Electrochemical treatment of ammonia in wastewater by RuO<Subscript>2</Subscript>–IrO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>/Ti electrodes

This study investigated the removal of ammonia in wastewater by an electrochemical method using titanium electrodes coated with ruthenium and iridium (RuO₂–IrO₂–TiO₂/Ti) with low chlorine evolution over-voltage. The effects of operating parameters, including chloride ion concentration, current density and initial pH, were also investigated. The results were evaluated primarily by considering the efficiency of the elimination of NH₄⁺-N. The removal of ammonia by electrochemical oxidation mainly resulted from the indirect oxidation effect of chlorine/hypochlorite produced during electrolysis. The direct anodic oxidation efficiency of ammonia was less than 5%, and the current efficiency was less than 10%. The ammonia removal followed pseudo-first-order kinetics. The electrochemical process can be applied successfully as a final polishing step, or as an alternative method to biological nitrification. The process seems to be most beneficial for small coastal cities     

Electrochemical oxidation of an acid dye by active chlorine generated using Ti/Sn<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Ir<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript> electrodes

The generation of active chlorine on Ti/Sn_(1−x)Ir _x O₂ anodes, with different compositions of Ir (x = 0.01, 0.05, 0.10 and 0.30 ), was investigated by controlled current density electrolysis. Using a low concentration of chloride ions (0.05 mol L⁻¹) and a low current density (5 mA cm⁻²) it was possible to produce up to 60 mg L⁻¹ of active chlorine on a Ti/Sn_0.99Ir_0.01O₂ anode. The feasibility of the discoloration of a textile acid azo dye, acid red 29 dye (C.I. 16570), was also investigated with in situ electrogenerated active chlorine on Ti/Sn_(1−x)Ir _x O₂ anodes. The best conditions for 100% discoloration and maximum degradation (70% TOC reduction) were found to be: NaCl pH 4, 25 mA cm⁻² and 6 h of electrolysis. It is suggested that active chlorine generation and/or powerful oxidants such as chlorine radicals and hydroxyl radicals are responsible for promoting faster dye degradation. Rate constants calculated from color decay versus time reveal a zero order reaction at dye concentrations up to 1.0 × 10⁻⁴ mol L⁻¹. Effects of other electrolytes, dye concentration and applied density currents also have been investigated and are discussed.     

Comparison of Cu–Ce–Zr and Cu–Zn–Al mixed oxide catalysts for water-gas shift

Cu–Zn–Al and Cu–Ce–Zr mixed oxide catalysts were prepared by two different methods, co-precipitation and flame spray pyrolysis. The performance of the catalysts was evaluated using the water-gas shift reaction with and without CO₂ and H₂ added to the feed. Cu–Ce–Zr catalysts are found not to be superior to Cu–Zn–Al catalysts in terms of initial activity and short-term stability. Their apparent activation energy appears to be less affected by increased concentrations of CO₂ and H₂.     

Partial oxidation of methane over Ni/Ce-Zro<Subscript>2</Subscript>/θ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The catalytic behavior of Ni/Ce-ZrO₂/θ-Al₂O₃ has been investigated in the partial oxidation of methane (POM) toward synthesis gas. The catalyst showed high activity and selectivity due to the heat treatment of the support and the promotional effect of Ce-ZrO₂. It is suggested that the support was stabilized through the heat treatment of γ-Al₂O₃ and the precoating of Ce-ZrO₂, on which a protective layer was formed. Moreover, sintering of the catalyst was greatly suppressed for 24 h test. Pulse experiments of CH₄, O₂ and/or CH₄/O₂ with a molar ratio of 2 were systematically performed over fresh, partially reduced and well reduced catalyst. Results indicate that CH₄ can be partially oxidized to CO and H₂ by the reactive oxygen in complex NiO_x species existing over the fresh catalyst. It is demonstrated that POM over Ni/Ce-ZrO₂/θ-Al₂O₃ follows the pyrolysis mechanism, and both the carbonaceous materials from CH₄ decomposition over metallic nickel and the reactive oxygen species present on NiO_x and Ce-ZrO₂ are intermediates for POM.     

