Synthesis and Fluorescence Spectroscopy of Sulphonic Acid-Doped Polyaniline When Exposed to Oxygen Gas

Three sulphonic acid-doped polyanilines were synthesized through chemical oxidation at low temperature (0-5 oC) and potential of these polymers as sensing agent for O2 gas detection in terms of fluorescence quenching was studied. Sulphuric acid, dodecylbenzene sulphonic acid (DBSA) and camphor sulphonic acid (CSA) were used as doping agents. All polymers obtained were dark green powder. Polymers obtained were characterized by Fourier transform infrared spectroscopy, ultraviolet-visible absorption spectroscopy, thermogravimetry analysis, elemental analysis, differential scanning calorimeter and gel permeation chromatography. Characterizations carried out showed that polymers were successfully synthesized with mass recovery for sulphuric aciddoped polyaniline (SPAN), DBSA-doped polyaniline (DBSA-doped PANI) and CSA-doped polyaniline (CSA-doped PANI) of 71.40%, 75.00% and 39.96%, respectively. Doping level of SPAN, DBSAdoped PANI and CSA-doped PANI were 32.86%, 33.13% and 53.96%, respectively as determined based on elemental analysis. Sensing test was carried out on polymer sample in the form of solution and film by using fluorescence spectrophotometer. Samples of polymer solution and polymer film showed positive response towards O2 exposure. All polymer solutions and films were fully regenerated by using N2 gas within 1 hour period. Photostability study showed that all samples of polymer solutions and films were stable towards light when continuously exposed to xenon lamp for 9 hours. The relative standard deviation (RSD) values for SPAN solution, DBSA-doped PANI solution and CSA-doped PANI solution for repeatability were 0.23%, 0.64% and 0.76%, respectively. Meanwhile RSD values for reproducibility were 2.36%, 6.98% and 1.27%, respectively. Results for SPAN film, DBSAdoped PANI film and CSA-doped PANI film showed the same pattern with RSD values for repeatability of 0.52%, 4.05% and 0.90%, respectively. Meanwhile RSD values for reproducibility were 2.91%, 10.05% and 7.42%, respectively. The study on effect of the flow rate on response time was carried out using 3 different rates which were 0.25 mL/s, 1.00 mL/s and 2.00 mL/s. Results obtained showed that the higher the flow rate, the shorter the response time.

Modeling of CO2 Removal from Gas Mixtureby 2-amino-2-methyl-1-propanol (AMP) Using the Modified Kent Eisenberg Model

In this paper, the solubility of CO2 in AMP solution have been measured at temperature range of ( 293, 303 ,313,323) K.The amine concentration ranges studied are (2.0, 2.8, and 3.4) M. A solubility apparatus was used to measure the solubility of CO2 in AMP solution on samples of flue gases from Thermal and Central Power Plants of Esfahan Steel Company. The modified Kent Eisenberg model was used to correlate and predict the vapor-liquid equilibria of the (CO2 + AMP + H2O) system. The model predicted results are in good agreement with the experimental vapor-liquid equilibrium measurements.

Spectroscopic and SEM Investigation of TCPP in Titanium Matrix

Titanium gels doped with water-soluble cationic porphyrin were synthesized by the sol–gel polymerization of Ti (OC4H9)4. In this work we investigate the spectroscopic properties along with SEM images of tetra carboxyl phenyl porphyrin when incorporated into porous matrix produced by the sol–gel technique.

Development of a Porous Silica Film by Sol-gel Process

In the present work homogeneous silica film on silicon was fabricated by colloidal silica sol. The silica sol precursor with uniformly granular particle was derived by the alkaline hydrolysis of tetraethoxyorthosilicate (TEOS) in presence of glycerol template. The film was prepared by dip coating process. The templated hetero-structured silica film was annealed at elevated temperatures to generate nano- and meso porosity in the film. The film was subsequently annealed at different temperatures to make it defect free and abrasion resistant. The sol and the film were characterized by the measurement of particle size distribution, scanning electron microscopy, XRD, FTIR spectroscopy, transmission electron microscopy, atomic force microscopy, measurement of the refractive index, thermal conductivity and abrasion resistance. The porosity of the films decreased whereas refractive index and dielectric constant of it `increased with the increase in the annealing temperature. The thermal conductivity of the films increased with the increase in the film thickness. The developed porous silica film holds strong potential for use in different areas.

