A scheme for solving strongly coupled chemical reaction equations appearing in the removal of SO2 and NOx from flue gases

The removal of NO_x from mixtures of NO-NO₂-N₂ and NO-NO₂-O₂-H₂O is discussed theoretically in this study, and the removal of ₂SO and xNO is further discussed when a gas system of NO_x-N₂-O₂-H₂O contains CO₂ and SO₂. The involved chemical reaction rate equations in the process of SO₂/NO_x removal are solved numerically using Treanor's method, in which a scheme separating chemical reactions into fast and slow groups has been proposed for improving the numerical stability. Numerical results show that the contribution of ion reactions to xNO removal is negligible, and that high temperature is not beneficial for the NO oxidation. However, high concentration of O₂ is conducive to the NO oxidation. Addition of water facilitates the NO_x removal, and increasing water vapor concentration enhances the NO_x removal efficiency; inclusion of CO₂ and SO₂ into the system favors the NO removal.     

Photocatalytic degradation of NOx gases using TiO2-containing paint: a real scale study

An indoor car park was appropriately equipped in order to test the de-polluting efficiency of a TiO(2)-containing paint in an indoor polluted environment, under real scale configuration. Depollution tests were performed in an artificially closed area of the parking, which was polluted by a car exhaust during the testing period. The ceiling surface of the car park was covered with white acrylic TiO(2)-containing paint (PP), which was developed in the frame of the EU project 'PICADA' (Photocatalytic Innovative Coverings Application for Depollution Assessment). The closed area was fed with car exhaust gases. As soon as the system reached steady state, the UV lamps were turned on for 5h. The difference between the final and the initial steady state concentration indicates the removal of the pollutants due to both the photocatalytic paint and car emission reduction. Results showed a significant photocatalytic oxidation of NO(x) gases. The photocatalytic removal of NO and NO(2) was calculated to 19% and 20%, respectively, while the photocatalytic rate (microgm(-2)s(-1)) ranged between 0.05 and 0.13 for NO and between 0.09 and 0.16 for NO(2).     

Diesel emission control system using combined process of nonthermal plasma and exhaust gas components' recirculation

A NO_x aftertreatment system, using nonthermal plasma (NTP) reduction and exhaust gas components' recirculation, is investigated. A pilot-scale system is applied to a stationary diesel engine. In this system, NO_x is first removed by adsorption, and subsequently, the adsorbent is regenerated by thermal desorption. NO_x desorbed is reduced by using nitrogen NTP. Moreover, NO_x, CO₂, and water vapor recirculated into the engine intake reduce NO_x. In this study, approximately 57% of the NO_x of the exhaust (NO_x: 240-325 ppm, flow rate = 300 NL/min) can be continuously treated for 58 h. A system energy efficiency of 120 g (NO₂)/kWh is obtained.     

Desulfurization from thiophene by SO(4)(2-)/ZrO(2) catalytic oxidation at room temperature and atmospheric pressure

Thiophene, due to its poison, together with its combustion products which causes air pollution and highly toxic characteristic itself, attracted more and more attention to remove from gasoline and some high concentration systems. As the purpose of achieving the novel method of de-thiophene assisted by SO(4)(2-)/ZrO(2) (SZ), three reactions about thiophene in different atmosphere at room temperature and atmospheric pressure were investigated. SO(4)(2-)/ZrO(2) catalyst were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The products were detected by gas chromatography-mass spectrometry (GC-MS). XP spectra show that ozone-catalyst system (SZO) have two forms of sulfur element (S(6+) and S(2-)) on the catalyst surface, which distinguished from that of air-catalyst system (SZA) and blank-catalyst system (SZB) (S(6+)). And the results of GC-MS exhibited that some new compounds has been produced under this extremely mild condition. Especially, many kinds of sulfur compounds containing oxygen, that is easier to be extracted by oxidative desulfurization (ODS), have been detected in the SZA-1.5h and SZB-3h system. In addition, some long chain hydrocarbons have also been detected. While in SZO-0.5h system, only long chain hydrocarbons were found. The results show that total efficiency of desulfurization from thiophene with ozone near to 100% can be obtained with the SO(4)(2-)/ZrO(2) catalytic oxidation reaction.     

Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst

The effect of SO₂ gas was investigated on the activity of the photo-assisted selective catalytic reduction of nitrogen monoxide (NO) with ammonia (NH₃) over a TiO₂ photocatalyst in the presence of excess oxygen (photo-SCR). The introduction of SO₂ (300 ppm) greatly decreased the activity of the photo-SCR at 373 K. The increment of the reaction temperature enhanced the resistance to SO₂ gas, and at 553 K the conversion of NO was stable for at least 300 min of the reaction. X-ray diffraction, FTIR spectroscopy, thermogravimetry and differential thermal analysis, x-ray photoelectron spectroscopy (XPS), elemental analysis and N₂ adsorption measurement revealed that the ammonium sulfate species were generated after the reaction. There was a strong negative correlation between the deposition amount of the ammonium sulfate species and the specific surface area. Based on the above relationship, we concluded that the deposition of the ammonium sulfate species decreased the specific surface area by plugging the pore structure of the catalyst, and the decrease of the specific surface area resulted in the deactivation of the catalyst.     

Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst

Abstract

The effect of SO₂ gas was investigated on the activity of the photo-assisted selective catalytic reduction of nitrogen monoxide (NO) with ammonia (NH₃) over a TiO₂ photocatalyst in the presence of excess oxygen (photo-SCR). The introduction of SO₂ (300 ppm) greatly decreased the activity of the photo-SCR at 373 K. The increment of the reaction temperature enhanced the resistance to SO₂ gas, and at 553 K the conversion of NO was stable for at least 300 min of the reaction. X-ray diffraction, FTIR spectroscopy, thermogravimetry and differential thermal analysis, x-ray photoelectron spectroscopy (XPS), elemental analysis and N₂ adsorption measurement revealed that the ammonium sulfate species were generated after the reaction. There was a strong negative correlation between the deposition amount of the ammonium sulfate species and the specific surface area. Based on the above relationship, we concluded that the deposition of the ammonium sulfate species decreased the specific surface area by plugging the pore structure of the catalyst, and the decrease of the specific surface area resulted in the deactivation of the catalyst.     

SO2 and NOx removal by electron beam and electrical discharge induced non-thermal plasmas

An installation containing a DC negative corona discharge reactor, a pulse corona discharge reactor and a combined electron beam and microwave induced plasma reactor is presented. SO₂ is removed up to 42% through spontaneous reaction with ammonia without electron beam or microwave irradiation at the temperature below 70 °C. For the same removal efficiency of 98% for SO₂ and 80% for NO_x at separate EB irradiation of 40 kGy, the required absorbed dose is about two times smaller for simultaneous electron beam and microwave irradiation. The SO₂ removal efficiency of simultaneous DC or positive discharge and microwave discharge is higher than separate DC, pulse and MW discharge. Also, the applied voltage level at which the removal efficiency reaches the maximum value is less than for the separate application of DC or pulse discharge. The NO_x removal efficiency of DC or pulse discharge suffers little change by additional use of the microwave energy.     

Extinction Coefficients of NO2 and N2O4

The extinction coefficient of NO₂ has been measured in the spectral range 185 to 410 nm as a function of temperature between 235 and 298 K. In order to correct for the effect of the dimer absorption, the extinction coefficient of N₂O₄ has also been measured. The effect of a decrease in temperature upon the NO₂ absorption is a reduction in the extinction coefficient of approximately 10 percent in the range 320 to 380 nm.     

