Transesterification of Waste Cooking Oil for Biodiesel Production Using Modified Clinoptilolite Zeolite as a Heterogeneous Catalyst

Reduction of fossil fuels sources, increasing of pollution gases emission, and global warming effects increase the demand of renewable fuels. One of the main candidates of alternative fuels is biodiesel. Biodiesel limits greenhouse gas effects due to the closed CO2 cycle. Biodiesel has more biodegradability, lower combustion emissions such as CO, SOx, HC, PM and lower toxicity than petro diesel. However, biodiesel has high production cost due to high price of plant oils as raw material. So, the utilization of waste cooking oils (WCOs) as feedstock, due to their low price and disposal problems reduce biodiesel production cost. In this study, production of biodiesel by transesterification of methanol and WCO using modified sodic potassic (SP) clinoptilolite zeolite and sodic potassic calcic (SPC) clinoptilolite zeolite as heterogeneous catalysts have been investigated. These natural clinoptilolite zeolites were modified by KOH solution to increase the site activity. The optimum biodiesel yields for SP clinoptilolite and SPC clinoptilolite were 95.8% and 94.8%, respectively. Produced biodiesel were analyzed and compared with petro diesel and ASTM limits. The properties of produced biodiesel confirm well with ASTM limits. The density, kinematic viscosity, cetane index, flash point, cloud point, and pour point of produced biodiesel were all higher than petro diesel but its acid value was lower than petro diesel. Finally, the reusability and regeneration of catalysts were investigated. The results indicated that the spent zeolites cannot be reused directly for the transesterification, but they can be regenerated easily and can obtain high activity.

Structure and Activity Research of Hydrocarbons Refining Catalysts Based on Wastes of Ferroalloy Production

An effective way of utilization of ferroalloy production wastes is preparing hydrocarbon refining catalysts from them. It is possible due to accordable transition metals containing in the wastes. In the work, we are presenting the results on elemental analysis of sludge samples from Aksu ferroalloy plant (Aksu, Kazakhstan), method of catalysts preparing, results of physical-chemical analysis of obtained catalysts (X-ray analysis, electron microscopy, the BET method etc.), results of using the catalysts in some hydrocarbons refining processes such as hydrocracking of rubber waste, cracking of gasoil, oxidation of cyclohexane. The main results of catalytic activity research are: a) In hydrocracking of rubber waste 64.9% of liquid products were fuel fractions; b) In cracking of gasoil conversion was 51% and selectivity by liquid products was 99%; c) In oxidation of cyclohexane the maximal product yield 87.9% and selectivity by cyclohexanol 93.0% were achieved.

Integration of Unified Power Flow Controller with Backup Energy Supply System for Enhancing Power System Stability

An electrical power system has some negative aspects such as flickering and deviations of voltage/power. This can be eliminated using energy storage devices that will provide a backup energy at the time of voltage/power deviations. Energy-storage devices get charging when system voltage/power is higher than reference value and discharging when system voltage/power is lower than reference value, it is acting as catalysts to provide energy boost. In this paper, a dynamic control of Unified Power Flow Controller (UPFC) integrated with superconducting magnetic energy storage (SMES) is developed to improve the power quality, power oscillation damping, and dynamic voltage stability through the transmission line. UPFC inter-connected to SMES through an interface with DC-DC chopper. This inter-connected system is capable of injecting (absorbing) the real and reactive power into (from) the system at the beginning of stability problems. In this paper, the simulation results of UPFC integrated with SMES and UPFC integrated with fuel cells (FCs) are compared using MATLAB/Simulink software package.

The Performance of PtSn/Al₂O₃ with Cylindrical Particles for Acetic Acid Hydrogenation

Alumina supported PtSn catalysts with cylindrical particles were prepared and characterized by using low temperature N2 adsorption/desorption and X-ray diffraction. Low temperature N2 adsorption/desorption demonstrate that the tableting changed the texture properties of catalysts. XRD pattern indicate that the crystal structure of supports had no change after reaction. The performances over particles of PtSn/Al2O3 catalysts were investigated with regards to reaction temperature, pressure, and H2/AcOH mole ratio. After tableting, the conversion of acetic acid and selectivity of ethanol and acetyl acetate decreased. High reaction temperature and pressure can improve conversion of acetic acid. H2/AcOH mole ratio of 9.36 showed the best performance on acetic acid hydrogenation. High pressure had benefits for the selectivity of ethanol and other two parameters had no obvious effect on selectivity.  