Hydrothermal deactivation of Ce‐ZSM‐5, Ce‐beta, Ce‐mordenite and Ce‐Y zeolite deNOx catalysts

The hydrothermal stability of Ce³⁺ zeolite catalysts used for selective catalytic reduction of NO _x was investigated. Aging of Ce‐ZSM‐5, Ce‐beta, Ce‐mordenite and Ce‐Y catalysts consisted of steaming in 10 or 12 vol% water at 600°C for 3–99 h. Ce‐ZSM‐5 (Si/Al ratios: Si/Al = 17.1, 22.6 and 146.6) and Ce‐mordenite (Si/Al = 6.4, IE = 77.2%) showed fast deactivation. Ce‐beta (Si/Al = 12, IE = 68.4%) and Ce‐Y (Si/Al = 2.8, IE = 122%) are significantly more stable zeolite catalysts, Ce‐beta being the most active of these two. Ce‐beta and Ce‐ZSM‐5 catalysts – both having high initial activities – were characterized with ²⁹Si‐NMR and ²⁷Al‐NMR. Especially Ce‐ZSM‐5 showed an increase of non‐framework Al, meaning that the zeolite suffered from dealumination. This revised version was published online in July 2006 with corrections to the Cover Date.     

Performance of Ni catalyst supported on La-hexaaluminate in CO<Subscript>2</Subscript> reforming of CH<Subscript>4</Subscript>

CO₂ reforming of CH₄ was performed using Ni catalyst supported on La-hexaaluminate which has been an well-known material for high-temperature combustion. La-hexaaluminate was synthesized by sol-gel method at various conditions where different amount of Ni (5–20 wt%) was loaded. Ni/La-hexaaluminate experienced 72 h reaction and its catalytic activity was compared with that of Ni/Al₂O₃, Ni/La-hexaaluminate shows higher reforming activity and resistance to coke deposition compared to the Ni/Al₂O₃ model catalyst. Coke deposition increases proportionally to Ni content. Consequently, Ni(5)/La-hexaaluminate(700) is the most efficient catalyst among various Ni/La-hexaaluminate catalysts regarding the cost of Ni in Ni(X)/La-hexaaluminate catalysts. BET surface area, XRD, EA, TGA and TPO were performed for surface characterization. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Trapping characteristics of volatile ruthenium oxides by Y<Subscript>2</Subscript>O<Subscript>3</Subscript> filter

Yttria filter has been suggested as a trapping agent for gaseous oxides of ruthenium volatilized during DUPIC fuel fabrication process. Experiments were performed to evaluate the trapping characteristics of gaseous ruthenium oxides by yttria ceramic foam filters in the two-zone furnace under air condition. Yttria filter is expected to offer stable material in which the volatility of the ruthenium can be effectively trapped because of its incorporation into a lattice of high stability over 900 ‡C under air condition. The XRF result of ruthenium trapped on an yttria filter under air condition showed that concentrations of ruthenium on the back and the front faces of the filter decreased linearly with increasing superficial air velocity, and the back face concentration of filter was lower than the front face concentration by about 30-45%. The TGA result of ruthenium trapped on an yttria filter indicates that there is weight loss of 5.8 wt% up to 1,400 ‡C, which is believed to be due to the fact that the thermally stable Y₂Ru₂O₇ phase was formed on an yttria filter.     

Method of estimating absolute concentrations of C<Subscript>2</Subscript>H<Subscript>5</Subscript> and H radicals in hydrocarbon diffusion flames

A method for estimating absolute concentrations of C₂H₅ and H radicals in hydrocarbon diffusion flames is proposed and substantiated. Concentration profiles of C₂H₅ and H on the flame axis are obtained. In the method proposed, the concentration of C₂H₅ is determined from the equality of two quantities — the rate of loss of n-butane by diffusion and the rate of its formation by recombination of two C₂H₅ radicals. The concentration of H radicals is determined from the relation between the ratio C₂H₅/H and experimental profiles of C₂H₄, C₂H₆, and O₂. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 6, pp. 13–20, November–December, 2007.     

Influences of A- or B-site substitution on the activity of LaMnO<Subscript>3</Subscript> perovskite-type catalyst in oxidation of diesel particle

LaMnO₃ was partially substituted at A- or B-site by Sol-Gel method and characterized by XRD, SEM and BET. Perovskite oxides were formed in all substitutions. The catalytic activities of substituted catalysts on carbon black oxidation were measured by Temperature Programming Oxidation (TPO). Experimental results showed that all substitutions increased the catalytic activity of LaMnO₃, and La_0.8Cs_0.2MnO₃ showed the highest catalytic activity. Under tight contact, the activity enhancement of different substitutions decreased in the order Cs>K>V>Ce>Co>Cu>Fe. Dynamic analysis showed that partial substitutions increased the pre-exponential factor and the catalytic activity by increasing the oxygen vacancy on the catalyst surface. The active components on the surfaces of La_0.8Ce_0.2MnO₃ and LaMn_0.8V_0.2O₃ included CeO₂ and LaVO₄, which changed the apparent activities and dynamic parameters of these two catalysts. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

