The Partition Behavior of Zn(II) using Halide Ions Extractants in Aqueous Peg‐Based Two‐Phase Systems

Abstract

The partition behavior of Zn(II) has been studied in aqueous polyethylene glycol PEG(1550) – (NH₄)₂SO₄ two‐phase system using halide ions (Cl^?, Br^? and I^?) as extracting agents, at two different values of salt stock solution pH. The efficiency of extractants increase in this order: Cl^?>Br^?>I^?. The extracted species were estimated from the distribution coefficients' values determined as a function of halide ions concentration, and the “conditional extraction constants” were calculated. The experimental results suggest that the Zn(II) partition in presence of halide ions in such systems is the result of two competitive processes. The IR spectra of solidified PEG‐rich phases show that the passing of metal species into PEG‐rich phases bring a supplementary water contribution, which makes the extraction process to occurs until it reaches an “equilibrium state”, dependent on the hydrophobicity of these phases and not on the type of extracted metal species.     

Uptake and apparent utilization of urea and ammonium nitrate in wheat seedlings

Intact wheat (Triticum aestivum cv. Quern) seedlings that were grown in presence or absence of NH₄NO₃ were exposed to solutions containing CO(NH₂)₂, NH₄NO₃, CO(NH₂)₂ + NH₄NO₃, CO(NH₂)₂ + KNO₃ and CO(NH₂)₂ + (NH₄)₂SO₄ for consecutive periods of 3, 3, 6, 12 and 24h and N uptake determined by solution depletion measurements. Differences in ethanol-soluble N and ethanol-insoluble N content of roots and shoots of control (zero time) seedlings and seedlings exposed to CO(NH₂)₂, NH₄NO₃ and CO(NH₂)₂ + NH₄NO₃ for 48 h were used to characterize N utilization during/following uptake.Regardless of initial N status, uptake of N from CO(NH₂)₂ was less than one-third of that from NH₄NO₃. Relative absorption of the CO(NH₂)₂ and NH₄NO₃ was not substantially altered by acidity control of the uptake solutions. There was a reciprocal antagonism between uptake of CO(NH₂)₂ and uptake of NH₄NO₃. Whereas CO(NH₂)₂ inhibited NH₄ absorption in each set of seedlings, it decreased NO₃ uptake only in seedlings that had been pretreated with N. Simultaneous presence of KNO₃ enhanced CO(NH₂)₂ uptake but presence of (NH₄)₂SO₄ decreased it to the same extent as NH₄NO₃. All absorption processes involving CO(NH₂)₂ and NH₄ were substantially restricted by pretreatment of the seedlings with NH₄NO₃. The results suggest that apparent utilization of ambient N was dependent on initial N status of the seedlings and on the nature of the N species to which they were exposed.     

Preparation and characterization of SO42-/TiO2 and S2O82-/TiO2 catalysts

Nanosized solid superacids SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂, as well as MCM-41-supported SO₄ ²⁻/ZrO₂, were prepared. Their structures, acidities, and catalytic activities were investigated and compared using XRD, N₂ adsorption-desorption, and in situ FTIR-pyridine adsorption, as well as an evaluation reaction with pseudoionone cyclization. The results showed that SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ possess not only nanosized particles with diameters < 7.0 nm, a BET surface greater than 140 cm²/g and relatively regular mesostructures with pores around 4.0 nm, but also a pure anatase phase and strong acidity. Different from the Lewis acid nature of SO₄ ²⁻/ZrO₂/MCM-41, SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ exhibit mainly Bronsted acidities. The strongest Bronsted acid sites were produced on SO₄ ²⁻/TiO₂ promoted with H₂SO₄, while Lewis acid sites on S₂O₈ ²⁻/TiO₂ even stronger than those on SO₄ ²⁻/ZrO₂/MCM-41 were generated when persulfate solution was used as sulfating agent. Because of their distinct acid natures, SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ exhibited catalytic activities for the cyclization of pseudoionone that were much higher than that of SO₄ ²⁻/ZrO₂/MCM-41. It can be concluded that the existence of more Br?nsted acid sites was favorable for proton participation in the cyclization reaction. Translated from Journal of Chemical Engineering of Chinese Universities, 2006, 20(2): 239–244 [译自: 高校化学工程学报]     

