Effect of chloride ions on the corrosion behaviour of steel in 0.1 M citrate

The corrosion behaviour of steel was studied in aerated near neutral citrate solutions without and with various concentrations of NaCl. The potentiodynamic anodic polarization curve in 0.1 M citrate solution exhibits four anodic peaks A1, A2, A3 and A4 prior to the oxygen evolution reaction. Addition of Cl⁻ ions to the solution enhances the four peaks currents, specially A3, which is followed by pitting corrosion. The negative going scans of the cyclic voltammograms show two anodic reactivation peaks A5 and A6 and one cathodic plateau P1. A diffusion controlled process in the potential range of A1, A2 and P1 was detected by RDE experiments. The potentiostatic current time transients, at different concentrations of NaCl and applied potentials E_a > A3, were studied. The pit nucleation rate (t_i⁻¹) is found to increase with increasing the concentration of NaCl and the applied anodic potential. The impedance spectra exhibit four different behaviours depending on the potential range used. They were fitted with a single time constant circuit at E_a < −700 mV. However, at −700 mV < E_a < −480 mV, they were fitted with a circuit with two time constants. At E_a > −480 mV, the second semicircle is replaced by negative polarization resistance which is disappeared at E_a > −300 mV. The electrode impedance was found to decrease with the applied potential.     

The investigation of grinding kinetics of power plant solid fossil fuel in ball mill

The kinetics of batch dry grinding of power plant solid fossil fuel, from the feeds of sieve sizes −3.350 + 2.360, −2.360 + 1.700, −1.180 + 0.850, −0.425 + 0.300 and −0.212 + 0.150 mm have been determined using a Bond ball mill with a mixture of five ball sizes. The mill used has a diameter of 30.5 cm, length of 30.5 cm, providing a total mill volume of 22.272 cm³ with a total mass of 20.125 g steel ball mixtures of 38.10, 31.75, 25.40, 19.05 and 12.70 mm diameters. The balls occupied 22% of mill volume. The speed of rotation of the mill was chosen as 70 rpm. The specific rates of breakage (S_i) and primary breakage distribution (B_i,j) values, called as grinding breakage parameters, were determined for those feed size fractions to simulate the product size distributions for comparison to the experimentally obtained data. As the feed sizes increase, the S_i values also increase, that is, faster breakage values from higher to lower values were in the order of solid fossil fuel by comparing to its α values. Breakage distribution functions were found non-normalizable. It is dependent upon the initial feed particle sizes. In other words, the simulations of product size distributions for fossil fuels were in good agreement with the experimental data using a ball mill simulation program, called JKSimMet.     

Use of pyrogenic silicas for petroleum oil polar fraction characterisation. Fourier transform infrared spectroscopy and microelectrophoresis studies

In the power transformer, the presence of polar or charged species in the insulating oil can cause failure and electric discharges. Solid substrates such as silica can be used to extract the polar species and to refine the oil in order to prevent future failure in the power transformer. However, the use of silica for petroleum oil separation and refining will depend on the silica characteristics such as surface charge, surface composition, specific surface area and particle size.Various pyrogenic silicas having various specific surface areas (49-200 m² g⁻¹) and particle sizes (207-500 nm) were used to extract the polar fractions from the neat transformer insulating oils (a new, NO, and used, UO2, oils). The oil covered silica samples were investigated by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy in the range 4000-600 cm⁻¹. The bare silica surfaces present two main hydroxyl components, a sharper peak at 3745 cm⁻¹, I₃₇₄₅, due to isolated silanols and a second broad, which spreads over 3745-3000 cm⁻¹, I_3745-3000, due to H-bonded silanols. The relative intensities of the two components, I₃₇₄₅/I_3745-3000, varied for the bare and the oil covered silicas depending on the solid surface characteristics. The adsorption of the NO polar fraction onto silica leads to strong reduction in intensity of the sharper peak in favour of the broad one. However, the adsorption of the UO2 polar fraction onto silica leads in all cases to the decrease in the intensity of the both silica OH components. Further, the UO2 adsorption on the silica leads to the apparition of a broad peak at low frequency in the region 3250-3300 cm⁻¹ which, is due to the associated phenolic groups of UO2 oil polar fraction. The analysis of the DRIFT spectra for various samples indicates that the oil polar fraction resembles to asphaltenes compounds.The microelectrophoresis method used to investigate the surface charge at the water/oil polar fraction covered silica interface, indicates negatively charged particles. Further, the negative charge increased with the pH, as resulting from the increase of the ionisation and/or the amount of the oil polar carboxylic and phenolic groups. The oil polar fraction, i.e. the asphaltene components, in contact with both the silica surface and water at high pH values rearrange, due to their amphiphilic character.Finally, the use of the silica substrates seems to be suited to extract and analyse polar species present in petroleum oil. A correlation is found between the nature of the oil, its functionalities, and the magnitude of its zeta potential value at the water/oil covered silica interface.     

