Ultrasound-assisted oxidative desulfurization process of liquid fuel by phosphotungstic acid encapsulated in a interpenetrating amine-functionalized Zn(II)-based MOF as catalyst

In this work, ultrasound-assisted oxidative desulfurization (UAOD) of liquid fuels performed with a novel heterogeneous highly dispersed Keggin-type phosphotungstic acid (H₃PW₁₂O₄₀, PTA) catalyst that encapsulated into an amino-functionalized MOF (TMU-17-NH₂). The prepared composite exhibits high catalytic activity and reusability in oxidative desulfurization of model fuel. Ultrasound-assisted oxidative desulfurization (UAOD) is a new way to performed oxidation reaction of sulfur-contain compounds rapidly, economically, environment-friendly and safely, under mild conditions. Ultrasound waves can be apply as an efficient tool to decrease the reaction time and improves oxidative desulfurization system performance. PTA@TMU-17-NH₂ could be completely performed desulfurization of the model oil by 20 mg of catalyst, O/S molar ratio of 1:1 in presence of MeCN as extraction solvent. The obtained results indicated that the conversions of DBT to DBTO₂ achieve 98% after 15 min in ambient temperature. In this work, we prepared TMU-17-NH₂ and PTA/TMU-17-NH₂ composite by ultrasound irradiation for first time and employed in UAOD process. Prepared catalyst exhibit an excellent reusability without PTA leaching and loss of activity.     

Investigation of process variables and intensification effects of ultrasound applied in oxidative desulfurization of model diesel over MoO3/Al2O3 catalyst

A new heterogeneous sonocatalytic system consisting of a MoO₃/Al₂O₃ catalyst and H₂O₂ combined with ultrasonication was studied to improve and accelerate the oxidation of model sulfur compounds of diesel, resulting in a significant enhancement in the process efficiency. The influence of ultrasound on properties, activity and stability of the catalyst was studied in detail by means of GC-FID, PSD, SEM and BET techniques. Above 98% conversion of DBT in model diesel containing 1000 μg/g sulfur was obtained by new ultrasound-assisted desulfurization at H₂O₂/sulfur molar ratio of 3, temperature of 318 K and catalyst dosage of 30 g/L after 30 min reaction, contrary to the 55% conversion obtained during the silent process. This improvement was considerably affected by operation parameters and catalyst properties. The effects of main process variables were investigated using response surface methodology in silent process compared to ultrasonication. Ultrasound provided a good dispersion of catalyst and oxidant by breakage of hydrogen bonding and deagglomeration of them in the oil phase. Deposition of impurities on the catalyst surface caused a quick deactivation in silent experiments resulting only 5% of DBT oxidation after 6 cycles of silent reaction by recycled catalyst. Above 95% of DBT was oxidized after 6 ultrasound-assisted cycles showing a great improvement in stability by cleaning the surface during ultrasonication. A considerable particle size reduction was also observed after 3 h sonication that could provide more dispersion of catalyst in model fuel.     

Efficient H2O2/CH3COOH oxidative desulfurization/denitrification of liquid fuels in sonochemical flow-reactors

The oxidative desulfurization/denitrification of liquid fuels has been widely investigated as an alternative or complement to common catalytic hydrorefining. In this process, all oxidation reactions occur in the heterogeneous phase (the oil and the polar phase containing the oxidant) and therefore the optimization of mass and heat transfer is of crucial importance to enhancing the oxidation rate. This goal can be achieved by performing the reaction in suitable ultrasound (US) reactors. In fact, flow and loop US reactors stand out above classic batch US reactors thanks to their greater efficiency and flexibility as well as lower energy consumption. This paper describes an efficient sonochemical oxidation with H₂O₂/CH₃COOH at flow rates ranging from 60 to 800 ml/min of both a model compound, dibenzotiophene (DBT), and of a mild hydro-treated diesel feedstock. Four different commercially available US loop reactors (single and multi-probe) were tested, two of which were developed in the authors’ laboratory. Full DBT oxidation and efficient diesel feedstock desulfurization/denitrification were observed after the separation of the polar oxidized S/N-containing compounds (S ⩽ 5 ppmw, N ⩽ 1 ppmw). Our studies confirm that high-throughput US applications benefit greatly from flow-reactors.     

