Examination of the Reasons for the Formation of Red Oil in Spent Caustic from Olefin Plant

Due to the complexity of olefinic plants, various environmental pollutants exist such as NOx, CO2, Tar Water, and most importantly Spent Caustic. In this paper, instead of investigating ways of treating this pollutant, we evaluated the production in relation to plant’s variable items. We primarily discussed the factors affecting the quality of the output spent caustic such as impurities in the feed of olefin plant, the amount of injected dimethyl disulfide (DMDS) in furnaces, variation in feed composition, differences among gas temperatures and the concentration of caustic solution at the bottom of the tower. The results of the laboratory proved that in the formation of Red Oil, 1,3butadiene and acetaldehyde followed free radical and aldol condensation mechanism respectively. By increasing the injection rate of DMDS, Mercaptide amount increases in the effluent. In addition, pyrolysis gasoline accumulation is directly related to caustic concentration in the tower. Increasing naphtenes in the liquid feed augments the amount of 1,3butadiene, as one of the sources of Red Oil formation. By increasing the oxygenated compound in the feed, the rate of acetaldehyde formation, as the main source of Red Oil formation, increases.

Natural Preservatives: An Alternative for Chemical Preservative Used in Foods

Microbial degradation of foods is defined as a decrease of food safety due to microorganism activity. Organic acids, sulfur dioxide, sulfide, nitrate, nitrite, dimethyl dicarbonate and several preservative gases have been used as chemical preservatives in foods as well as natural preservatives which are indigenous in foods. It is determined that usage of herbal preservatives such as blueberry, dried grape, prune, garlic, mustard, spices inhibited several microorganisms. Moreover, it is determined that animal origin preservatives such as whey, honey, lysosomes of duck egg and chicken egg, chitosan have antimicrobial effect. Other than indigenous antimicrobials in foods, antimicrobial agents produced by microorganisms could be used as natural preservatives. The antimicrobial feature of preservatives depends on the antimicrobial spectrum, chemical and physical features of material, concentration, mode of action, components of food, process conditions, and pH and storage temperature. In this review, studies about antimicrobial components which are indigenous in food (such as herbal and animal origin antimicrobial agents), antimicrobial materials synthesized by microorganisms, and their usage as an antimicrobial agent to preserve foods are discussed.

Cadmium Filter Cake of a Hydrometallurgical Zinc Smelter as a New Source for the Biological Synthesis of CdS Quantum Dots

The cadmium sulfide nanoparticles were synthesized from the nickel-cadmium cake of a hydrometallurgical zinc producing plant and sodium sulfide as Cd2+ and S-2 sources, respectively. Also, the synthesis process was performed by using the secretions of Bacillus licheniformis as bio-surfactant. Initially, in order to obtain a cadmium rich solution, two following steps were carried out: 1) Alkaline leaching for the removal of zinc oxide from the cake, and 2) acidic leaching to dissolve cadmium from the remained solid residue. Afterward, the obtained CdSO4 solution was used for the nanoparticle biosynthesis. Nanoparticles were characterized by the energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) to confirm the formation of CdS crystals with cubic structure. Also, transmission electron microscopy (TEM) was applied to determine the particle sizes which were in 2-10 nm range. Moreover, the presence of the protein containing bio-surfactants was approved by using infrared analysis (FTIR). In addition, the absorbance below 400 nm confirms quantum particles’ size. Finally, it was shown that valuable CdS quantum dots could be obtained from the industrial waste products via environment-friendly biological approaches.

Characterization and Geochemical Modeling of Cu and Zn Sorption Using Mixed Mineral Systems Injected with Iron Sulfide under Sulfidic-Anoxic Conditions I: Case Study of Cwmheidol Mine Waste Water, Wales, United Kingdom

This study investigates sorption of Cu and Zn contained in natural mine wastewater, using mixed mineral systems in sulfidic-anoxic condition. The mine wastewater was obtained from disused mine workings at Cwmheidol in Wales, United Kingdom. These contaminants flow into water courses. These water courses include River Rheidol. In this River fishing activities exist. In an attempt to reduce Cu-Zn levels of fish intake in the watercourses, single mineral systems and 1:1 mixed mineral systems of clay and goethite were tested with the mine waste water for copper and zinc removal at variable pH. Modelling of hydroxyl complexes was carried out using phreeqc method. Reactions using batch mode technique was conducted at room temperature. There was significant differences in the behaviour of copper and zinc removal using mixed mineral systems when compared  to single mineral systems. All mixed mineral systems sorb more Cu than Zn when tested with mine wastewater.