ΝΗ<Subscript>3</Subscript> decomposition in a proton conducting solid electrolyte cell

The reaction of NH₃ decomposition was studied on Ag in a proton conducting double chamber cell-reactor. The proton conductor was a strontia-ceria-ytterbia (SCY) perovskite of the form SrCe_0.95Yb_0.05O_3−α. The reaction was studied at 350–700 °C and atmospheric total pressure. The proton transference number (PTN) was calculated by simultaneous measurement of the imposed current and the proton flux and it was found to vary between 0.5 and 0.7. The effects of imposed current, temperature and inlet gas composition on the reaction rate and the PTN, were examined. Although the faradaic efficiency (Λ) remained near unity in all experiments, reaction rate enhancements (ρ) as high as 57 were achieved. An up to 90% decrease in the activation energy of the reaction was observed when protons were electrochemically “pumped” away from the catalyst.     

Reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> in diesel engine emissions by using a plasmatron fuel reformer

An experimental study of diesel exhaust cleaning by means of the plasma chemical pretreatment of fuel is described. Some portion of the fuel was activated in an arc discharge and turned into hydrogen-rich synthesis gas. Plasma chemical reformation of fuel was carried out by using a DC arc plasmatron that was fabricated to increase the ability of gas activation. The yield of diesel fuel reformation reached about 80−100% when small quantities of fuel (flow rate up to ∼6 ml/min) were reformed. The synthesis gas, containing H₂+CO, was supplied into the engine together with the rest of the fuel-air mixture, and the NO _x content in its emissions reduced up to 23%. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Effects of preparation methods for V<Subscript>2</Subscript>O<Subscript>5</Subscript>-TiO<Subscript>2</Subscript> aerogel catalysts on the selective catalytic reduction of NO with NH<Subscript>3</Subscript>

A series of V₂O₅-TiO₂ aerogel catalysts were prepared by the sol-gel method with subsequent supercritical drying with CO₂. The main variables in the sol-gel method were the amounts of V₂O₅ and when the vanadium precursor was introduced. V₂O₅-TiO₂ xerogel and V₂O₅/TiO₂ (P-25) were also prepared for comparison. The V₂O₅-TiO₂ aerogel catalysts showed much higher surface areas and total pore volumes than V₂O₅-TiO₂ xerogel and impregnated V₂O₅/TiO₂ (P-25) catalysts. The catalysts were characterized by N₂ physisorption, X-ray diffraction (XRD), FT-Raman spectroscopy, temperature-programmed reduction with H₂ (H₂-TPR), and temperature-programmed desorption of ammonia (NH₃-TPD). The selective catalytic reduction of NOx with ammonia in the presence of excess O₂ was studied over these catalysts. Among various V₂O₅-TiO₂ catalysts, V₂O₅ supported on aerogel TiO₂ showed a wide temperature window exhibiting high NOx conversions. This superior catalytic activity is closely related to the large amounts of strong acidic sites as well as the surface vanadium species with characteristics such as easy reducibility and monomeric and polymeric vanadia surface species. This work was presented at the 7 ^th Korea-China Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Hydrotreating of Heavy Gas Oil Derived from Athabasca Bitumen Over Co–Mo/γ-Al2O3 Catalyst Prepared by Sonochemical Method

Co–Mo/γ-Al₂O₃ oxide containing 9.8 wt% Mo and 2.9 wt% Co was prepared by high-intensity ultrasonic irradiation of Mo(CO)₆, Co₂(CO)₈, and γ-Al₂O₃ in decahydronapthalene under air flow. The oxidic Co–Mo catalyst thus formed was characterized by elemental analysis, BET N₂ adsorption and XRD. The surface sites on the sulfided Co–Mo/γ-Al₂O₃ catalyst were characterized by infrared spectroscopy of CO adsorption. Hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) activities were evaluated for heavy gas oil derived from Athabasca bitumen in a trickle bed reaction system using the following conditions: temperatures ranging from 370 to 400 °C, a pressure of 8.8 MPa, a liquid hourly space velocity of 1 h⁻¹, and a H₂/feed ratio of 600 ml/ml. The dispersion, nature of active sites and hydrotreating activity of this catalyst were compared with the conventionally prepared Co–Mo/γ-Al₂O₃ catalyst containing similar wt% of Mo and Co. The Co–Mo catalyst prepared by sonochemical method has higher HDN and HDS rate constants than the conventional catalyst due to an improved dispersion of MoS₂.     