Enhanced desulfurizing flotation of coal using sonoelectrochemical method

Enhanced desulfurizing flotation of low sulfur coal was investigated using sonoelectrochemical method. The supporting electrolyte used in this process was sodium chloride and the additive was anhydrous ethanol. The effects of treatment conditions on desulfurization were studied by a single-factor method. The conditions include anhydrous ethanol concentration, sodium chloride concentration, sonoelectrolytic voltage, sonoelectrolytic temperature, sonoelectrolytic time and coal sample granulometry. The optimal experimental conditions achieved for anhydrous ethanol concentration, sodium chloride concentration, sonoelectrolytic voltage, sonoelectrolytic temperature and sonoelectrolytic time are 1.7 mol L^?1, 5.1 × 10^?3 mol L^?1, 10 V, 70 °C, 50 min achieved for a ?0.18 mm coal sample. Optimal conditions cause a sulfur reduction of up to 69.4%. The raw and treated coals were analyzed by infrared spectroscopy and a chemical method. Pyritic sulfur, organic sulfur, ash as well as moisture are partially removed. The combination of high sulfur reduction, high yield, as well as high ash reduction was obtained in the newly developed method of enhanced flotation by sonoelectrochemistry. Ultrasound irradiation promotes electron transfer efficiency and increases clean coal yield.     

Ultrasound-assisted oxidation of dibenzothiophene with phosphotungstic acid supported on activated carbon

Phosphotungstic acid (HPW) supported on activated carbon (AC) was applied to catalyze deep oxidation desulfurization of fuel oil with the assist of ultrasound. The sulfur-conversion rate was evaluated by measuring the concentration of dibenzothiophene (DBT) in n-octane before and after the oxidation. Supporting HPW on AC has been verified to play a positive role in UAOD process by a series of contrast tests, where only HPW, AC or a mixture of free HPW and AC was used. The influences of catalyst dose, ultrasound power, reaction temperature, H₂O₂:oil volume ratio and the reuse of catalyst on the catalytic oxidation desulfurization kinetics were investigated. The DBT conversion rate of the reaction catalyzed by supported HPW under ultrasound irradiation was higher than the summation of the reactions with HPW only and AC only as catalyst. With the increase of loading amount of HPW on AC, ultrasound power, H₂O₂:oil volume ratio and reaction temperature, the catalytic oxidation reactivity of DBT would be enhanced. The optimum loading amount of HPW was 10%, exceed which DBT conversion would no longer increase obviously. DBT could be completely converted under the optimized conditions (volume ratio of H₂O₂ to model oil: 1:10, mass ratio of the supported HPW to model oil: 1.25%, temperature: 70 °C) after 9 min of ultrasound irradiation.     

Ultrasound assisted oxidative desulfurization of model diesel fuel

Very stringent environmental regulations have limited the level of sulfur in diesel, therefore deep desulfurization of fuels is required. For that purpose, the frequently used industrial process is hydrodesulfurization (HDS) which enables effective elimination of sulfur compounds such as mercaptanes, thiols, sulfides, disulfides from diesel oil, but removal of thiophene sulfur compounds (benzothiophene, dibenzothiophene, 4,6 dimethyldibenzothiophene) is insufficient. Ultrasound assisted oxidative desulfurization (UAOD) as one of several new technologies enables performance under mild conditions without use of explosive hydrogen. A higher reactivity of thiophene sulfur compounds during UAOD also provides conversion into highly polar sulfoxides and sulfones that are easily removed by adsorption or extraction. Nowadays, different catalyst/oxidants systems are being studied to improve oxidation reaction efficiency and enhance the mass transfer in the interfacial region. In this paper, the effect of reaction temperature (40–70 °C) and oxidation time (5–150 min) for UAOD of model diesel fuel with a catalyst/oxidants system (acetic acid/hydrogen peroxide) was investigated in a 70 ml batch reactor. Furthermore, the effects of different initial concentrations of dibenzothiophene (DBT) and of ultrasound amplitude were additionally examined to achieve efficient sulfur removal. The obtained results indicated that temperature and US amplitude of 70 °C and 80% respectively were efficient for conversion of DBT (sulfur concentration up to 3976.86 ppm). The results indicate a rise in the yield of sulfones at higher temperatures and subsequent extraction with N,N-dimethylformamide conducted after the process of oxidation at different solvent/oil ratio revealed sulfur removal efficiency of 98.35%.     