Precipitation of asphaltenes from solvent-diluted heavy oil and thermodynamic properties of solvent-diluted heavy oil solutions

Ratios of n-heptane (hep) to toluene (tol) affect the solubility of the asphaltenes in heavy oil extraction processes. Consequently phase changes and time after mixing n-heptane and heavy oil in toluene are important for understanding produced emulsions. The kinetics of phase change when n-heptane is added to toluene-diluted heavy oils, and the thermodynamic properties of partially deasphalted heavy oils were studied. The methods used were monitoring precipitation in time using light microscopy, quantitative asphaltenes analysis by near infrared spectroscopy, refractive index and densities measurements, and calculated solubility parameters of mixtures. At critical mass ratios of hep/tol from 1.37 to 2.0 in diluted heavy oil the precipitated asphaltene particles were observed under the microscope after lag times from 2 h to instantly. Lag times were longer at low initial oil concentration. The floc growth time decreased as heavy oil concentration in toluene increased. The growth patterns in time appeared as dots to beads (strings) to clusters (fractal-like flocs). Final wt% precipitated asphaltenes vs. mass fraction (hep+tol)/heavy oil followed sigmoidal relationships. Curves showing wt% soluble asphaltenes vs. mass fraction hep/tol after 24 h initially followed the same shape as time zero curves and diverged at the onset ratios of hep/tol. Slope for precipitated asphaltenes vs. solubility parameters curve showed a break at 16.4 MPa^1/2. Linear correlations were established for concentrations of soluble asphaltenes in residual oils and density, for refractive index and density and for refractive index and solubility parameter. The latter correlation was in accordance with Lorenz-Lorentz theory. These equations provided a means by which oil density, refractive index and solubility parameter can be predicted when these measurements are difficult to measure practically.     

Prediction of mass transport profiles in a laboratory filter-press electrolyser by computational fluid dynamics modelling

A commercial computational fluid dynamics code (Fluent) has been used to analyze the performance of a unit cell laboratory; the filter-press reactor (FM01-LC) operating with characteristic linear flow velocities between 0.024 m s⁻¹ and 0.110 m s⁻¹. The electrolyte flow through the reactor channel was numerically simulated using a finite volume approach to the solution of the Navier-Stokes equations. The flow patterns in the reactor were obtained and the mean linear electrolyte velocity was evaluated and substituted into a general mass transport correlation to calculate the mass transport coefficients. In the region of 150 < Re < 550, mass transport coefficients were obtained with a relative error between 5% and 29% respect to the experimental k_m values. The differences between theoretical and experimental values are discussed.     