Physicochemical Characterization of MFI–Ceramic Hollow Fibres Membranes for CO2 Separation with Alkali Metal Cation

This paper present some preliminary work on the preparation and physicochemical caracterization of nanocomposite MFI-alumina structures based on alumina hollow fibres. The fibers are manufactured by a wet spinning process. α-alumina particles were dispersed in a solution of polysulfone in NMP. The resulting slurry is pressed through the annular gap of a spinneret into a precipitation bath. The resulting green fibres are sintered. The mechanical strength of the alumina hollow fibres is determined by a three-point-bending test while the pore size is characterized by bubble-point testing. The bending strength is in the range of 110 MPa while the average pore size is 450 nm for an internal diameter of 1 mm and external diameter of 1.7 mm. To characterize the MFI membranes various techniques were used for physicochemical characterization of MFI–ceramic hollow fibres membranes: The nitrogen adsorption, X-ray diffractometry, scanning electron microscopy combined with X emission microanalysis. Scanning Electron Microscopy (SEM) and Energy Dispersive Microanalysis by the X-ray were used to observe the morphology of the hollow fibre membranes (thickness, infiltration into the carrier, defects, homogeneity). No surface film, has been obtained, as observed by SEM and EDX analysis and confirmed by high temperature variation of N2 and CO2 gas permeances before cation exchange. Local analysis and characterise (SEM and EDX) and overall (by ICP elemental analysis) were conducted on two samples exchanged to determine the quantity and distribution of the cation of cesium on the cross section fibre of the zeolite between the cavities.

Conversion in Chemical Reactors using Hollow Cylindrical Catalyst Pellet

Heterogeneous catalysis is vital for a number of chemical, refinery and pollution control processes. The use of catalyst pellets of hollow cylindrical shape provide several distinct advantages over other common shapes, and can therefore help to enhance conversion levels in reactors. A better utilization of the catalytic material is probably most notable of these features due to the absence of the pellet core, which helps to significantly lower the effect of the internal transport resistance. This is reflected in the enhancement of the effectiveness factor. For the case of the first order irreversible kinetics, a substantial increase in the effectiveness factor can be obtained by varying shape parameters. Important shape parameters of a finite hollow cylinder are the ratio of the inside to the outside radii (κ) and the height to the diameter ratio (γ). A high value of κ the generally helps to enhance the effectiveness factor. On the other hand, lower values of the effectiveness factors are obtained when the dimension of the height and the diameter are comparable. Thus, the departure of parameter γ from the unity favors higher effectiveness factor. Since a higher effectiveness factor is a measure of a greater utilization of the catalytic material, higher conversion levels can be achieved using the hollow cylindrical pellets possessing optimized shape parameters.

Recovery of Cu, Zn, Ni and Cr from Plating Sludge by Combined Sulfidation and Oxidation Treatment

The selective recovery of heavy metals of Cu, Zn, Ni and Cr from a mixed plating sludge by sulfidation and oxidation treatment was targeted in this study. At first, the mixed plating sludge was simultaneously subjected to an extraction and Cu sulfidation process at pH=1.5 to dissolve heavy metals and to precipitate Cu2+ as CuS. In the next step, the sulfidation treatment of Zn was carried out at pH=4.5 and the residual solution was subjected to an oxidation treatment of chromium with H2O2 at pH=10.0. After the experiments, the selectivity of metal precipitation and the chromium oxidation ratio were evaluated. As results, it was found that the filter cake obtained after selective sulfidation of Cu was composed of 96.6% of Cu (100% equals to the sum of Cu, Zn, Ni and Cr contents). Such findings confirmed that almost complete extraction of heavy metals was achieved at pH=1.5 and also that Cu could be selectively recovered as CuS. Further, the filter cake obtained at pH=4.5 was composed of 91.5% Zn and 6.83% of Cr. Regarding the chromium oxidation step, the chromium oxidation ratio was found to increase with temperature and the addition of oxidation agent of H2O2, but only oxidation ratio of 59% was achieved at a temperature of 60°C and H2O2 to Cr3+ equivalent ratio of 180.