Electrical effect of soot depositions in a co-axial wire pipe flow

An investigation was performed to study the electrical effects on the soot deposition in a co-axial wire cylinder with cooled walls. Experiments were performed for applied voltages from 0 to ?5 kV or +5 kV and a diesel exhaust mass flow rate of 20 kg/h or Reynolds number of approximately 9000. The outer wall was cooled using water with a temperature of approximately 40 °C, and the experiments were performed for exposure times of 2 h. The soot deposition layer thickness was measured using a non-destructive neutron radiography technique at the end of each experiment. The results show that the electric field had a significant effect on the soot deposition and increases it by a factor of approximately 4 at the applied voltage of 5 kV before spark on-set. The soot thickness was similar for the positive and negative polarities and the results show that there was significant deposition on the wire as well as the outer wall for both polarities. Since soot deposition even occurs on both corona wire and grounded pipe below corona on-set voltages of the clean system, there may be a significant pre-charging of the diesel soot with both polarities in the diesel exhaust gas as has been observed by the recent measurements of Marieq [On the electrical charge of motor vehicle exhaust particles, Journal of Aerosol Science 37 (7) (2006) 858–874].     

Ultrasonic pilot-scale reactor for enzymatic bleaching of cotton fabrics

The potential of ultrasound-assisted technology has been demonstrated by several laboratory scale studies. However, their successful industrial scaling-up is still a challenge due to the limited pilot and commercial sonochemical reactors. In this work, a pilot reactor for laccase-hydrogen peroxide cotton bleaching assisted by ultrasound was scaled-up. For this purpose, an existing dyeing machine was transformed and adapted by including piezoelectric ultrasonic devices. Laboratory experiments demonstrated that both low frequency, high power (22 kHz, 2100 W) and high frequency, low power ultrasounds (850 kHz, 400 W) were required to achieve satisfactory results. Standard half (4 g/L H₂O₂ at 90 °C for 60 min) and optical (8 g/L H₂O₂ at 103 °C for 40 min) cotton bleaching processes were used as references. Two sequential stages were established for cotton bleaching: (1) laccase pretreatment assisted by high frequency ultrasound (850 kHz, 400 W) and (2) bleaching using high power ultrasound (22 kHz, 2100 W). When compared with conventional methods, combined laccase-hydrogen peroxide cotton bleaching with ultrasound energy improved the whitening effectiveness. Subsequently, less energy (temperature) and chemicals (hydrogen peroxide) were needed for cotton bleaching thus resulting in costs reduction. This technology allowed the combination of enzyme and hydrogen peroxide treatment in a continuous process. The developed pilot-scale reactor offers an enhancement of the cotton bleaching process with lower environmental impact as well as a better performance of further finishing operations.     

Advanced oxidation processes (AOPs) involving ultrasound for waste water treatment: A review with emphasis on cost estimation