Methane production from anaerobic soil amended with rice straw and nitrogen fertilizers

Laboratory experiments were conducted on the effects of rice straw application and N fertilization on methane (CH₄) production from a flooded Louisiana, USA, rice soil incubated under anaerobic conditions. Rice straw application significantly increased CH₄ production; CH₄ production increased in proportion to the application rate. Urea fertilization also enhanced CH₄ production. The maximum production rate was 17% higher, and occurred 1 week earlier, than that of soil samples which did not receive urea, possibly due to the increase in soil pH following urea hydrolysis. The increase in soil pH following urea hydrolysis may have stimulated CH₄-generating bacteria by providing more optimal soil pH conditions or contributed to the drop in redox potential (Eh). The significant decrease in both the production rate and the total amount of CH₄ by application of NH₄NO₃ was associated with increases in soil Eh after addition of this oxidant. Addition of 300 mg. kg^–1 NO ₃ ^- -N increased soil Eh by 220 mV and almost completely inhibited CH₄ production. However, this inhibitory effect was short-termed. Soon after the applied NO ₃ ^- -N was reduced through denitrification, CH₄ production increased. When (NH₄)₂SO₄ was applied, the inhibition of CH₄ production was not associated with an increase in soil Eh which did not change significantly. A direct inhibitory effect of sulphate on methanogenesis might have been more important.     

An assessment of N loss from agricultural fields to the environment in China

Using the 1997 IPCC Guidelines for National Greenhouse Gas Inventory Methodology, and statistical data from the China Agricultural Yearbook, we estimated that the direct N₂O emission from agricultural fields in China in 1990 was 0.282 Tg N. Based on micro-meteorological field measurement of NH₃ volatilization from agricultural fields in different regions and under different cropping systems, the total NH₃ volatilization from agricultural fields in China in 1990 was calculated to be 1.80 Tg N, which accounted for 11% of the applied synthetic fertilizer N. Ammonia volatilization from agricultural soil was related to the cropping system and the form of N fertilizer. Ammonia volatilization from paddy fields was higher than that from uplands, and NH₄HCO₃ had a higher potential of NH₃ volatilization than urea. N loss through leaching from uplands in north China accounted for 0.5–4.2% of the applied synthetic fertilizer N. In south China, the leaching of applied N and soil N from paddy fields ranged from 6.75 to 27.0 kg N ha^-1 yr^-1, while N runoff was between 2.45 and 19.0 kg N ha^-1 yr^-1.     

Novel promoting effect of SO2 on the selective catalytic reduction of NOx by ammonia over Co3O4 catalyst

Spinel nano-Co₃O₄ was prepared by solid-state reaction at room temperature and investigated for selective catalytic reduction of NO_x by NH₃ (NH₃-SCR). Although suffering from pore filling and plugging, treatment of this catalyst by SO₂ showed novel promoting effect on NH₃-SCR above 250 °C. Bulk cobalt sulfate was observed over the sulfated Co₃O₄ with XRD, which would be an active component for NH₃-SCR. The sulphated Co₃O₄ catalyst exhibited good resistance to SO₂ (500 ppm, 100 ppm) and 10% H₂O at a space velocity of about 25 000 h⁻¹ at 300 °C, as tested for 12 h.     