Effect of Biomass Feedstocks on the Production of Hydrogenated Biodiesel

Hydrogenated biodiesel is one of the most promising renewable fuels. It has many advantages over conventional biodiesel, including higher cetane number, higher heating value, lower viscosity, and lower corrosiveness due to its absence of oxygen. From previous work, Pd/TiO2 gave high conversion and selectivity in hydrogenated biodiesel. In this work, the effect of biomass feedstocks (i.e. beef fat, chicken fat, pork fat, and jatropha oil) on the production of hydrogenated biodiesel over Pd/TiO2 has been studied. Biomass feedstocks were analyzed by ICP-OES (inductively coupled plasma optical emission spectrometry) to identify the content of impurities (i.e. P, K, Ca, Na, and Mg). The deoxygenation catalyst, Pd/TiO2, was prepared by incipient wetness impregnation (IWI) and tested in a continuous flow packed-bed reactor at 500 psig, 325°C, H2/feed molar ratio of 30, and LHSV of 4 h-1 for its catalytic activity and selectivity in hydrodeoxygenation. All feedstocks gave high selectivity in diesel specification range hydrocarbons and the main hydrocarbons were n-pentadecane (n-C15) and n-heptadecane (n- C17), resulting from the decarbonylation/decarboxylation reaction. Intermediates such as oleic acid, stearic acid, palmitic acid, and esters were also detected in minor amount. The conversion of triglycerides in jatropha oil is higher than those of chicken fat, pork fat, and beef fat, respectively. The higher concentration of metal impurities in feedstock, the lower conversion of feedstock.

Used Frying Oil for Biodiesel Production Over Kaolinite as Catalyst

Biodiesel production with used frying by transesterification reaction with methanol, using a commercial kaolinite thermally-activated solid acid catalyst was investigated. The surface area, the average pore diameter and pore volume of the kaolinite catalyst were 10 m2/g, 13.0 nm and 30 mm3/g, respectively. The optimal conditions for the transesterification reaction were determined to be oil/methanol, in a molar ratio 1:31, temperature 160 ºC and catalyst concentration of 3% (w/w). The yield of fatty acids methyl esters (FAME) was 92.4% after 2 h of reaction. This method of preparation of biodiesel can be a positive alternative for utilizing used frying corn oil for feedstock of biodiesel combined with the inexpensive catalyst.

Carbon Dioxide Removal from Flue Gas Using Amine-Based Hybrid Solvent Absorption

This study was to investigate the performance of hybrid solvents blended between primary, secondary, or tertiary amines and piperazine (PZ) for CO2 removal from flue gas in terms of CO2 absorption capacity and regeneration efficiency at 90 oC. Alkanolamines used in this work were monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA). The CO2 absorption was experimentally examined under atmospheric pressure and room temperature. The results show that MEA blend with PZ provided the maximum CO2 absorption capacity of 0.50 mol CO2/mol amine while TEA provided the minimum CO2 absorption capacity of 0.30 mol CO2/mol amine. TEA was easier to regenerate for both first cycle and second cycle with less loss of absorption capacity. The regeneration efficiency of TEA was 95.09 and 92.89 %, for the first and second generation cycles, respectively.

Chemical Degradation of Dieldrin using Ferric Sulfide and Iron Powder

The chemical degradation of dieldrin in ferric sulfide and iron powder aqueous suspension was investigated in laboratory batch type experiments. To identify the reaction mechanism, reduced copper was used as reductant. More than 90% of dieldrin was degraded using both reaction systems after 29 days. Initial degradation rate of the pesticide using ferric sulfide was superior to that using iron powder. The reaction schemes were completely dissimilar even though the ferric ion plays an important role in both reaction systems. In the case of metallic iron powder, dieldrin undergoes partial dechlorination. This reaction proceeded by reductive hydrodechlorination with the generation of H+, which arise by oxidation of ferric iron. This reductive reaction was accelerated by reductant but mono-dechlorination intermediates were accumulated. On the other hand, oxidative degradation was observed in the reaction with ferric sulfide, and the stable chemical structure of dieldrin was decomposed into water-soluble intermediates. These reaction intermediates have no chemical structure of drin class. This dehalogenation reaction assumes to occur via the adsorbed hydroxyl radial generated on the surface of ferric sulfide.