Co-Disposal of Coal Ash with Mine Tailings in Surface Paste Disposal Practices: A Gold Mining Case Study

The present paper describes the study of paste tailings prepared in laboratory using gold tailings, produced in a Finnish gold mine with the incorporation of coal ash. Natural leaching tests were conducted with the original materials (tailings, fly and bottom ashes) and also with paste mixtures that were prepared with different percentages of tailings and ashes. After leaching, the solid wastes were physically and chemically characterized and the results were compared to those selected as blank – the unleached samples. The tailings and the coal ash, as well as the prepared mixtures, were characterized, in addition to the textural parameters, by the following measurements: grain size distribution, chemical composition and pH. Mixtures were also tested in order to characterize their mechanical behavior by measuring the flexural strength, the compressive strength and the consistency. The original tailing samples presented an alkaline pH because during their processing they were previously submitted to pressure oxidation with destruction of the sulfides. Therefore, it was not possible to ascertain the effect of the coal ashes in the acid mine drainage. However, it was possible to verify that the paste reactivity was affected mostly by the bottom ash and that the tailings blended with bottom ash present lower mechanical strength than when blended with a combination of fly and bottom ash. Surface paste disposal offer an attractive alternative to traditional methods in addition to the environmental benefits of incorporating large-volume wastes (e.g. bottom ash). However, a comprehensive characterization of the paste mixtures is crucial to optimize paste design in order to enhance engineer and environmental properties.

Noninvasive Disease Diagnosis through Breath Analysis Using DNA-Functionalized SWNT Sensor Array

Noninvasive diagnostics of diseases via breath analysis has attracted considerable scientific and clinical interest for many years and become more and more promising with the rapid advancements in nanotechnology and biotechnology. The volatile organic compounds (VOCs) in exhaled breath, which are mainly blood borne, particularly provide highly valuable information about individuals’ physiological and pathophysiological conditions. Additionally, breath analysis is noninvasive, real-time, painless, and agreeable to patients. We have developed a wireless sensor array based on single-stranded DNA (ssDNA)-functionalized single-walled carbon nanotubes (SWNT) for the detection of a number of physiological indicators in breath. Seven DNA sequences were used to functionalize SWNT sensors to detect trace amount of methanol, benzene, dimethyl sulfide, hydrogen sulfide, acetone, and ethanol, which are indicators of heavy smoking, excessive drinking, and diseases such as lung cancer, breast cancer, and diabetes. Our test results indicated that DNA functionalized SWNT sensors exhibit great selectivity, sensitivity, and repeatability; and different molecules can be distinguished through pattern recognition enabled by this sensor array. Furthermore, the experimental sensing results are consistent with the Molecular Dynamics simulated ssDNAmolecular target interaction rankings. Thus, the DNA-SWNT sensor array has great potential to be applied in chemical or biomolecular detection for the noninvasive diagnostics of diseases and personal health monitoring.

Ferrites of the MeFe2O4 System (Me – Zn, Cu, Cd) and Their Two Faces

The ferrites ZnFe2O4, CdFe2O4 and CuFe2O4 are synthesized in laboratory conditions using ceramic technology. Their homogeneity and structure are proven by X-Ray diffraction analysis and Mössbauer spectroscopy. The synthesized ferrites are subjected to strong acid and high temperature leaching with solutions of H2SO4, HCl and HNO3. The results indicate that the highest degree of leaching of Zn, Cd and Cu from the ferrites is achieved by use of HCl. The charging of five zinc sulfide concentrates was optimized using the criterion of minimal amount of zinc ferrite produced when roasting the concentrates in a fluidized bed. The results obtained are interpreted in terms of the hydrometallurgical zinc production and maximum recovery of zinc, copper and cadmium from initial zinc concentrates after their roasting.