Reduction of lean NOx by ethanol over Ag/Al2O3 catalysts in the presence of H2O and SO2

The reduction of lean NOx using ethanol in simulated diesel engine exhaust was carried out over Ag/Al₂O₃ catalysts in the presence of H₂O and SO₂. The Ag/Al₂O₃ catalysts are highly active for the reduction of lean NOx by ethanol but the reaction is accompanied by side reactions to form CH₃CHO, CO along with small amounts of hydrocarbons (C₃H₆, C₂H₄, C₂H₂ and CH₄) and nitrogen compounds such as NH₃ and N₂O. The presence of H₂O enhances the NOx reduction while SO₂ suppresses the reduction. The presence of SO₂ along with H₂O suppresses the formation of acetaldehyde and NH₃. By infrared spectroscopy, it was revealed that the reactivity of NCO species formed in the course of the reaction was greatly enhanced in the presence of H₂O. The NCO species readily reacts with NO in the presence of O₂ and H₂O at room temperature, being converted to N₂ and CO₂ (CO). Addition of SO₂ suppresses the formation of NCO species and lowers the reactivity of the NCO species. However, the reduction of NOx is still kept at high conversion levels in the presence of H₂O and SO₂ over the present catalysts. About 80% of NOx in the simulated diesel engine exhaust was removed at 743 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

Protection of mild steel corrosion with Schiff bases in 0.5 M H2SO4 solution

Three new Schiff bases, viz., N,N′-ethylen-bis (salicylidenimine) [S₁], N,N′-isopropylien-bis (salicylidenimine) [S₂], and N-acetylacetone imine, N′-(2-hydroxybenzophenone imine) ortho-phenylen [S₃] have been investigated as corrosion inhibitors for mild steel in 0.5 M H₂SO₄ using Tafel polarization and electrochemical impedance spectroscopy (EIS). The three Schiff bases function as good inhibitors reaching inhibition efficiencies of ∼97-98% at 300 ppm concentration. The fraction <theta> of the metal surface covered by the inhibitor is found to increase with inhibitor concentration. Of the three Schiff bases, the S2 shows better efficiency than the other two Schiff bases. The adsorption of the inhibitor follows Langmuir isortherm. Thermodynamic calculations indicate the adsorption to be physical in nature.     

Mechanochemical synthesis of kaolin-KH2PO4 and kaolin-NH4H2PO4 complexes for application as slow release fertilizer

A milling process to reduce kaolin to amorphous phase in the presence of KH₂PO₄ or NH₄H₂PO₄ and allow mechanochemical (MC) reaction for incorporation of KH₂PO₄ and NH₄H₂PO₄ into the kaolin structure was investigated in this work. Mixtures of kaolin and KH₂PO₄ and NH₄H₂PO₄ in separate systems were prepared by milling in a planetary ball mill. Tests with kaolin contents ranging from 25 to 75 wt.% and mill rotational speeds from 200 to 700 rpm were performed to evaluate incorporation of KH₂PO₄ and NH₄H₂PO₄ and release of K⁺, NH₄⁺ and PO₄³⁻ ions into solution. Analyses by XRD, DTA and ion chromatography indicated that the MC process was successfully applied to incorporate both KH₂PO₄ and NH₄H₂PO₄ into the amorphous kaolin structure. Release of K⁺ and PO₄³⁻ ions from the system (kaolin-KH₂PO₄) when dispersed in water for 24 h reached only up to 10%. Under similar conditions for the system (kaolin-NH₄H₂PO₄), release of NH₄⁺ and PO₄³⁻ ions reached between 25 and 40%. These results indicated that the MC process can be developed to allow amorphous kaolin to act as a carrier of K⁺, NH₄⁺ and PO₄³⁻ nutrients to be released slowly for use as fertilizer.     