Influence of flue gas SO2 on the toxicity of heavy metals in municipal solid waste incinerator fly ash after accelerated carbonation stabilization

The influence of CO₂ content and SO₂ presence on the leaching toxicity of heavy metals in municipal solid waste incinerator (MSWI) fly ash was studied by examining the carbonation reaction of MSWI fly ash with different combinations of simulated incineration flue gases. Compared with raw ash, the leaching solution pH of carbonated ash decreased by almost 1 unit and the leaching concentrations of heavy metals were generally lower, with that of Pb decreasing from 19.45 mg/L (raw ash) to 4.08 mg/L (1# carbonated ash). The presence of SO₂ in the incineration flue gas increased the leaching concentrations of heavy metals from the fly ash to different extents after the carbonation stabilization reaction. The pH of the leaching solution was the main factor influencing the leaching concentrations of heavy metals. The increase in buffer capacity with the pH of carbonated ash caused an increase in heavy metal stability after the carbonation reaction. Accelerated carbonation stabilization of MSWI fly ash could reduce its long-term leaching concentrations (toxicity) of Cu, Pb, Se, and Zn. The leaching concentrations of heavy metals from carbonated ash also likely had better long-term stability than those from raw ash. The presence of SO₂ in the incineration flue gas increased the proportion of exchangeable state species of heavy metals; slightly increased the long-term leaching toxicity of Cu, Pb, Se, and Zn; and reduced the long-term stability of these metals in the fly ash after the carbonation reaction.     

Visible light absorption ability and photocatalytic oxidation activity of various interstitial N-doped TiO2 prepared from different nitrogen dopants

Nitrogen-doped TiO₂ was developed to enable photocatalytic reactions using the visible range of the solar spectrum. This work reports on the synthesis, characterisation and kinetic study of interstitial N-doped TiO₂ prepared by the sol–gel method using three different types of nitrogen dopants: diethanolamine, triethylamine and urea. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and UV–visible spectroscopy were used to analyse the titania. Different interstitial N-doped TiO₂ properties, such as absorption ability in the UV–visible light region, redshift in adsorption edge, good crystallisation and composition ratio of titania structures (anatase and rutile) could be obtained from different nitrogen dopants. Amongst investigated nitrogen precursors, diethanolamine provided the highest visible light absorption ability of interstitial N-doped TiO₂ with the smallest energy bandgap and the smallest anatase crystal size, resulting in the highest efficiency in 2-chlorophenol degradation. The photocatalytic activity of all N-doped TiO₂ can be arranged in the following order: TiO₂/diethanolamine > TiO₂/triethylamine > TiO₂/urea > un-doped TiO₂. The initial rate of 2-chlorophenol degradation using the interstitial N-doped TiO₂ with diethanolamine was 0.59 mg/L-min and the kinetic constant was 2.34 × 10⁻² min⁻¹ with a half-life of 98 min. In all cases, hydroquinone was detected as a major intermediate in the degradation of 2-chlorophenol.     

Simple synthesis of ZrO2/SiOx core/shell nanofibers using ZrSi2 with gallium

ZrO₂/SiO_x core/shell nanofibers with diameter ~ 50 nm were synthesized by the thermal oxidation of ZrSi₂ substrates with gallium. The crystalline ZrO₂ cores were grown with amorphous SiO_x shells. It is proposed that the growth of crystalline ZrO₂ core was guided by the prior supersaturation of Zr species in the molten gallium film, whereas the amorphous SiO_x shell could be attributed to the deposition of SiO vapor on the surface of ZrO₂ core. In addition, the ZrO₂/SiO_x core/shell nanofibers show a wide visible photoluminescence (PL) emission at 480 nm, which should originate from the SiO_x shells.     

Characterization of N-doped TiO2 films prepared by reactive sputtering using air/Ar mixtures

Nitrogen-doped titanium dioxide (TiO_2 − xN_x) thin films desirable for visible light photocatalysts were prepared by reactive sputtering using air/Ar mixtures. Using air as the reactive gas allows the process to conduct at high base pressures (low vacuum), which reduces substantially the processing time. The obtained films transformed from mixed phases to anatase phase as the air/Ar flow ratio increased. Substitutional doping of nitrogen verified by X-ray photoelectron spectroscopy accounts for the red-shift of absorption edge in the absorption spectra. Anatase TiO_2 − xN_x films could incorporate up to about 7.5 at.% substitutional nitrogen and a maximum of 23 at.% nitrogen was determined in the films with mixed phases. The optical band gaps of the TiO_2 − xN_x films calculated from Tauc plots varied from 3.05 to 3.11 eV and those of the mixed phase ranged from 2.77 to 3.00 eV, which are all lower than that for pure anatase TiO₂ and fall into the visible light regime.     