Rigorous Modeling of Fixed-Bed Reactors Containing Finite Hollow Cylindrical Catalyst with Michaelis-Menten Type of Kinetics

A large number of chemical, bio-chemical and pollution-control processes use heterogeneous fixed-bed reactors. The use of finite hollow cylindrical catalyst pellets can enhance conversion levels in such reactors. The absence of the pellet core can significantly lower the diffusional resistance associated with the solid phase. This leads to a better utilization of the catalytic material, which is reflected in the higher values for the effectiveness factor, leading ultimately to an enhanced conversion level in the reactor. It is however important to develop a rigorous heterogeneous model for the reactor incorporating the two-dimensional feature of the solid phase owing to the presence of the finite hollow cylindrical catalyst pellet. Presently, heterogeneous models reported in the literature invariably employ one-dimension solid phase models meant for spherical catalyst pellets. The objective of the paper is to present a rigorous model of the fixed-bed reactors containing finite hollow cylindrical catalyst pellets. The reaction kinetics considered here is the widely used Michaelis–Menten kinetics for the liquid-phase bio-chemical reactions. The reaction parameters used here are for the enzymatic degradation of urea. Results indicate that increasing the height to diameter ratio helps to improve the conversion level. On the other hand, decreasing the thickness is apparently not as effective. This could however be explained in terms of the higher void fraction of the bed that causes a smaller amount of the solid phase to be packed in the fixed-bed bio-chemical reactor.

Biodiesel Production from High Iodine Number Candlenut Oil

Transesterification of candlenut (aleurites moluccana) oil with methanol using potassium hydroxide as catalyst was studied. The objective of the present investigation was to produce the methyl ester for use as biodiesel. The operation variables employed were methanol to oil molar ratio (3:1 – 9:1), catalyst concentration (0.50 – 1.5 %) and temperature (303 – 343K). Oil volume of 150 mL, reaction time of 75 min were fixed as common parameters in all the experiments. The concentration of methyl ester was evaluated by mass balance of free glycerol formed which was analyzed by using periodic acid. The optimal triglyceride conversion was attained by using methanol to oil ratio of 6:1, potassium hydroxide as catalyst was of 1%, at room temperature. Methyl ester formed was characterized by its density, viscosity, cloud and pour points. The biodiesel properties had properties similar to those of diesel oil, except for the viscosity that was higher.

pH-Responsiveness Properties of a Biodigradable Hydrogels Based on Carrageenan-g-poly(NaAA-co-NIPAM)

A novel thermo-sensitive superabsorbent hydrogel with salt- and pH-responsiveness properties was obtained by grafting of mixtures of acrylic acid (AA) and N-isopropylacrylamide (NIPAM) monomers onto kappa-carrageenan, kC, using ammonium persulfate (APS) as a free radical initiator in the presence of methylene bisacrylamide (MBA) as a crosslinker. Infrared spectroscopy was carried out to confirm the chemical structure of the hydrogel. Moreover, morphology of the samples was examined by scanning electron microscopy (SEM). The effect of MBA concentration and AA/NIPAM weight ratio on the water absorbency capacity has been investigated. The swelling variations of hydrogels were explained according to swelling theory based on the hydrogel chemical structure. The hydrogels exhibited salt-sensitivity and cation exchange properties. The temperature- and pH-reversibility properties of the hydrogels make the intelligent polymers as good candidates for considering as potential carriers for bioactive agents, e.g. drugs.

Contaminated Soil Remediation with Hydrogen Peroxide Oxidation

The hydrogen peroxide treatment was able to remediate chlorophenols, polycyclic aromatic hydrocarbons, diesel and transformer oil contaminated soil. Chemical treatment of contaminants adsorbed in peat resulted in lower contaminants- removal and required higher addition of chemicals than the treatment of contaminants in sand. The hydrogen peroxide treatment was found to be feasible for soil remediation at natural soil pH. Contaminants in soil could degrade with the addition of hydrogen peroxide only indicating the ability of transition metals ions and minerals of these metals presented in soil to catalyse the reaction of hydrogen peroxide decomposition.

The Effect of Mixture Velocity and Droplet Diameter on Oil-water Separator using Computational Fluid Dynamics (CFD)

The characteristics of fluid flow and phase separation in an oil-water separator were numerically analysed as part of the work presented herein. Simulations were performed for different velocities and droplet diameters, and the way this parameters can influence the separator geometry was studied. The simulations were carried out using the software package Fluent 6.2, which is designed for numerical simulation of fluid flow and mass transfer. The model consisted of a cylindrical horizontal separator. A tetrahedral mesh was employed in the computational domain. The condition of two-phase flow was simulated with the two-fluid model, taking into consideration turbulence effects using the k-ε model. The results showed that there is a strong dependency of phase separation on mixture velocity and droplet diameter. An increase in mixture velocity will bring about a slow down in phase separation and as a consequence will require a weir of greater height. An increase in droplet diameter will produce a better phase separation. The simulations are in agreement with results reported in literature and show that CFD can be a useful tool in studying a horizontal oilwater separator.