Results from trialling aqueous NH3 based post-combustion capture in a pilot plant at Munmorah power station: Absorption

Australia's Commonwealth Scientific and Industrial Research Organization (CSIRO) and Delta Electricity have developed, commissioned and operated an A$7 million aqueous NH₃ based post-combustion capture (PCC) pilot plant at the Munmorah black coal fired power station in Australia. The results from the pilot plant trials will be used to address the gap in know-how on application of aqueous NH₃ for post-combustion capture of CO₂ and other pollutants in the flue gas and explore the potential of the NH₃ process for application in the Australia power sector. This paper is one of a series of publications to report and discuss the experimental results obtained from the pilot plant trials and primarily focuses on the absorption section.The pilot plant trials have confirmed the technical feasibility of the NH₃ based capture process. CO₂ removal efficiency of more than 85% can be achieved even with low NH₃ content of up to 6 wt%. The NH₃ process is effective for SO₂ but not for NO in the flue gas. More than 95% of SO₂ in the flue gas is removed in the pre-treatment column using NH₃. The mass transfer coefficients for CO₂ in the absorber as functions of CO₂ loading and NH₃ concentration have been obtained based on pilot plant data.     

Surface characterization of sulfated zirconia and its catalytic activity for epoxidation reaction of castor oil

The solid acid catalysts SO₄^2?/ZrO₂ were prepared by impregnation technique at different calcination temperatures. The surface characterizations were carried out by using scanning electron microscope (SEM), Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), temperature programed desorption of NH₃ (NH₃-TPD), and N₂-BET. The SEM results showed that the size of the SO₄^2?/ZrO₂ was not uniform and varied from about 1 to 20?µm. The characteristic peaks in FTIR spectra were essentially the same within the calcination temperature range of 400–700?°C. The XRD results indicated that the transition temperature from amorphous to tetragonal phase was up to 500?°C. The strong acid and superacid sites of the samples could be observed by the NH₃-TPD results. The largest BET surface area was 140 m²/g, when the calcination temperature was at 500?°C, and all the pore size distributions belong to mesoporous range. The solid acid SO₄^2?/ZrO₂ was used for the epoxidation of castor oil. When the calcination temperature of SO₄^2?/ZrO₂ was 600?°C, reaction temperature 45?°C, and reaction time 8?h, the reaction effect was better with an iodine value of 33.0?±?1.6?g/100?g and an epoxy value of 2.45?±?0.11?mol/100?g.     

Development of Catalyst-Sorbents for Simultaneous Removal of SO2 From Flue Gas by Low Temperature Ozone Oxidation

One technological process employing ozone and heterogeneous catalyst-sorbents was proposed for removal of SO₂ from flue gas. The catalyst-sorbents were developed and tested especially for adsorption and oxidation of SO₂. Alternative catalyst-supporters including γ-Al₂O₃, permutite, silica gel, activated carbon and diatomite combined with different metal oxides (MnO₂, Cr₂O₃, Fe₂O₃, CuO, CoO and NiO) were evaluated and tested. It was found that γ-Al₂O₃ doped with MnO₂ can be considered as removal-effective sorbent for adsorption and oxidation of SO₂. The synergetic effect between ozone and catalyst was found to be dominated. Effects of catalyst preparation parameters like calcination temperature, metal loaded and reaction temperature, etc. were investigated based on the MnO₂/Al₂O₃ catalyst-sorbents. Results show that γ-Al₂O₃ combined with 8% Mn, calcinated under 573 K and reacted at 413 K are the optimal parameters for removal of SO₂. Extra NO in flue gas can slightly enhance the capture efficiency of SO₂.     

Molten V2O5/Cs0.9K0.9Na0.2S2O7 and V2O5/K2S2O7 catalysts as electrolytesin an electrocatalytic membrane separation device for SO2 removal

Bench scale fuel cell tests have been carried out on the SO₂ oxidation catalyst systems V₂O₅/M₂S₂O₇ (M = alkali) used as electrolytes in a standard molten carbonate fuel cell (MCFC) fuel cell setup for removal of SO₂ from power plant flue gases. Porous Li _x Ni_(1–x)O electrodes were used both as anode and cathode. The cleaning cell removes SO₂ when a potential is applied across the membrane, potentially providing cheap and ecological viable means for regeneration of SO₂ from off-gases into high quality H₂SO₄. Results show that successful removal of up to 80% SO₂ at 450 °C can be achieved at approximately 5 mAcm^–2. However, the data obtained during the experiments explain the current limitations of the process, especially in terms of electrolyte wetting capability and acid/base chemistry of the electrolyte.     