Nonlinear Absorption and Scattering in Wide Band Gap Silver Sulfide Nanoparticles Colloid and Their Effects on the Optical Limiting

In this paper, we study the optical nonlinearities of Silver sulfide (Ag2S) nanostructures dispersed in the Dimethyl sulfoxide (DMSO) under exposure to 532 nm, 15 nanosecond (ns) pulsed laser irradiation. Ultraviolet–visible absorption spectrometry (UV-Vis), X-ray diffraction (XRD), and transmission electron microscopy (TEM) are used to characterize the obtained nanocrystal samples. The band gap energy of colloid is determined by analyzing the UV–Vis absorption spectra of the Ag2S NPs using the band theory of semiconductors. Z-scan technique is used to characterize the optical nonlinear properties of the Ag2S nanoparticles (NPs). Large enhancement of two photon absorption effect is observed with increase in concentration of the Ag2S nanoparticles using open Zscan measurements in the ns laser regime. The values of the nonlinear absorption coefficients are determined based on the local nonlinear responses including two photon absorption. The observed aperture dependence of the Ag2S NP limiting performance indicates that the nonlinear scattering plays an important role in the limiting action of the sample. The concentration dependence of the optical liming is also investigated. Our results demonstrate that the optical limiting threshold decreases with increasing the silver sulfide NPs in DMSO.

Exploring the Influences on Entrainment of Serpentines by Grinding and Reagents

This paper presents the influences on the entrainment of serpentines by grinding and reagents during copper–nickel sulfide flotation. The previous bench flotation tests were performed to extract the metallic values from the ore in Yunnan Mine, China and the relatively satisfied results with recoveries of 86.92% Cu, 54.92% Ni, and 74.73% Pt+Pd in the concentrate were harvested at their grades of 4.02%, 3.24% and 76.61 g/t, respectively. However, the content of MgO in the concentrate was still more than 19%. Micro-flotation tests were conducted with the objective of figuring out the influences on the entrainment of serpentines into the concentrate by particle size, flocculants or depressants and collectors, as well as visual observations in suspension by OLYMPUS camera. All the tests results pointed to the presences of both “entrapped-in” serpentines and its coating on the hydrophobic flocs resulted from strong collectors (combination of butyl xanthate, butyl ammonium dithophosphate, even after adding carboxymethyl cellulose as effective depressant. And fine grinding may escalate the entrainment of serpentines in the concentrate.

Comparison of Transparent Nickel Doped Cobalt Sulfide and Platinum Counter Electrodes Used in Quasi-Solid State Dye Sensitized Solar Cells

Transparent nickel doped cobalt sulfide was fabricated on a SnO2:F electrode and tested as an efficient electrocatalyst and as an alternative to the expensive platinum counter electrode. In order to investigate how this electrode could affect the electrical characteristics of a dye-sensitized solar cell, we manufactured cells with the same TiO2 photoanode sensitized with dye (N719) and employing the same quasi-solid electrolyte, altering only the counter electrode used. The cells were electrically and electrochemically characterized and it was observed that the ones with the Ni doped CoS2 outperformed the efficiency of the cells with the Pt counter electrode (3.76% and 3.44% respectively). Particularly, the higher efficiency of the cells with the Ni doped CoS2 counter electrode (CE) is mainly because of the enhanced photocurrent density which is attributed to the enhanced electrocatalytic ability of the CE and the low charge transfer resistance at the CE/electrolyte interface.

Wet Flue Gas Desulfurization Using a New O-Element Design Which Replaces the Venturi Scrubber

Scrubbing by a liquid spraying is one of the most effective processes used for removal of fine particles and soluble gas pollutants (such as SO2, HCl, HF) from the flue gas. There are many configurations of scrubbers designed to provide contact between the liquid and gas stream for effectively capturing particles or soluble gas pollutants, such as spray plates, packed bed towers, jet scrubbers, cyclones, vortex and venturi scrubbers. The primary function of venturi scrubber is the capture of fine particles as well as HCl, HF or SO2 removal with effect of the flue gas temperature decrease before input to the absorption column. In this paper, sulfur dioxide (SO2) from flue gas was captured using new design replacing venturi scrubber (1st degree of wet scrubbing). The flue gas was prepared by the combustion of the carbon disulfide solution in toluene (1:1 vol.) in the flame in the reactor. Such prepared flue gas with temperature around 150°C was processed in designed laboratory O-element scrubber. Water was used as absorbent liquid. The efficiency of SO2 removal, pressure drop and temperature drop were measured on our experimental device. The dependence of these variables on liquid-gas ratio was observed. The average temperature drop was in the range from 150°C to 40°C. The pressure drop was increased with increasing of a liquid-gas ratio, but no too much as for the common venturi scrubber designs. The efficiency of SO2 removal was up to 70 %. The pressure drop of our new designed wet scrubber is similar to commonly used venturi scrubbers; nevertheless the influence of amount of the liquid on pressure drop is not so significant.