Nanostructured optical waveguide films of TiO2 and WO3−x for photonic gas sensors

Pulsed laser deposition technique was used to fabricate successfully nanostructured optical waveguide films of TiO₂ and WO_3 − x for gas-sensing applications. High-quality mode spectra, consisting of well-defined bright mode lines were observed in the samples with smooth surface. Films' structural, morphological and optical properties as well as the chemical composition were investigated by using x-ray diffraction, scanning electron and atomic force microscopy, UV-VIS-NIR, m-line and x-ray photoelectron spectroscopy, respectively.Gas sensitivity was investigated at room temperature using m-line spectroscopy technique on basis of reversible variations of the refractive index of the samples under gas exposure. Testing scheme recording the bright m-line shift as optical response was proposed.     

Structural and photocatalytic properties of TiO2/SiOx/TiOx multi-layer prepared by electron-beam evaporation method

TiO₂/SiO_x/TiO_x multi-layers on quartz glass were prepared by electron-beam evaporation method and their structural and photocatalytic properties were investigated. The photocatalytic activity of the TiO₂/SiO_x/TiO_x multi-layer was evaluated by the photodecomposition of methylene blue in aqueous solution. As the thickness of the SiO_x inter-layer increased, the surface roughness of the TiO₂/SiO_x/TiO_x multi-layer increased but the anatase crystallite size decreased. The TiO₂/SiO_x(80 nm)/TiO_x multi-layer exhibited excellent photocatalytic activity resulting from higher surface roughness and more trap levels in the SiO_x(80 nm) inter-layer.     

Composition dependent thermoelectric properties of sintered Mg2Si1−xGex (x = 0 to 1) initiated from a melt-grown polycrystalline source

Fabrication of Mg₂Si_1−xGe_x (x = 0-1.0) was carried out using a spark plasma sintering technique initiated from melt-grown polycrystalline Mg₂Si_1−xGe_x powder. The thermoelectric properties were evaluated from RT to 873 K. The power factor of Mg₂Si_1−xGe_x with higher Ge content (x = 0.6-1.0) tends to decrease at higher temperatures, and the maximum value of about 2.2 × 10^− 5 Wcm^− 1K^− 2 was observed at 420 K for Mg₂Si and Mg₂Si_0.6Ge_0.4. The coexistence of Si and Ge gave rise to a decrease in the thermal conductivity in the Mg₂Si_1−xGe_x. The values close to 0.02 Wcm^− 1K^− 1 were obtained for Mg₂Si_1−xGe_x (x = 0.4-0.6) over the temperature range from 573 to 773 K, with the minimum value being about 0.018 Wcm^− 1K^− 1 at 773 K for Mg₂Si_0.4Ge_0.6. The maximum dimensionless figure of merit was estimated to be 0.67 at 750 K for samples of Mg₂Si_0.6Ge_0.4.     

Optical constants of β-FeSi2 thin film on Si(001) substrate obtained by simultaneous equations from reflectance and transmittance spectra

β-FeSi₂ films were prepared on Si(001) substrates by the molecular beam epitaxy method using an Fe source. The crystallinity and crystallographic orientation of β-FeSi₂ films on Si(001) substrates were characterized by using X-ray diffraction. Optical constants and the onset of the absorption edge of β-FeSi₂ films on Si(001) substrates were evaluated by solving simultaneous equations of reflectance and transmittance data. The extinction coefficient calculated by the simultaneous equation method showed abrupt absorption onset near the band-edge of β-FeSi₂.     