Synthesis and post-annealing effects on the transport properties of thermoelectric oxide (ZnO)mIn2O3 ceramics

The synthesis and transport properties of n-type thermoelectric oxide (ZnO)_mIn₂O₃ (Z_mIO) ceramics prepared by conventional solid-state reaction method have been reported. It is found that the transport properties of Z_mIO ceramics are very sensitive to the post-annealing temperature as well as the zinc content m. The resistivity of Z₅IO annealed at 1400 °C decreases by more than 2 orders of magnitude in comparison with that of Z₅IO annealed at 1200 °C, while the resistivities of Z₆IO compounds annealed at 1250 and 1350 °C are more than 3 orders of magnitude larger than that of Z₆IO annealed at 1300 °C. All the Z_mIO compounds annealed at 1300 °C show electron-type conduction with a lowest resistivity at m = 6. It is suggested that the oxygen defects or vacancies in the InO₂ layers play a major role on the carrier scattering mechanism, and the observed temperature-dependent resistivity for Z₅IO and Z₆IO compounds can be satisfactorily described by the variable-range hopping conduction. Furthermore, it is found that the values of Seebeck coefficient for Z_mIO are also very sensitive to the zinc content m. The dimensionless figure of merit of 0.0045 at 300 K for m = 6 has been obtained.     

Kinetics of asphaltene thermal cracking and catalytic hydrocracking

A pentane-insoluble asphaltene was processed by thermal cracking and catalytic hydrocracking over NiMo/γ-Al₂O₃ in a microbatch reactor at 430 °C. Kinetic analysis shows that the first-order kinetics fits the data of conversion in reaction times ≤ 30 min approximately, but deviates from the data of times over 30 min significantly; whereas the second-order kinetics fits the data of the reaction times up to 60 min adequately, to give the apparent rate constants of 1.704 × 10⁻² and 9.360 × 10⁻² wt frac⁻¹min⁻¹ for the two cracking processes. Furthermore, a three-lump kinetic model is proposed to include parallel reactions of asphaltenes to produce liquid oil (k₁) and gas + coke (k₃), and consecutive reaction from liquid to gas + coke (k₂). The evaluated value of k₁ is 1.697 × 10⁻² and 9.355 × 10⁻² wt frac⁻¹min⁻¹, k₂ is 3.605 × 10⁻² and 6.347 × 10⁻³ min⁻¹ , and k₃ is 6.934 × 10⁻⁵ and 4.803 × 10⁻⁵ wt frac⁻¹min⁻¹ for asphaltenes thermal cracking and catalytic hydrocracking, respectively. Selectivity analysis shows that the catalytic hydrocracking process promotes liquid production and inhibits coke formation effectively.     

Optimization of process variables for essential oil components from Satureja hortensis by supercritical fluid extraction using Box-Behnken experimental design

The oil and extracts of Satureja hortensis cultivated in Iran were extracted using supercritical carbon dioxide and hydrodistillation method. The oil and extracts were analyzed by GC-FID and GC/MS. The compounds were identified according to their retention indices and mass spectra (EI, 70 eV). The effects of various parameters such as pressure, temperature, percent of modifier (methanol) and extraction time, were investigated by a fractional factorial design (2^4-1) to determine the significant parameters and their interactions. The results showed that the pressure, temperature and percent of modifier are significant (p < 0.05), but the extraction time was found to be insignificant. The response surface methodology (RSM), based on Box-Behnken design was employed to obtain the optimum conditions of the significant parameters (pressure, temperature and percent of modifier). The optimal conditions could be obtained at a pressure of 35.0 MPa, temperature of 72.6 °C, and 8.6% (v/v) for methanol. The main extracted components using SFE were γ-Terpinene (35.5%), Thymol (18.2%) and Carvacrol (29.7%).     