Absorption of NO by Aqueous Solutions of KMnO4/H2SO4

The absorption of NO in aqueous solutions of KMnO₄ and H₂SO₄ was carried out in a stirred tank reactor under atmosphere pressure. The results indicated that the absorption process was under a fast pseudo-m th reaction regime. The reaction between NO and aqueous solutions of KMnO₄/H₂SO₄ was found to be first-order with respect both to NO and to KMnO₄. The addition of H₂SO₄ to KMnO₄ solutions increased the absorption rate of NO and increasing reaction temperature was also favorable to the absorption of NO.     

Nonoxidative dehydrogenation and aromatization of methane over W/HZSM‐5‐based catalysts

Highly active and heat‐resisting W/HZSM‐5‐based catalysts for nonoxidative dehydro‐aromatization of methane (DHAM) have been developed and studied. It was found from the experiments that the W−H₂SO₄/HZSM−5 catalyst prepared from a H₂SO₄‐acidified solution of ammonium tungstate (with a pH value at 2–3) displayed rather high DHAM activity at 973–1023 K, whereas the W/HZSM‐5 catalyst prepared from an alkaline or neutral solution of (NH₄)₂WO₄ showed very little DHAM activity at the same temperatures. Laser Raman spectra provided evidence for existence of (WO₆)^n- groups constructing polytungstate ions in the acidified solution of ammonium tungstate. The H₂‐TPR results showed that the reduction of precursor of the 3% W–H₂SO₄/HZSM‐5 catalyst may occur at temperatures below 900 K, producing W species with mixed valence states, W⁵⁺ and W⁴⁺, whereas the reduction of the 3% W/HZSM‐5 occurred mainly at temperatures above 1023 K, producing only one type of dominant W species, W⁵⁺. The results seem to imply that the observed high DHAM activity on the W–H₂SO₄/HZSM‐5 catalyst was closely correlated with (WO₆)^n- groups with octahedral coordination as the precursor of catalytically active species. Incorporation of Zn (or La) into the W–H₂SO₄/HZSM‐5 catalyst has been found to pronouncedly improve the activity and stability of the catalyst for DHAM reaction. Over a 2.5% W–1.5% Zn–H₂SO₄/HZSM‐5 catalyst and under reaction conditions of 1123 K, 0.1 MPa, and GHSV=1500 ml/(h g−cat.), methane conversion (XCH₄) reached 23% with the selectivity to benzene at ∼96% and an amount of coke for 3 h of operation at 0.02% of the catalyst weight used. This revised version was published online in July 2006 with corrections to the Cover Date.     

SO2 Oxidation Catalyst Model Systems Characterized by Thermal Methods

The molten salts M₂S₂O₇ and MHSO₄, the binary molten salt systems M₂S₂O₇—MHSO₄ and the molten salt-gas systems M₂S₂O₇—V₂O₅ and M₂S₂O₇—M₂SO₄—V₂O₅ (M = Na, K, Rb, Cs) in O₂, SO₂ and Ar atmospheres have been investigated by thermal methods like calorimetry, Differential Enthalpic Analysis (DEA) and Differential Scanning Calorimetry (DSC). Fundamental thermodynamic data like temperatures and molar heats of solid--solid transition and fusion, phase diagrams, heat capacities of solids and liquids, heat of mixing and heats of complex formation have been obtained and the results are discussed in relation to the mechanism of SO₂ oxidation by V₂O₅ based industrial catalysts.     

