscript>2</Subscript> production and spectroscopic/microscopic evidence

A microscale zero-valent iron (mZVI)-based in situ reactive zone is a promising technology for contaminated groundwater remediation. Estimation of mZVI aging behavior after its injection into the subsurface is essential for efficiency and longevity assessments. In this study, batch tests were conducted to investigate the effect of initial pH on mZVI aging dynamics, as well as the formation and evolution of aging products over 112 days. Results indicated that mZVI aging accelerated with decreasing initial pH. Corrosion rates of mZVI particles under pH 6.0 and 7.5 were approximately two orders of magnitude higher than those observed at pH 9.0. The morphological, structural, and compositional evolution of mZVI particles in three systems (pH = 6.0, 7.5, and 9.0) were investigated using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. In acidic and neutral solutions, a thick passivation layer with loosely and unevenly distributed aging precipitates was observed, and Fe₃O₄ was the final aging precipitate. Nevertheless, in alkaline solutions, minute aging precipitates were detected on the mZVI surface at 112 day. Characterization results suggested that mZVI was oxidized via the Fe⁰–Fe(OH)₂–Fe₃O₄ route. These findings shed new light on mZVI aging mechanisms, particularly its physicochemical characteristics and the structural evolution of mZVI in field-scale groundwater remediation applications.     

Degradation of bisphenol A in aqueous solution by persulfate activated with ferrous ion

Degradation of bisphenol A (BPA) in aqueous solution was studied with high-efficiency sulfate radical (SO₄ ^?·), which was generated by the activation of persulfate (S₂O₈ ^2?) with ferrous ion (Fe²⁺). S₂O₈ ^2? was activated by Fe²⁺ to produce SO₄ ^?·, and iron powder (Fe⁰) was used as a slow-releasing source of dissolved Fe²⁺. The major oxidation products of BPA were determined by liquid chromatography-mass spectrometer. The mineralization efficiency of BPA was monitored by total organic carbon (TOC) analyzer. BPA removal efficiency was improved by the increase of initial S₂O₈ ^2? or Fe²⁺ concentrations and then decreased with excess Fe²⁺ concentration. The adding mode of Fe²⁺ had significant impact on BPA degradation and mineralization. BPA removal rates increased from 49 to 97 % with sequential addition of Fe²⁺, while complete degradation was observed with continuous diffusion of Fe²⁺, and the latter achieved higher TOC removal rate. When Fe⁰ was employed as a slow-releasing source of dissolved Fe²⁺, 100 % of BPA degradation efficiency was achieved, and the highest removal rate of TOC (85 %) was obtained within 2 h. In the Fe⁰–S₂O₈ ^2? system, Fe⁰ as the activator of S₂O₈ ^2? could offer sustainable oxidation for BPA, and higher TOC removal rate was achieved. It was proved that Fe⁰–S₂O₈ ^2? system has perspective for future works.     

Inactivation of <Emphasis Type="Italic">Escherichia coli</Emphasis> in fresh water with advanced oxidation processes based on the combination of O<Subscript>3</Subscript>, H<Subscript>2</Subscript>O<Subscript>2</Subscript>, and TiO<Subscript>2</Subscript>. Kinetic modeling