Transformer oils prepared from the vacuum distillates of Egyptian crude paraffinic petroleum

Vacuum gas oil and spindle oil obtained from the vacuum distillation of paraffinic crude oil from the Western Desert region of Egypt were utilized for transformer oils production. The vacuum gas oil, spindle oil and blends therefrom containing different percentages of these oils and were subjected to aromatic extraction, dewaxing catalytic hydrogenation processes. The aromatic extraction process used N-methyl-2-pyrrolidone as solvent, for a feed ratio of 0.7:1 (wt/wt) at an extraction temperature of 55 °C, while in the dewaxing process the wax is removed by chilling the raffinate at − 42 °C using MEK-toluene (60:40,vol/vol). The hydrofinishing process was achieved in a pilot plant using NiO–MoO₃/Al₂O₃ catalyst. These refining processes improved the viscosity indices and the pour points of the resulting oils and removed most of the polar impurities. It was found that, the transformer oil formulated from 7:3 b.w. vacuum gas oil:spindle oil respectively meets the IEC 60296-2003 standard specifications requirements. Its sulfur content is very low and non-corrosive. The gassing tendency is also low due to its low aromatic content. Further, the electrical properties which are significant for transformer oils fulfill the standard specifications as a result of the low water content and polar contaminants. Moreover, addition of 2,4-dimethyl-6-tertiary butyl phenol increases the oxidation stability of the produced oil, by acting as a free radical inhibitor.     

Modeling of Rayleigh convection in gas–liquid interfacial mass transfer using lattice Boltzmann method

Interfacial Rayleigh convection can be generated by concentration gradient near the interface in mass transfer processes. In the present study, a 2D time-dependent lattice Boltzmann method (LBM) with a double distribution model was established for simulating the liquid-phase Rayleigh convection in the mass transfer process of CO₂ absorption into various solvents. Two random parameters P and C_D denoting respectively the possibility and the magnitude of concentration perturbation at interface were introduced to model the interfacial disturbance, which is known as one of the necessary conditions of onset of Rayleigh convection. The values of the parameters were identified (0.05 ≤ P < 0.3 and 0 < C_D ≤ 10⁻⁹ kg m⁻³) by comparing simulated critical onset times of the Rayleigh convection with the experimental result from Blair and Quinn (1969) and theoretical predictions proposed by Kim et al. (2006) and 0245 and 0250. The maximum penetration depths, maximum transient Rayleigh numbers, and critical times for the onset of Rayleigh convection were obtained by the proposed model. The simulations captured the detailed information of the onset and the temporal–spatial evolution of Rayleigh convection, and gave the concentration contours of typical plume convection patterns which were well consistent with literatures. Enhancement of mass transfer by the Rayleigh convection was also demonstrated by comparing the simulated instantaneous mass flux across the interface with that predicted by penetration theory.     

Solubility of Jatropha and Aquilaria oils in supercritical carbon dioxide at elevated pressures

This study investigated experimental equilibrium solubilities of Jatropha curcas and Aquiliaria crassna oils dissolved in supercritical carbon dioxide at temperatures of 318-338 K and pressures of 20, 25, 30, 35 MPa. The highest solubility of J. curcas and A. crassna oil were 29.8 and 28.4 mg L⁻¹, respectively, at 338 K and 35 MPa. The oil solubilities and the concentration of triglycerides both increased with increasing temperature and pressure. Triglyceride molecules surrounded by carbon dioxide molecules may be proposed since solubilities increased with the flux of supercritical carbon dioxide. The solubility of these two oils linearly increased with the density of supercritical carbon dioxide. Experimental data of the oil solubility were successfully correlated by the Chrastil equation.     

Current efficiency studies of the zinc electrowinning process on aluminum rotating cylinder electrode (RCE) in sulfuric acid medium: Influence of different additives

This work studies the effect of three additives, sodium lauryl sulfate (SLS), cetyltrimethylammonium bromide (CTABr) and arabic gum (AG) on zinc electrowinning on aluminum in a solution of 85 g L⁻¹ Zn(II) (1.3 M) in 108 g L⁻¹ H₂SO₄ (1.1 M). The influence of these three additives is analyzed during the different stages of the reduction process using chronopotentiometric techniques on an aluminum rotating disk electrode (RDE). Potential ranges (−1.05 < E < −0.85 V versus SHE) and current density (−51 < i < −0.2 mA cm⁻²) within which zinc electrodeposition takes place in the presence of the three different additives were established. These parameters were used to determine current efficiencies (Φ), evaluated by electrolysis on an aluminum rotating cylinder electrode (RCE); the zinc deposition efficiency in the presence of SLS, CTABr and AG, was 95%, 96% and 99%, respectively, were all greater than the efficiency obtained without any additive (WA), Φ = 84%. The homogeneity of the deposits at the end of electrolyses implied that the (RCE) promotes uniform current density on the electrode surface and, hence, can be considered a model cell to evaluate current efficiencies.     