Two things are needed for any technology to be suitable for use in the industry, viz. 1. Technical feasibility and 2. Economical feasibility. The use of ultrasound for waste water treatment has been shown to be technically feasible by numerous reports in the literature over the years. But there are hardly any exhaustive reports which address the issue of economical feasibility of the use of ultrasound for waste water treatment on industrial scale.Hence an attempt was made to estimate the cost for the waste water treatment using ultrasound. The costs have been calculated for 1000 L/min capacity treatment plant. The costs were calculated based upon the rate constants for pollutant degradation. The pollutants considered were phenol, trichloroethylene (TCE) and reactive azo dyes. Time required for ninety percent degradation of pollutant was taken as the residence time. The amount of energy required to achieve the target degradation was calculated from the energy density (watt/ml) used in the treatability study. The cost of treatment was calculated by considering capital cost and operating cost involved for the waste water treatment. Quotations were invited from vendors to ascertain the capital cost of equipments involved and operating costs were calculated based on annual energy usage. The cost was expressed in dollars per 1000 gallons of waste water treated. These treatment costs were compared with other established Advanced Oxidation Process (AOP) technologies. The cost of waste water treatment for phenol was in the range of $89 per 1000 gallons for UV/US/O₃ to $15,536 per 1000 gallons for US alone. These costs for TCE were in the range of $25 per 1000 gallons to $91 for US + UV treatment and US alone, respectively. The cost of waste water treatment for reactive azo dyes was in the range of $65 per 1000 gallon for US + UV + H₂O₂ to $14,203 per 1000 gallon for US alone.This study should help in quantifying the economics of waste water treatment using ultrasound on industrial scale. We strongly believe that this study will immensely help the researchers working in the area of applications of ultrasound for waste water treatment in terms of where the technology stands today as compared to other available commercial AOP technologies. This will also help them think for different ways to improve the efficiency of using ultrasound or search for other ways of generating cavitation which may be more efficient and help reduce the cost of treatment in future.     

Ultrasound-assisted oxidative process for sulfur removal from petroleum product feedstock

A procedure using ultrasonic irradiation is proposed for sulfur removal of a petroleum product feedstock. The procedure involves the combination of a peroxyacid and ultrasound-assisted treatment in order to comply with the required sulfur content recommended by the current regulations for fuels. The ultrasound-assisted oxidative desulfurization (UAOD) process was applied to a petroleum product feedstock using dibenzothiophene as a model sulfur compound. The influence of ultrasonic irradiation time, oxidizing reagents amount, kind of solvent for the extraction step and kind of organic acid were investigated. The use of ultrasonic irradiation allowed higher efficiency for sulfur removal in comparison to experiments performed without its application, under the same reactional conditions. Using the optimized conditions for UAOD, the sulfur removal was about 95% after 9 min of ultrasonic irradiation (20 kHz, 750 W, run at 40%), using hydrogen peroxide and acetic acid, followed by extraction with methanol.     

Photoelectron spectroscopy study of irradiation damage and metal–sulfur bonds of thiol on silver and copper surfaces

Self-assembled 1-dodecanethiol monolayers (SAMs) on silver and copper surfaces have been characterized with X-ray photoelectron spectroscopy (XPS) using both the synchrotron radiation and conventional Mg Kα excitation. Irradiation-induced changes in thiolate SAMs on Cu and Ag were observed. The identification of the sulfur species has been done. Results obtained confirm earlier studies of n-alkanethiols on silver. On copper (C₁₂S/Cu), the observed S 2p spectrum is quite broad but the use of different excitation energies enabled us to identify four sulfur species on the surface. A S 2p_3/2 component of copper thiolate is observed at 162.6 eV. Three more doublets (161.9 eV, 163.2 eV and 163.8 eV) have been observed to develop during irradiation and they are assigned to chemisorbed sulfur on copper, to different dialkylsulfides and to sulfur–sulfur bonding.     

Synthesis of biodiesel from waste cooking oil using sonochemical reactors

Investigation into newer routes of biodiesel synthesis is a key research area especially due to the fluctuations in the conventional fuel prices and the environmental advantages of biodiesel. The present work illustrates the use of sonochemical reactors for the synthesis of biodiesel from waste cooking oil. Transesterification of used frying oil with methanol, in the presence of potassium hydroxide as a catalyst has been investigated using low frequency ultrasonic reactor (20 kHz). Effect of different operating parameters such as alcohol–oil molar ratio, catalyst concentration, temperature, power, pulse and horn position on the extent of conversion of oil have been investigated. The optimum conditions for the transesterification process have been obtained as molar ratio of alcohol to oil as 6:1, catalyst concentration of 1 wt.%, temperature as 45 °C and ultrasound power as 200 W with an irradiation time of 40 min. The efficacy of using ultrasound has been compared with the conventional stirring approach based on the use of a six blade turbine with diameter of 1.5 cm operating at 1000 rpm. Also the purification aspects of the final product have been investigated.     