Experimental study of N<Subscript>2</Subscript> dilution on bluff-body stabilized LPG jet diffusion flame

The present paper reports the effects of N₂ addition and preheating of reactants on bluff-body stabilized coaxial LPG jet diffusion flame for two cases, namely, (I) preheated air and (II) preheated air and fuel. Experimental results confirm that N₂ addition to the fuel stream leads to an enhancement in flame length, which may be attributed to the reduction in flame temperature. The soot free length fraction (SFLF) also increases, which might be caused by the decrease in fuel concentration and flame temperature. The flame length and also the SFLF are observed to be reduced with increasing temperature of reactants and lip thickness of the bluff body. The NO _x emission level for all burner configurations are found to be attenuated with nitrogen addition, which can be attributed to the reduction of the residence time of the gas mixture in the flame. The emission index of NO _x (EINO _x ) also becomes enhanced with increasing lip thickness and reactant temperature due to an increased residence time and thermal effect, respectively. __________ Translated from Fizika Goreniya i Vzryva, Vol. 45, No. 1, pp. 3–10, January–February, 2009.     

Industrial test on coal re-burning at a 600 MW utility boiler and NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reduction

This research conducts a series of industrial tests on coal reburning of a 600 MW pulverized coal boiler firing lignite, which is one part of a coal reburning demonstration project. When running steadily under 600 MW load, the boiler has an average NO _x emission of 274 mg/m³ (O₂ content in flue gas is converted to 6%), the NO _x emission is reduced by 65.36%. In the meanwhile, loss of ignition (LOI) under coal reburning rarely increases. Three operation conditions — traditional air feeding, air staging and coal reburning — are realized, respectively, during the industrial tests, and the results indicate that coal reburning has the lowest NO _x emission, while the traditional air feeding has the highest NO _x emission. Under the test conditions, the higher the proportion of the reburning coal, the higher the NO _x control can reach. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Interaction Between Atmospheric CO<Subscript>2</Subscript> and Glucosinolates in Broccoli

Total and individual glucosinolate contents of broccoli cv Marathon were assessed at ambient CO₂ (430–480 ppm) and elevated atmospheric CO₂ (685–820 ppm) to determine the ecological relationship between changing atmospheric CO₂ concentrations and phytochemicals. Elevated atmospheric CO₂ concentration had a differing effect on individual glucosinolates and glucosinolate groups. Total glucosinolate content increased at elevated atmospheric CO₂ concentration as a result of a strong increase in both methylsulfinylalkyl glucosinolates glucoraphanin and glucoiberin. In contrast, indole glucosinolates simultaneously decreased, predominantly because of a reduction of glucobrassicin and 4-methoxy-glucobrassicin contents. We conclude that changes in N content and N/S ratios as well as alterations in photochemical processes at elevated atmospheric CO₂ concentration can influence total and individual glucosinolates contents of Brassicaceae, as demonstrated in the greenhouse, for broccoli.     

Synthesis of cathode material LiNi<Subscript>1-<Emphasis Type="Italic">y</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>O<Subscript>2</Subscript> by a simplified combustion method

The optimum conditions for synthesizing LiNi_1-y Co _y O₂ (y=0.1, 0.3 and 0.5) by a simplified combustion method, in which the preheating step is omitted, and the electrochemical properties of these materials were investigated. The optimum condition for synthesizing LiNi_0.9Co_0.1O₂ by the simplified combustion method is calcination at 800 °C for 12 h in air in 3.6 mole ratio of urea to nitrate. The LiNi_0.9Co_0.1O₂ synthesized under these conditions shows the smallest R-factor{(I ₀₀₆+I ₁₀₂)/I ₁₀₁} and the largest I ₀₀₃/I ₁₀₄, indicating better hexagonal ordering and less cation mixing, respectively. The LiNi_0.7Co_0.3O₂ synthesized at 800 °C for 12 h in air in 3.6 mole ratio of urea to nitrate has the largest first discharge capacity 156.2 mA h g⁻¹ at 0.5C and shows relatively good cycling performance. This sample shows better hexagonal ordering and less cation mixing than the other samples. The particle size of the LiNi_0.7Co_0.3O₂ is relatively small and its particles are spherical with uniform particle size.     