Mass transfer limitations on fixed-bed reactor for Fischer-Tropsch synthesis

Mass transfer limitations on fixed-bed for Fischer-Tropsch synthesis were investigated by changing synthesis gas superficial velocity, catalyst pellet size, and catalyst amount. To study external mass transfer limitation, synthesis gas superficial velocity was changed from 8.47 × 10^− 4 m s^− 1 to 3.39 × 10^− 3 m s^− 1. As a result, the synthesis gas superficial velocity of 3.39 × 10^− 3 m s^− 1 was most suitable for hydrocarbon chain growth resulting to liquid hydrocarbon formation. In case of internal mass transfer limitations, the effects of catalyst pellet size and catalyst amount (W_cat/F) were discussed. The large catalyst pellet showed higher C₅₊ selectivity and a lower α value compared to the small pellet because of more severe internal mass transfer limitations of α-olefin and long-chained hydrocarbons in the large pellet, respectively. Catalyst amount (W_cat/F) was inversely proportional to the internal mass transfer limitation because increased catalyst amount gave more time for liquid hydrocarbon products to diffuse from the catalyst pellet and, therefore, the catalyst amount of 4.5 g (W_cat/F = 45 g_cat min L^− 1) was most appropriate for liquid hydrocarbon formation.     

Determination of the kinetic parameters of oxygen reduction on copper using a rotating ring single crystal disk assembly (RRDCu(h k l)E)

The kinetics of the oxygen reduction reaction (orr) on Cu(h k l) surfaces are investigated in perchloric acid and sulfuric acid solutions using rotating ring disk electrode (RRD_Cu(h k l)E). Parameters, such as reaction order, kinetic current, rate constant, Tafel slopes as well as the number of electrons transferred are determined. The variation in the activity and reaction pathway with the crystal faces in different electrolytes is related to the surface characteristics of Cu(h k l) and the structure-sensitive inhibiting effect of the adsorbed anions on their surfaces. In 0.1 M HClO₄, the difference in activity is clearly observed on Cu(h k l) surfaces (Cu(1 0 0) > Cu(1 1 1) although it is relatively small). The higher activity of Cu(1 0 0) arises from its more open characteristics which may facilitate the co-adsorption of O₂. On the other hand, the adsorption of oxygenated species on Cu(1 1 1) at E > −0.35 V induces a 2 e⁻ pathway; while a 4 e⁻ reduction is observed on Cu(1 0 0) in the entire potential region (−0.70 V < E < −0.10 V). In 0.5 M H₂SO₄, the sequence in activity between Cu(1 1 1) and Cu(1 0 0) varies with the potentials, i.e., Cu(1 0 0) is initially more active than Cu(1 1 1) at −0.35 V < E < −0.15 V, however, the reversal in the activity between Cu(1 1 1) and Cu(1 0 0) is observed at more negative potentials (−0.45 V < E < −0.35 V). The desorption of strongly adsorbed (bi)sulfate anions on Cu(1 1 1) induces the 2 e⁻ reduction via peroxide formation, however, a 4 e⁻ reduction is dominant on the Cu(1 0 0) surfaces. The major effect of (bi)sulfate anions and oxygenated species on the orr kinetics and reaction pathway on Cu(h k l) surfaces is the blocking of active copper sites for the adsorption of O₂ molecules.     