Solubility of Organics in Water and Silicon Oil: A Comparative Study

The aim of this study was to compare the solubility of selected volatile organic compounds in water and silicon oil using the simple static headspace method. The experimental design allowed equilibrium achievement within 30 – 60 minutes. Infinite dilution activity coefficients and Henry-s law constants for various organics representing esters, ketones, alkanes, aromatics, cycloalkanes and amines were measured at 303K. The measurements were reproducible with a relative standard deviation and coefficient of variation of 1.3x10-3 and 1.3 respectively. The static determined activity coefficients using shaker flasks were reasonably comparable to those obtained using the gas liquid - chromatographic technique and those predicted using the group contribution methods mainly the UNIFAC. Silicon oil chemically known as polydimethysiloxane was found to be better absorbent for VOCs than water which quickly becomes saturated. For example the infinite dilution mole fraction based activity coefficients of hexane is 0.503 and 277 000 in silicon oil and water respectively. Thus silicon oil gives a superior factor of 550 696. Henry-s law constants and activity coefficients at infinite dilution play a significant role in the design of scrubbers for abatement of volatile organic compounds from contaminated air streams. This paper presents the phase equilibrium of volatile organic compounds in very dilute aqueous and polymeric solutions indicating the movement and fate of chemical in air and solvent. The successful comparison of the results obtained here and those obtained using other methods by the same authors and in literature, means that the results obtained here are reliable.

n-Butanol as an Extractant for Lactic Acid Recovery

Extraction of lactic acid from aqueous solution using n-butanol as an extractant was studied. Effect of mixing time, pH of the aqueous solution, initial lactic acid concentration, and volume ratio between the organic and the aqueous phase were investigated. Distribution coefficient and degree of lactic acid extraction was found to increase when the pH of aqueous solution was decreased. The pH Effect was substantially pronounced at pH of the aqueous solution less than 1. Initial lactic acid concentration and organic-toaqueous volume ratio appeared to have positive effect on the distribution coefficient and the degree of extraction. Due to the nature of n-butanol that is partially miscible in water, incorporation of aqueous solution into organic phase was observed in the extraction with large organic-to-aqueous volume ratio.

Volatile Organochlorine Compounds Emitted by Temperate Coniferous Forests

Chlorine is one of the most abundant elements in nature, which undergoes a complex biogeochemical cycle. Chlorine bound in some substances is partly responsible for atmospheric ozone depletion and contamination of some ecosystems. As due to international regulations anthropogenic burden of volatile organochlorines (VOCls) in atmosphere decreases, natural sources (plants, soil, abiotic formation) are expected to dominate VOCl production in the near future. Examples of plant VOCl production are methyl chloride, and bromide emission from (sub)tropical ferns, chloroform, 1,1,1-trichloroethane and tetrachloromethane emission from temperate forest fern and moss. Temperate forests are found to emit in addition to the previous compounds tetrachloroethene, and brominated volatile compounds. VOCls can be taken up and further metabolized in plants. The aim of this work is to identify and quantitatively analyze the formed VOCls in temperate forest ecosystems by a cryofocusing/GC-ECD detection method, hence filling a gap of knowledge in the biogeochemical cycle of chlorine.

Fluorescence Spectroscopy of Lysozyme-Silver Nanoparticles Complex

Identifying the nature of protein-nanoparticle interactions and favored binding sites is an important issue in functional characterization of biomolecules and their physiological responses. Herein, interaction of silver nanoparticles with lysozyme as a model protein has been monitored via fluorescence spectroscopy. Formation of complex between the biomolecule and silver nanoparticles (AgNPs) induced a steady state reduction in the fluorescence intensity of protein at different concentrations of nanoparticles. Tryptophan fluorescence quenching spectra suggested that silver nanoparticles act as a foreign quencher, approaching the protein via this residue. Analysis of the Stern-Volmer plot showed quenching constant of 3.73 μM−1. Moreover, a single binding site in lysozyme is suggested to play role during interaction with AgNPs, having low affinity of binding compared to gold nanoparticles. Unfolding studies of lysozyme showed that complex of lysozyme- AgNPs has not undergone structural perturbations compared to the bare protein. Results of this effort will pave the way for utilization of sensitive spectroscopic techniques for rational design of nanobiomaterials in biomedical applications.