The Preparation and Characterization of High-Strength PMMA-Na2SO4 Composite Film

PMMA-Na₂SO₄ composite films were prepared by a solvent casting method and were characterized by SEM, EDX, DSC, UTM, TG/DTA and FTIR techniques. From the SEM it is clear that Na₂SO₄ were well dispersed, having sizes ranging from micrometer to nanometer. EDX results confirm the presence of Na₂SO₄ particles in a polymer matrix. UTM studies show that the tensile strength of PMMA-Na₂SO₄ composite is better than pure PMMA. FTIR spectra indicates the strong interaction between C=O of PMMA and Na₂SO₄. According to DSC, TG/DTA analysis the thermal stability and glass transition temperature of PMMA-Na₂SO₄ has increased as compared with that of pure PMMA.     

Low cost coal-based carbons for combined SO2 and NO removal from exhaust gas

The aim of this paper is to show how a cheap carbonaceous material such as low rank coal-based carbon (or char) can be used in the combined SO₂/NO removal from exhaust gas at the linear gas velocity used in commercial systems (0.12 m s⁻¹). Char is produced from carbonization and optionally activated with steam. This char is used in a first step to abate the SO₂ concentration at the following conditions: 100 °C, space velocity of 3600 h⁻¹, 6% O₂, 10% H₂O, 1000 ppmv SO₂, 1000 ppmv NO and N₂ as remainder. In a second step, when the SO₂ concentration in the flue gas is low, NO is reduced to N₂ and steam at the following experimental conditions: 150 °C, space velocity of 900 h⁻¹, 6% O₂, 10% H₂O, 0-500 ppmv SO₂, 1000 ppmv NO, 1000 ppmv NH₃ and N₂ as remainder.It has been shown that the presence of NO has no effect on SO₂ abatement during the first step of combined SO₂/NO removal system and that low SO₂ inlet concentration has a negligible effect on NO reduction in the second step. Moreover, this char can be thermally regenerated after use for various cycles without loss of activity. On the other hand, this regenerated char shows the highest NO removal activity (compared to parent chars, either carbonized or steam activated) which can be attributed to the activating effect of the sulfuric acid formed during the first step of the combined SO₂/NO removal system.     

Effect of SO2 on a cordierite honeycomb supported CuO catalyst for NO reduction by NH3

Supporting CuO on a Al₂O₃-coated cordierite honeycomb yields a good catalyst (CuO/HC–Al) for selective catalytic reduction (SCR) of NO with NH₃ at 350–500 °C. SO₂ has complex effects on the catalysts activity. It significantly promotes the SCR activity through conversion of CuO to CuSO₄, however, when a certain amount of CuO is converted, it slightly decreases the SCR activity through competitive adsorption with NH₃. This competitive adsorption reduces the amount of NH₃ adsorbed on the catalyst surface, especially on the sites highly active to the SCR. It also prevents transformation of CuO to CuSO₄ and as a result, the catalysts subjected to pre-sulfation and in situ sulfation show different SCR behaviors.     

Control of interfacial barriers in n-type FeS2 (pyrite) by electrodepositing metals (Co, Cu) forming isostructural disulfides

Cobalt and copper were electrodeposited on n-type, 100-oriented, pyrite slices. The occurrence of a favorable chemical interaction with the pyrite interface is marked by the appearance of pronounced prebulk deposition (PBD) features in the case of Co. This metal leads to the formation of highly ohmic metallic contact, while deposition of Cu provides a significant Schottky barrier. The effects of electrodeposited Co and Cu can be explained by the formation of the pyrite-type compounds CoS₂ and CuS₂, at the interface, which are n- and p-type metallic compounds, respectively. When time for diffusion is allowed, mixed Co_xFe_1−xS₂ and Cu_xFe_1−xS₂ phases are also to be expected as learned from XPS experiments on (electron beam evaporated) Co/(MOCVD) pyrite layers. A model is proposed which links the electronic properties of these disulfides with their solid state chemical behavior in the pyrite structure and with their ability to form PBD layers (Co).