The purpose of this work was to study the efficiency of different treatments, based on the combination of O₃, H₂O₂, and TiO₂, on fresh surface water samples fortified with wild strains of Escherichia coli. Moreover, an exhaustive assessment of the influence of the different agents involved in the treatment has been carried out by kinetic modeling of E. coli inactivation results. The treatments studied were (i) ozonation (O₃), (ii) the peroxone system (O₃/0.04 mM H₂O₂), (iii) catalytic ozonation (O₃/1 g/L TiO₂), and (iv) a combined treatment of O₃/1 g/L TiO₂/0.04 mM H₂O₂. It was observed that the peroxone system achieved the highest levels of inactivation of E. coli, around 6.80 log after 10 min of contact time. Catalytic ozonation also obtained high levels of inactivation in a short period of time, reaching 6.22 log in 10 min. Both treatments, the peroxone system (O₃/H₂O₂) and catalytic ozonation (O₃/TiO₂), produced a higher inactivation rate of E. coli than ozonation (4.97 log after 10 min). While the combination of ozone with hydrogen peroxide or titanium dioxide thus produces an increase in the inactivation yield of E. coli regarding ozonation, the O₃/TiO₂/H₂O₂ combination did not enhance the inactivation results. The fitting of experimental values to the corresponding equations through non-linear regression techniques was carried out with Microsoft® Excel GInaFiT software. The inactivation results of E. coli did not respond to linear functions, and it was necessary to use mathematical models able to describe certain deviations in the bacterial inactivation processes. In this case, the inactivation results fit with mathematical models based on the hypothesis that the bacteria population is divided into two different subgroups with different degrees of resistance to treatments, for instance biphasic and biphasic with shoulder models.

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Graphical abstract ?

     

Simultaneous removal of NOx,SO2, and Hg from flue gas in FGD absorber with oxidant injection (NaClO2)– full-scale investigation

ABSTRACT

This article presents the results of an industrial-scale study (on 400 MW_e lignite fired unit) of simultaneous NO_x, SO₂, and Hg^T removal in FGD absorber with oxidant injection (NaClO₂) into flue gas. It was confirmed that the injection of sodium chlorite upstream the FGD (Flue Gas Desulfurization) absorber oxidize NO to NO₂, Hg⁰ to Hg²⁺, and enhancing NO_x and Hg^T removal efficiency from exhaust gas in FGD absorber. Mercury removal efficiency grows with the rise of degree of oxidation NO to NO₂ and was limited by the phenomenon of re-emission. For NO_x removal the most critical parameters is slurry pH and temperature. There was no negative effect on sulfur dioxide removal efficiency caused by oxidant injection in tested FGD absorber. Based on the data provided, NO_x and Hg^T emissions can be reduced by adjusting the FGD absorber operating parameters combined with oxidant injection.     

Low Concentration Mercury Sorption Mechanisms and Control by Calcium-Based Sorbents: Application in Coal-Fired Processes

ABSTRACT

The capture of elemental mercury (Hg⁰) and mercuric chloride (HgCl₂) by three types of calcium (Ca)-based sor-bents was examined in this bench-scale study under conditions prevalent in coal-fired utilities. Ca-based sorbent performances were compared with that of an activated carbon. Hg⁰ capture of about 40% (nearly half that of the activated carbon) was achieved by two of the Ca-based sorbents. The presence of sulfur dioxide (SO₂) in the simulated coal combustion flue gas enhanced the Hg⁰ capture from about 10 to 40%. Increasing the temperature in the range of 65-100 °C also caused an increase in the Hg⁰ capture by the two Ca-based sorbents. Mercuric chloride (HgCl₂) capture exhibited a totally different pattern. The presence of SO₂ inhibited the HgCl₂ capture by Ca-based sorbents from about 25 to less than 10%. Increasing the temperature in the studied range also caused a decrease in HgCl₂ capture. Upon further pilot-scale confirmations, the results obtained in this bench-scale study can be used to design and manufacture more cost-effective mercury sorbents to replace conventional sorbents already in use in mercury control.     

Effects of Sulfur Dioxide and Nitric Oxide on Mercury Oxidation and Reduction under Homogeneous Conditions

Abstract

This paper is particularly related to elemental mercury (Hg⁰) oxidation and divalent mercury (Hg²⁺) reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO₂). As a powerful oxidant and chlorinating reagent, Cl₂ has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO₂, NO, as well as H₂O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO₂ and NO on Hg⁰ oxidation and Hg²⁺ reduction with the intent of unraveling unrecognized interactions among Cl species, SO₂, and NO most importantly in the presence of H₂O. The experimental results demonstrated that SO₂ and NO had pronounced inhibitory effects on Hg⁰ oxidation at high temperatures when H₂O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg²⁺ back into its elemental form. Data revealed that SO₂ and NO were capable of promoting homogeneous reduction of Hg²⁺ to Hg⁰ with H₂O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H₂O was removed from the gas blend.     