Planar sulfur-doped silicon detectors for high-speed infrared thermography

Planar extrinsic sulfur-doped silicon detectors for infrared (IR) semiconductor-discharge gap image converters intended for use in high-speed thermography of remote objects have been developed. The detectors were fabricated by high-temperature diffusion of sulfur into silicon wafers from the vapor phase. The dependence of doping efficiency on the sulfur vapor pressure in the course of diffusion was analyzed. The detector fabrication technology was optimized to meet the specific requirements for their operation in the microdischarge devices considered. The detectors were tested in a laboratory setup comprising a blackbody source of IR light, an image converter, and a pulsed CCD camera for recording the converted images. The converter equipped with the detector can provide imaging of objects heated to a temperature, T_min ≈ 200 °C, with a temporal resolution on the order of 10^?6 s and spatial resolution of about 5 lines/mm.     

Large scale environmental applications of high power ultrasound

In the present work, the use of high power ultrasound as a process tool for the removal of persistent organic pollutants (POPs) from soil and the treatment of bauxite red mud waste from the Bayer process is discussed. Laboratory scale experiments have confirmed that the application of high power ultrasound to slurries of contaminated soil and of bauxite ore can treat two major environmental problems cost-effectively. Destruction rates of POPs in soil of 90% and higher have been achieved whereas 85% iron oxide has been extracted from red mud waste leaving a low-iron fraction of approximately 50% by weight which is more environmentally friendly.A 4 × 4 kW pilot plant capable of treating 2.5 tonnes of slurry per day has been commissioned to provide more accurate estimates of power and energy requirements to allow scale-up to industrial use.     

Detection of sulfur in the reinforced concrete structures using a dual pulsed LIBS system

In concrete structures, an excessive amount of sulfate ions can cause severe damage to the strength and the stability of the building structures and hence a sensitive and reliable technique for sulfate ion detection in concrete is highly desirable. Laser-induced breakdown spectroscopy (LIBS) is one of the most reliable and sensitive techniques to identify the presence of potentially dangerous sulfur in the concrete structure. The atomic emission lines of sulfur lying in the 200–900 nm region are mostly singly ionized states and hence inherently very weak. In order to enhance the sensitivity of the conventional LIBS system, we employed a dual pulsed LIBS system for detection of weak spectral line of sulfur in concrete using the S II peak at 545.38 nm as a marker for quantifying sulfur content in the concrete. The 1064 nm fundamental and 266 nm fourth harmonic of the Nd:YAG laser in conjunction with Spectrograph/gated ICCD camera are the core factors in improvement of sensitivity. Furthermore, the dual pulsed LIBS system and the fine maneuvering of the gate parameters and interpulse delay yielded improvement in the sensitivity, and resulted in a systematic correlation of the LIBS signal with the concentration of sulfur in the concrete sample. In order to quantify the sulfur content in concrete, a calibration curve was also drawn by recording the LIBS spectra of sample having sulfur in various concentrations. The limit of detection achieved with our dual pulsed LIBS system is approximately 38 μg/g.     

Fire safety distances for open pool fires

Fire accidents that carry huge loss with them have increased in the previous two decades than at any time in the history. Hence, there is a need for understanding the safety distances from different fires with different fuels. Fire safety distances are computed for different open pool fires. Diesel, gasoline and hexane are used as fuels for circular pool diameters of 0.5 m, 0.7 m and 1.0 m. A large square pool fire of 4 m × 4 m is also conducted with diesel as a fuel. All the prescribed distances in this study are purely based on the thermal analysis. IR camera is used to get the thermal images of pool fires and there by the irradiance at different locations is computed. The computed irradiance is presented with the threshold heat flux limits for human beings.     