Structure,dielectric and optical properties of Bi1.5+xZnNb1.5O7+1.5x pyrochlores

Non-stoichiometric pyrochlore ceramics with formula Bi_1.5+xZnNb_1.5O_7+1.5x were systematically investigated. Crystal structures of the compounds were studied by X-ray diffraction (XRD) technique. The structures were identified as pure cubic pyrochlores when |x| < 0.1. Dielectric and optical properties of the compositions when x = −0.1, 0 and 0.1 were studied. All samples have high resistivities and low dielectric loss. With increasing x in Bi_1.5+xZnNb_1.5O_7+1.5x, the lattice constant, permittivity, temperature coefficient of permittivity and thermal expansion coefficient increased, while dielectric loss decreased. Raman spectra indicated that the intensity of Bi–O stretching become stronger with increasing x. A vibration mode emerging at 861 cm⁻¹ when x = −0.1 means that the B–O coordination environment is significantly more disordered. Absorption spectra suggested that the bandgap energy become lower from 2.86 to 2.70 eV as lattice constants increased. Strong absorption occurs at wavelengths from 433 to 459 nm, shows that samples have the ability to respond to wavelengths in the visible light region.     

Molecular characteristics of poly(1-trimethylsilyl-1-propyne) in dilute solutions

Samples and fractions of a membrane-forming polymer, poly(1-trimethylsilyl-1-propyne) (PTMSP), were studied by methods of molecular hydrodynamics (velocity sedimentation, translational isothermal diffusion and viscometry) in cyclohexane in the molecular mass range 60<M×10⁻³ g mol⁻¹<430. The following molecular-mass dependencies of the hydrodynamic characteristics (intrinsic viscosity [η] (cm³ g⁻¹), sedimentation coefficient s₀(s) and translational diffusion coefficient D₀ (cm² s⁻¹)) were established: [η]=0.198 M^0.50±0.06; s₀=8.66×10⁻¹⁶M^0.50±0.04; D₀=9.30×10⁻⁵M^{−0.50±0.04}. On the basis of the hydrodynamics data the equilibrium rigidity and hydrodynamic diameter of PTMSP chains were evaluated. The equilibrium properties of the different disubstituted polyacetylenes molecules are compared on the base of the normalised scaling plots.     

The continuing development of Magnéli phase titanium sub-oxides and Ebonex electrodes

Magnéli phase titanium sub-oxides were identified (via X-ray diffraction) in the 1950s as a distinct series of electrically conducting compounds having the general formula Ti_nO_2n−1 where 3 < n < 10. Early research on the characterisation of materials based on Ti_nO_2n−1 has been well documented. This concise review, which is illustrated by data from the literature and our own laboratory, concerns more recent research on Magnéli phase titanium oxide materials. A brief overview of chemical and physical properties is followed by the applications of electrode materials based on these titanium oxides. Energy conversion technologies (particularly batteries and fuel cells) are shown to be a continued area of research that particularly suits the relatively high electrical conductivity and chemical stability inherent in these materials.     

Imidazolium-based alkylphosphate ionic liquids - A potential solvent for extractive desulfurization of fuel

N-ethyl-imidazolium-based alkylphosphate ionic liquid (IL), viz. N-ethyl-N-methyl-imidazolium dimethylphosphate ([EMIM][DMP]), N-ethyl-N-ethyl-imidazolium diethylphosphate ([EEIM][DEP]) and N-butyl-N-ethyl-imidazolium dibutylphosphate ([BEIM][DBP]) were demonstrated to be effective for the removal of aromatic sulfur compounds (S-compound) 3-methylthiophene (3-MT), benzothiophene (BT) and dibenzothiophene (DBT) from fuel oils in terms of sulfur partition coefficients (K_N) at 298.15 K. It was shown that the extractive ability of the alkylphosphate ILs was dominated by the structure of the cation and followed the order [BEIM][DBP] > [EEIM][DEP] > [EMIM][DMP] for each S-compound studied with their K_N-value being 1.72, 1.61 and 1.17, respectively for DBT. For a specified IL the sulfur selectivity followed the order DBT > BT > 3-MT with their K_N-value being 1.61, 1.39 and 0.78, respectively for [EEIM][DEP]. The alkylphosphate ILs are insoluble in fuel while the fuel solubility in ILs varies from 20.6 mg(fuel)/g(IL) for [EMIM][DMP] to 266.9 mg(fuel)/g(IL) for [BEIM][DBP]. The results suggest that [EEIM][DEP] might be used as a promising solvent for the extractive desulfurization of fuel, considering its higher sulfur extractive ability, lower solubility for fuel and thus negligible influence on the constituent of fuel, and the ease of regeneration for the spent IL via water dilution process.     