Hg<Superscript>2+</Superscript> detection using a disposable and miniaturized screen-printed electrode modified with nanocomposite carbon black and gold nanoparticles

A miniaturized screen-printed electrode (SPE) modified with a carbon black-gold nanoparticle (CBNP-AuNP) nanocomposite has been developed as an electrochemical sensor for the detection of inorganic mercury ions (Hg²⁺). The working electrode surface has been modified with nanocomposite constituted of CBNPs and AuNPs by an easy drop casting procedure that makes this approach extendible to an automatable mass production of modified SPEs. Square wave anodic stripping voltammetry (SWASV) was adopted to perform Hg²⁺ detection, revealing satisfactory sensitivity and detection limit, equal to 14 μA ppb^?1 cm^?2 and 3 ppb, respectively. The applicability of the CBNP-AuNP-SPE for the determination of inorganic mercury has been assessed in river water by a simple filtration and acidification of the sample as well as in soil by means of a facile acidic extraction procedure assisted by ultrasound.     

Selective Reduction of Nitrogen Oxides In Combustion Flue Gases

The body of Information presented in this paper is directed to those Individuals concerned with the removal of NO_x in combustion flue gases. A catalytic process for the selective reduction of nitrogen oxides by ammonia has been investigated. Efforts were made toward the development of catalysts resistant to SO_x poisoning. Nitrogen oxides were reduced over various metal oxide catalysts in the presence or absence of SO_x(SO₂ and SO₃). Catalysts consisting of oxides of base metals (for example, Fe₂O₃) were easily poisoned by SO₃, forming sulfates of the base metals. A series of catalysts which are not susceptible to the SO_x poisoning has been developed. The catalysts possess a high activity and selectivity over a wide range of temperatures, 250—450°C. The catalysts were tested in a pilot plant which treated a flue gas containing 110-150 ppm NO_x, 660-750 ppm SO₂, and 40-90 ppm SO₃. The pilot plant was operated at 350°C and at a space velocity of 10,000 h^-1. The removal of nitrogen oxides was more than 90% for several months.

A mechanism of the NO-NH₃ reaction has also been investigated. It is found that NO reacts with NH₃ at a 1:1 mole ratio in the presence of oxygen and the reaction is completely inhibited by the absence of oxygen. The experimental data show that the NO-NH₃ reaction in the presence of oxygen is represented byNO + NH₃ + 1/4 O₂ = N₂ + 3/2 H₂O.     

The effects and the toxicity increases caused by bicarbonate,chloride, and other water components during the UV/TiO<Subscript>2</Subscript> degradation of oxazaphosphorine drugs

The influences of HCO₃ ^?, Cl^?, and other components on the UV/TiO₂ degradation of the antineoplastic agents ifosfamide (IFO) and cyclophosphamide (CP) were studied in this work. The results indicated that the presence of HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2? in water bodies resulted in lower degradation efficiencies. The half-lives of IFO and CP were 1.2 and 1.1 min and increased 2.3–7.3 and 3.2–6.3 times, respectively, in the presence of the four anions (initial compound concentration = 100 μg/L, TiO₂ loading =100 mg/L, anion concentration = 1000 mg/L, and pH = 8). Although the presence of HCO₃ ^? in the UV/TiO₂/HCO₃ ^? system resulted in a lower degradation rate and less byproduct formation for IFO and CP, two newly identified byproducts, P11 (M.W. = 197) and P12 (M.W. = 101), were formed and detected, suggesting that additional pathways occurred during the reaction of ?CO₃ ^? in the system. The results also showed that ?CO₃ ^? likely induces a preferred ketonization pathway. Besides the inorganic anions HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2?, the existence of dissolved organic matter in the water has a significant effect and inhibits CP degradation. Toxicity tests showed that higher toxicity occurred in the presence of HCO₃ ^? or Cl^? during UV/TiO₂ treatment and within 6 h of reaction time, implying that the effects of these two anions should not be ignored when photocatalytic treatment is applied to treat real wastewater.     