S-S Coupling of Thiols to Disulfides Using Ionic Liquid in the Presence of Free Nano-Fe2O3 Catalyst

An efficient and green method for oxidation of thiols to the corresponding disulfides is reported using ionic liquid [HSO3N(C2H4OSO3H)3] in the presence of free nano-Fe2O3 at 60°C. Ionic liquid is selective oxidant for S-S Coupling variety aliphatic and aromatic of thiols to corresponding disulfide in the presence of free nano-Fe2O3 as recoverable catalyst. Reaction has been performed in methanol as an inexpensive solvent. This reaction is clean and easy work-up with no side reaction.

Influence and Interaction of Temperature, H2S and pH on Concrete Sewer Pipe Corrosion

Concrete sewer pipes are known to suffer from a process of hydrogen sulfide gas induced sulfuric acid corrosion. This leads to premature pipe degradation, performance failure and collapses which in turn may lead to property and health damage. The above work reports on a field study undertaken in working sewer manholes where the parameters of effluent temperature and pH as well as ambient temperature and concentration of hydrogen sulfide were continuously measured over a period of two months. Early results suggest that effluent pH has no direct effect on hydrogen sulfide build up; on average the effluent temperature is 3.5°C greater than the ambient temperature inside the manhole and also it was observed that hydrogen sulfate concentration increases with increasing temperature.

Comparison of Bioleaching of Metals from Spent Petroleum Catalyst Using Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans

The present investigation deals with bioleaching of spent petroleum catalyst using At. ferrooxidans and At. thiooxidans. The spent catalyst used in the present study was pretreated with acetone to remove the oily hydrocarbons. FESEM and XPS analysis indicated the presence of metals in sulfide and oxide forms in spent catalyst. Both At. ferrooxidans and At. thiooxidans were found to be highly effective in producing the acid. Bioleaching with At. ferrooxidans and At. thiooxidans led to higher recovery of metals compare to control. During bioleaching similar recoveries of metals were obtained using At. ferrooxidans and At. thiooxidans. This might be due to the presence of metals as soluble oxides and sulphides in the spent catalyst. At the end of bioleaching, about 87-90% Ni, 34% Al, 65-73% Mo and 92-97% V were leached using above bacteria. It is elucidated that bioleaching with At. thiooxidans is comparatively more advantageous due to lower cost of sulphur.  

Removal of Iron from Groundwater by Sulfide Precipitation

Iron in groundwater is one of the problems that render the water unsuitable for drinking. The concentration above 0.3 mg/L is common in groundwater. The conventional method of removal is by precipitation under oxic condition. In this study, iron removal under anaerobic conditions was examined by batch experiment as a main purpose. The process involved by purging of groundwater samples with H2S to form iron sulfide. Removal up to 83% for 1 mg/L iron solution was achieved. The removal efficiency dropped to 82% and 75% for the higher initial iron concentrations 3.55 and 5.01 mg/L, respectively. The average residual sulfide concentration in water after the process was 25*g/L. The Eh level during the process was -272 mV. The removal process was found to follow the first order reaction with average rate constant of 4.52 x 10-3. The half-life for the concentrations to reduce from initial values was 157 minutes.

Preparation and Evaluation of New Nanocatalysts for Selective Oxidation of H2S to Sulfur

Selective oxidation of H2S to elemental sulfur in a fixed bed reactor over newly synthesized alumina nanocatalysts was physio-chemically investigated and results compared with a commercial Claus catalyst. Amongst these new materials, Al2O3- supported sodium oxide prepared with wet chemical technique and Al2O3 nanocatalyst prepared with spray pyrolysis method were the most active catalysts for selective oxidation of H2S to elemental sulfur. Other prepared nanocatalysts were quickly deactivated, mainly due to the interaction with H2S and conversion into sulfides.