Polypyrrole and La1−xSrxMnO3 (0≤ x ≤0.4) composite electrodes for electroreduction of oxygen in alkaline medium

Composite G/PPy/PPy(La_1−xSr_xMnO₃)/PPy electrodes made of the perovskite La_1−xSr_xMnO₃ embedded into a polypyrrole (PPy) layer, sandwiched between two pure PPy films, electrodeposited on a graphite support were investigated for electrocatalysis of the oxygen reduction reaction (ORR). PPy and PPy(La_1−xSr_xMnO₃) (0≤ x ≤0.4) successive layers have been obtained on polished and pretreated graphite electrodes following sequential electrodeposition technique. The electrolytes used in the electrodeposition process were Ar saturated 0.1 mol dm⁻³ pyrrole (Py) plus 0.05 mol dm⁻³ K₂SO₄ with and without containing a suspension of 8.33 g L⁻¹ oxide powder. Films were characterized by XRD, SEM, linear sweep voltammetry, cyclic voltammetry (CV) and electrochemical impedance (EI) spectroscopy. Electrochemical investigations were carried out at pH 12 in a 0.5 mol dm⁻³ K₂SO₄ plus 5 mmol dm⁻³ KOH, under both oxygenated and deoxygenated conditions. Results indicate that the porosity of the PPy matrix is considerably enhanced in presence of oxide particles. Sr substitution is found to have little influence on the electrocatalytic activity of the composite electrode towards the ORR. However, the rate of oxygen reduction decreases with decreasing pH of the electrolyte from pH 12 to pH 6. It is noteworthy that in contrast to a non-composite electrode of the same oxide in film form, the composite electrode exhibits much better electrocatalytic activity for the ORR.     

Oxidative desulfurization of Gas oil by polyoxometalates catalysts

Several polyoxometalates: Na₂HPM₁₂O₄₀, H₃PM₁₂O₄₀, Na₂HPM₁₂O₄₀, (VO)H[PM₁₂O₄₀] and (n-Bu₄N)₃[PM₁₂O₄₀] (M = Mo and W) as well as (n-Bu₄N)_3 + x[PW_12−xV_xO₄₀] (x = 0–3) were synthesized and characterized. Benzothiophene, dibenzothiophene and 4,6-dimethyl-dibenzothiophene were used as model sulfur compounds in gas oil. The oxidation reaction was performed using different polyoxometalates as catalyst and H₂O₂/acetic acid. The experimental results show that the W-based polyoxometalate catalysts are more active than the Mo catalysts. The oxidation reactivity of the catalysts depends on the type of countercation: Na⁺ > H⁺ > (VO)⁺ > (n-Bu₄N)⁺. In a series of (n-Bu₄N)_3 + x [PW_12−xV_xO₄₀] (x = 0–3) the order of catalytic activity is V₃ > V₂ > V₁ > V₀. The reactivity order of the sulfur compounds is: dibenzothiophene > 4,6-dimethyldibenzo-thiophene > benzothiophene. The catalytic system in this work was used for the oxidation of gas oil combined with solvent extraction to remove sulfur content in gas oil. Under mild reaction condition, high sulfur removal up to 98% can be achieved with high oil recovery (90%).