Use of carbon-based composites to enhance performance of TiO<Subscript>2</Subscript> for the simultaneous removal of nitrates and organics from aqueous environments

The simultaneous photocatalytic removal of nitrate from aqueous environment in presence of organic hole scavenger using TiO₂ has long been explored. However, the use of unmodified TiO₂ in such reaction resulted in non-performance or release of significant amount of undesirable reaction products in the process, a problem that triggered surface modification of TiO₂ for enhanced photocatalytic performance. Previous studies focused on decreasing rate of charge carrier recombination and absorption of light in the visible region. Yet, increasing active sites and adsorption capacity by combining TiO₂ with a high surface area adsorbent such as activated carbon (AC) remains unexploited. This study reports the potential of such modification in simultaneous removal of nitrates and oxalic acid in aqueous environment. The adsorptive behaviour of nitrate and oxalic acid on TiO₂ and TiO₂/AC composites were studied. The Langmuir adsorption coefficient for nitrate was four times greater than that of oxalic acid. However, the amount of oxalic acid adsorbed was about 10 times greater than the amount of nitrate taken up. Despite this advantage, the materials did not appear to produce more active photocatalysts for the simultaneous degradation of nitrate and oxalic acid. The photocatalytic activity of TiO₂ and its carbon-based composites was improved by combination with Cu₂O particles. Consequently, 2.5 Cu₂O/TiO₂ exhibited the maximum photocatalytic performance with 57.6 and 99.8% removal of nitrate and oxalic acid, respectively, while selectivity stood at 45.7, 12.4 and 41.9% for NH₄⁺, NO₂^? and N₂, respectively. For the carbon based, 2.5 Cu₂O/TiO₂-20AC showed removal of 12.7% nitrate and 80.3% oxalic acid and achieved 21.6, 0 and 78.4% selectivity for NH₄⁺, NO₂^? and N₂, respectively. Using the optimal AC loading (20 wt%) resulted in significant decrease in the selectivity for NH₄⁺ with no formation of NO₂^?, which unveils that selectivity for N₂ and low/no selectivity for undesirable products can be manipulated by controlling the rate of consumption of oxalic acid. In contract, no nitrate reduction was observed with Cu₂O promoted TiO₂-T and its TiO₂-(T)-20AC, which may be connected to amorphous nature of TiO₂-T and perhaps served as charge carrier trapping sites that impeded activity.     

Photocatalytic decomposition of N<Subscript>2</Subscript>O over g-C<Subscript>3</Subscript>N<Subscript>4</Subscript>/WO<Subscript>3</Subscript> photocatalysts

Although the nitrous oxide belongs among three of the most contributing greenhouse gases to global warming, it is quite neglected by photocatalytic society. The g-C₃N₄ and WO₃ composites were therefore tested for the photocatalytic decomposition of N₂O for the first time. The pure photocatalysts were prepared by simple calcination of precursors, and the composites were prepared by mixing of suspension of pure components in water followed by calcination. The structural (X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy), textural (N₂ physisorption), and optical properties (diffuse reflectance spectroscopy, photoluminescence spectroscopy, photoelectrochemical measurements) of all composites were correlated with photocatalytic activity. The experimental results and results from characterization techniques confirmed creation of Z-scheme in the WO₃/g-C₃N₄ composites, which was confirmed by hydroxyl radicals’ trapping measurements. The photocatalytic decomposition of N₂O was carried out in the presence of UVA light (peak intensity at 365 nm) and the 1:2 WO₃/g-C₃N₄ composite was the most active one, but the photocatalytic activity was just negligibly higher than that of pure WO₃. This is caused by relatively weak interaction between WO₃ and g-C₃N₄ which was revealed from XPS.