The Effect of Cyclic Speed on the Wear Properties of Molybdenum Disulfide Greases under Extreme Pressure Loading Using 4 Balls Wear Tests

The relationship between different types of Molybdenum disulfide greases under extreme pressure loading and different speed situations have been studied using Design of Experiment (DOE) under 1200rpm steady state rotational speed and cyclic frequencies between 2400 and 1200rpm using a Plint machine software to set up the different rotational speed situations.  Research described here is aimed at providing good friction and wear performance while optimizing cyclic frequencies and MoS2 concentration due to the recent concern about grease behavior in extreme pressure applications. Extreme load of 785 Newton was used in conjunction with different cyclic frequencies (2400rpm -3.75min, 1200rpm -7.5min, 2400rpm -3.75min, 1200rpm -7.5min), to examine lithium based grease with and without MoS2 for equal number of revolutions, and a total run of 36000 revolutions; then compared to 1200rpm steady speed for the same total number of revolutions. 4 Ball wear tester was utilized to run large number of experiments randomly selected by the DOE software. The grease was combined with fine grade MoS2 or technical grade then heated to 750C and the wear scar width was collected at the end of each test. DOE model validation results verify that the data were very significant and can be applied to a wide range of extreme pressure applications. Based on simulation results and Scanning Electron images (SEM), it has been found that wear was largely dependent on the cyclic frequency condition. It is believed that technical grade MoS2 greases under faster cyclic speeds perform better and provides antiwear film that can resist extreme pressure loadings. Figures showed reduced wear scars width and improved frictional values.  

Reactive Absorption of Hydrogen Sulfide in Aqueous Ferric Sulfate Solution

Many commercial processes are available for the removal of H2S from gaseous streams. The desulfurization of gas streams using aqueous ferric sulfate solution as washing liquor is studied. Apart from sulfur, only H2O is generated in the process, and consequently, no waste treatment facilities are required. A distinct advantage of the process is that the reaction of H2S with is so rapid and complete that there remains no danger of discharging toxic waste gas. In this study, the reactive absorption of hydrogen sulfide into aqueous ferric sulfate solution has been studied and design calculations for equipments have been done and effective operation parameters on this process considered. Results show that high temperature and low pressure are suitable for absorption reaction. Variation of hydrogen sulfide concentration and Fe3+ concentration with time in absorption reaction shown that the reaction of ferric sulfate and hydrogen sulfide is first order with respect to the both reactant. At low Fe2(SO4)3 concentration the absorption rate of H2S increase with increasing the Fe2(SO4)3 concentration. At higher concentration a decrease in the absorption rate was found. At higher concentration of Fe2(SO4)3, the ionic strength and viscosity of solution increase remarkably resulting in a decrease of solubility, diffusivity and hence absorption rate.

Optimum Operating Conditions for Direct Oxidation of H2S in a Fluidized Bed Reactor

In this research a mathematical model for direct oxidization of hydrogen sulfide into elemental sulfur in a fluidized bed reactor with external circulation was developed. As the catalyst is deactivated in the fluidized bed, it might be placed in a reduction tank in order to remove sulfur through heating above its dew point. The reactor model demonstrated via MATLAB software. It was shown that variations of H2S conversion as well as; products formed were reasonable in comparison with corresponding results of a fixed bed reactor. Through analyzing results of this model, it became possible to propose the main optimized operating conditions for the process considered. These conditions included; the temperature range of 100-130ºC and utilizing the catalyst as much as possible providing the highest bed density respect to dimensions of bed, economical aspects that the bed ever remained in fluidized mode. A high active and stable catalyst under the optimum conditions exhibited 100% conversion in a fluidized bed reactor.

Optical Characterization of a Microwave Plasma Torch for Hydrogen Production

Hydrogen sulfide (H2S) is a very toxic gas that is produced in very large quantities in the oil and gas industry. It cannot be flared to the atmosphere and Claus process based gas plants are used to recover the sulfur and convert the hydrogen to water. In this paper, we present optical characterization of an atmospheric pressure microwave plasma torch for H2S dissociation into hydrogen and sulfur. The torch is operated at 2.45 GHz with power up to 2 kW. Three different gases can simultaneously be injected in the plasma torch. Visual imaging and optical emission spectroscopy are used to characterize the plasma for varying gas flow rates and microwave power. The plasma length, emission spectra and temperature are presented. The obtained experimental results validate our earlier published simulation results of plasma torch.