Synthesis and characterisation of W-doped VO2 by Aerosol Assisted Chemical Vapour Deposition

W-doped vanadium dioxide thin films were deposited by Aerosol Assisted Chemical Vapour Deposition. Samples were characterised with several different techniques (i.e. X-ray Diffraction, Raman, Scanning Electron Microscopy-Energy Dispersive X-ray Analysis), to determine their composition and morphology. A study of their optical properties was also performed, to test the suitability of these materials as intelligent window coatings. Good changes in the transmittance and reflectance were observed above the transition temperature (decrease and increase respectively). A linear decrease in the transition temperature with increasing tungsten content was also seen, lowering it to room temperature.     

Role of Brassica juncea (L.) Czern. (var. Vaibhav) in the phytoextraction of Ni from soil amended with fly ash: selection of extractant for metal bioavailability

A pot experiment was carried out to study the potential of the plant of Brassica juncea for the phytoextraction of metal from fly ash amended soil and to study correlation between different pool of metals (total, DTPA, CaCl(2) and NH(4)NO(3)) and metal accumulated in the plant in order to assess better extractant for plant available metals. The results of total metal analysis in the soil revealed the presence of Cr, which was found below detection limit (BDL) in the plants. The fly ash (FA) amendments and soil samples were extracted with different extractants and the level of metal vary from one extractant to another. The regression analysis between total and extractable metals showed better regression for all the tested metals except Mn (R(2)=0.001) in DTPA extraction. Correlation coefficient between metal accumulation by the plant tissues and different pool of metals showed better correlation with DTPA in case of Fe, Zn and Ni, whereas, Cu was significantly correlated with NH(4)NO(3) and other metals (Pb, Mn) with CaCl(2). The soil analysis results revealed that the mobility and plant availability of metals (Fe, Mn, Zn, Ni) within the profiles of amended soils was influenced by the change in pH, however, Pb and Cu was not affected. The metal accumulation in total plant tissues was found in the order of Fe>Ni>Zn>Mn>Cu>Pb and its translocation was found more in upper part. The plants grown on soil amended with 25%FA have shown significant increase in plant biomass, shoot and plant height, whereas, no significant effect was observed in root length. The cluster analysis showed 10%FA behave differently on the basis of physico-chemical properties and metal behavior. Thus, it may be concluded that B. juncea can be used for phytoextraction of metals, especially Ni in fly ash amendment soil.     

Synthesis and characterization of nanocrystalline manganese pyrophosphate Mn2P2O7

Mn₂P₂O₇ polyhedral particles were synthesized by simple and cost-effective method using manganese nitrate hydrate and phosphoric acid in the presence of nitric acid with further calcinations at the temperature of 800 °C. The crystallite size obtained from X-ray line broadening is 31 ± 13 nm for the Mn₂P₂O₇. The X-ray diffraction and SEM results indicated that the synthesized nanoparticles have only the structure without the presence of any other phase impurities. The FT-IR and FT-Raman spectra show characteristic bands of the P₂O₇⁴⁻ anion. The UV–Vis–NIR spectrum confirms the octahedral coordination of Mn²⁺ ion.     

Spatial regression analysis of NOx and O3 concentrations in Madrid urban area using Radial Basis Function networks

This paper discusses the performance of Radial Basis Function networks (RBF) in a problem of spatial regression of pollutants in Madrid. Specifically, the spatial regression of NO_x and O₃ is considered, in such a way that, starting from a set of measuring points provided by the air quality monitoring network of Madrid, the complete surface of the pollutants in the city is obtained. This pollutant surface can be used as an initial step for modeling intra-urban pollution using land-use regression techniques for example. Also, different works has used a pollutant surface to study the patterns of pollution in different cities in the world and also to establish their air monitoring networks under mathematical criteria. The paper is focussed in analyzing the performance of RBF networks to obtain this first pollutant surface, so different RBF training algorithms are tested in this paper. Specifically, evolutionary-based RBF training algorithms are described, and compared with classical training algorithms for RBF networks with Gaussian kernels. The inclusion of meteorological variables in the RBF networks are also discussed in the paper. The experimental part of the article studies real results of the application of RBF networks to obtain a first pollutant surface of NO_x and O₃, using the data of the air pollution monitoring network of Madrid and the meteorological network of the city.