<Emphasis Type="Italic">Phytolacca americana</Emphasis> from Contaminated and Noncontaminated Soils of South Korea: Effects of Elevated Temperature,CO<Subscript>2</Subscript> and Simulated Acid Rain on Plant Growth Response

Chemical analyses performed on the invasive weed Phytolacca americana (pokeweed) growing in industrially contaminated (Ulsan) and noncontaminated (Suwon) sites in South Korea indicated that the levels of phenolic compounds and various elements that include some heavy metals (Al, As, B, Cd, Co, Cu, Fe, Mn, Ni, Pb, and Zn) were statistically higher in Ulsan soils compared to Suwon soils with Al being the highest (>1,116 mg/l compared to 432 mg/l). Analysis of metals and nutrients (K, Na, Ca, Mg, Cl, NH₄, N, P, S) in plant tissues indicated that accumulation occurred dominantly in plant leaves with Al levels being 33.8 times higher in Ulsan plants (PaU) compared to Suwon plants (PaS). The ability of PaU and PaS to tolerate stress was evaluated under controlled conditions by varying atmospheric CO₂ and temperature and soil pH. When grown in pH 6.4 soils, the highest growth rate of PaU and PaS plants occurred at elevated (30°C) and non-elevated (25°C) temperatures, respectively. Both PaU and PaS plants showed the highest and lowest growth rates when exposed to atmospheric CO₂ levels of 360 and 650 ppm, respectively. The impact of soil pH (2–6.4) on seed germination rates, plant growth, chlorophyll content, and the accumulation of phenolics were measured to assess the effects of industrial pollution and global-warming-related stresses on plants. The highest seed germination rate and chlorophyll content occurred at pH 2.0 for both PaU and PaS plants. Increased pH from 2–5 correlated to increased phenolic compounds and decreased chlorophyll content. However, at pH 6.4, a marked decrease in phenolic compounds, was observed and chlorophyll content increased. These results suggest that although plants from Ulsan and Suwon sites are the same species, they differ in the ability to deal with various stresses.     

Synthesis of Heterogeneous Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> Nanostructured Anodes with Long-Term Cycle Stability

The 0D-1D Lithium titanate (Li₄Ti₅O₁₂) heterogeneous nanostructures were synthesized through the solvothermal reaction using lithium hydroxide monohydrate (Li(OH)·H₂O) and protonated trititanate (H₂Ti₃O₇) nanowires as the templates in an ethanol/water mixed solvent with subsequent heat treatment. A scanning electron microscope (SEM) and a high resolution transmission electron microscope (HRTEM) were used to reveal that the Li₄Ti₅O₁₂ powders had 0D-1D heterogeneous nanostructures with nanoparticles (0D) on the surface of wires (1D). The composition of the mixed solvents and the volume ratio of ethanol modulated the primary particle size of the Li₄Ti₅O₁₂ nanoparticles. The Li₄Ti₅O₁₂ heterogeneous nanostructures exhibited good capacity retention of 125 mAh/g after 500 cycles at 1C and a superior high-rate performance of 114 mAh/g at 20C.     

Sorption studies of CO<Subscript>2</Subscript>, CH<Subscript>4</Subscript>, N<Subscript>2</Subscript>, CO,O<Subscript>2</Subscript> and Ar on nanoporous aluminum terephthalate [MIL-53(Al)]

Aluminum terephthalate, MIL-53(Al), metal–organic framework synthesized hydrothermally and purified by solvent extraction method was used as an adsorbent for gas adsorption studies. The synthesized MIL-53(Al) was characterized by powder X-Ray diffraction analysis, surface area measurement using N₂ adsorption–desorption at 77 K, FTIR spectroscopy and thermo gravimetric analysis. Adsorption isotherms of CO₂, CH₄, CO, N₂, O₂ and Ar were measured at 288 and 303 K. The absolute adsorption capacity was found in the order CO₂>CH₄>CO>N₂>Ar>O₂. Henry’s constants, heat of adsorption in the low pressure region and adsorption selectivities for the adsorbate gases were calculated from their adsorption isotherms. The high selectivity and low heat of adsorption for CO₂ suggests that MIL-53(Al) is a potential adsorbent material for the separation of CO₂ from gas mixtures. The high selectivity for CH₄ over O₂ and its low heat of adsorption suggests that MIL-53(Al) could also be a compatible adsorbent for the separation of methane from methane–oxygen gas mixtures.