Sonochemical and hydrodynamic cavitation reactors for laccase/hydrogen peroxide cotton bleaching

The main goal of this work is to develop a novel and environmental-friendly technology for cotton bleaching with reduced processing costs. This work exploits a combined laccase–hydrogen peroxide process assisted by ultrasound. For this purpose, specific reactors were studied, namely ultrasonic power generator type K8 (850 kHz) and ultrasonic bath equipment Ultrasonic cleaner USC600TH (45 kHz). The optimal operating conditions for bleaching were chosen considering the highest levels of hydroxyl radical production and the lowest energy input. The capacity to produce hydroxyl radicals by hydrodynamic cavitation was also assessed in two homogenizers, EmulsiFlex®-C3 and APV-2000. Laccase nanoemulsions were produced by high pressure homogenization using BSA (bovine serum albumin) as emulsifier. The bleaching efficiency of these formulations was tested and the results showed higher whiteness values when compared to free laccase. The combination of laccase–hydrogen peroxide process with ultrasound energy produced higher whiteness levels than those obtained by conventional methods. The amount of hydrogen peroxide was reduced 50% as well as the energy consumption in terms of temperature (reduction of 40 °C) and operating time (reduction of 90 min).     

Coverage effects on the adsorption of sulfur on Co(0 0 0 1): A DFT study

The adsorption of sulfur on Co(0 0 0 1) was studied using density functional theory calculations at coverage from 0.11 ML to 1.0 ML. Calculated results indicate that atomic S favors in hollow sites with bond S–Co dominated at lower coverage and at higher coverage the strong adsorbate S–S interaction leads to the formation of S₂ species. It was shown that the adsorption energy generally increases (gets weaker) with the coverage in a near linear fashion for the most stable configurations. In addition, modification of the surface electronic properties has been discussed and some discrepancy are found between our calculations and the findings of O adsorption on Au(1 1 1) and Pt(1 1 1) surfaces.     

Ultrasound-assisted extraction of Na and K from swine feed and its application in a digestibility assay: A green analytical procedure

The study is aimed to evaluate the efficiency of ultrasound-assisted extraction (UAE) as a simple strategy focused on sample preparation for metal determination in biological samples. The extraction of sodium and potassium extraction was carried out from swine feed followed by determination of the concentration of these metals by flame atomic emission spectrometry (FAES). The experiment was performed to cover the study of the variables influencing the extraction process and its optimal conditions (sample mass, particle size, acid concentration, sonication time and ultrasound power); the determination of these analytical characteristics and method validation using certified reference material; and the analysis of pre-starter diets. The optimal conditions established conditions were as follows: mass: 100 mg, particle size:<60 μm, acid concentration: 0.10 mol L^?1 HCl, sonication time: 50 s and ultrasound power: 102 W. The proposed method (UAE) was applied in digestibility assays of those nutrients present in different piglet pre-starter feeds and their results proved to be compatible with those obtained from mineralized samples (P < 0.05). The ultrasound extraction method was demonstrated to be an excellent alternative for handless sampling and operational costs and the method also has the advantage of does not generating toxic residues that may negatively affect human health and contaminate the environment.     

Synergetic effects of ultrasound and slightly acidic electrolyzed water against Staphylococcus aureus evaluated by flow cytometry and electron microscopy

This study evaluated the synergetic effects of ultrasound and slightly acidic electrolyzed water (SAEW) on the inactivation of Staphylococcus aureus using flow cytometry and electron microscopy. The individual ultrasound treatment for 10 min only resulted in 0.36 log CFU/mL reductions of S. aureus, while the SAEW treatment alone for 10 min resulted in 3.06 log CFU/mL reductions. The log reductions caused by combined treatment were enhanced to 3.68 log CFU/mL, which were greater than the sum of individual treatments. This phenomenon was referred to as synergistic effects. FCM analysis distinguished live and dead cells as well as revealed dynamic changes in the physiological states of S. aureus after different treatments. The combined treatment greatly reduced the number of viable but nonculturable (VBNC) bacteria to 0.07%; in contrast, a single ultrasound treatment for 10 min induced the formation of VBNC cells to 45.75%. Scanning and transmission electron microscopy analysis revealed that greater damage to the appearance and ultrastructure of S. aureus were achieved after combined ultrasound-SAEW treatment compared to either treatment alone. These results indicated that combining ultrasound with SAEW is a promising sterilization technology with potential uses for environmental remediation and food preservation.