The Catalytic Properties of PtSn/Al2O3 for Acetic Acid Hydrogenation

Alumina supported platinum and tin catalysts with different loadings of Pt and Sn were prepared and characterized by low temperature N2 adsorption/desorption, H2-temperature programed reduction and CO pulse chemisorption. Pt and Sn below 1% loading were suitable for acetic acid hydrogenation. The best performance over 0.75Pt1Sn/Al2O3 can reach 87.55% conversion of acetic acid and 47.39% selectivity of ethanol. The operating conditions of acetic acid hydrogenation over 1Pt1Sn/Al2O3 were investigated. High reaction temperature can enhance the conversion of acetic acid, but it decreased total selectivity of ethanol and acetyl acetate. High pressure and low weight hourly space velocity were beneficial to both conversion of acetic acid and selectivity to ethanol.

Optimization of Quercus cerris Bark Liquefaction

The liquefaction process of cork based tree barks has led to an increase of interest due to its potential innovation in the lumber and wood industries. In this particular study the bark of Quercus cerris (Turkish oak) is used due to its appreciable amount of cork tissue, although of inferior quality when compared to the cork provided by other Quercus trees. This study aims to optimize alkaline catalysis liquefaction conditions, regarding several parameters. To better comprehend the possible chemical characteristics of the bark of Quercus cerris, a complete chemical analysis was performed. The liquefaction process was performed in a double-jacket reactor heated with oil, using glycerol and a mixture of glycerol/ethylene glycol as solvents, potassium hydroxide as a catalyst, and varying the temperature, liquefaction time and granulometry. Due to low liquefaction efficiency resulting from the first experimental procedures a study was made regarding different washing techniques after the filtration process using methanol and methanol/water. The chemical analysis stated that the bark of Quercus cerris is mostly composed by suberin (ca. 30%) and lignin (ca. 24%) as well as insolvent hemicelluloses in hot water (ca. 23%). On the liquefaction stage, the results that led to higher yields were: using a mixture of methanol/ethylene glycol as reagents and a time and temperature of 120 minutes and 200 ºC, respectively. It is concluded that using a granulometry of

Investigation on Fischer-Tropsch Synthesis over Cobalt-Gadolinium Catalyst

Cobalt-gadolinium catalyst for Fischer-Tropsch synthesis was prepared by impregnation method with commercial silica gel, and its texture properties were characterized by BET, XRD, and TPR. The catalytic performance of the catalyst was tested in a fixed bed reactor. The results showed that the addition of gadolinium to the cobalt catalyst might decrease the size of cobalt particles, and increased the dispersion of catalytic active cobalt phases. The carbon number distributions for the catalysts was calculated by ASF equation.

Alumina Supported Cu-Mn-La Catalysts for CO and VOCs Oxidation

Recently, copper and manganese-containing systems are recognized as active and selective catalysts in many oxidation reactions. The main idea of this study is to obtain more information about γ-Al2O3 supported Cu-La catalysts and to evaluate their activity to simultaneous oxidation of CO, CH3OH and dimethyl ether (DME). The catalysts were synthesized by impregnation of support with a mixed aqueous solution of nitrates of copper, manganese and lanthanum under different conditions. XRD, HRTEM/EDS, TPR and thermal analysis were performed to investigate catalysts’ bulk and surface properties. The texture characteristics were determined by Quantachrome Instruments NOVA 1200e specific surface area and pore analyzer. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor in a wide temperature range. On the basis of XRD analysis and HRTEM/EDS, it was concluded that the active component of the mixed Cu-Mn-La/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio and consisted of at least four compounds – CuO, La2O3, MnO2 and Cu1.5Mn1.5O4. A homogeneous distribution of the active component on the carrier surface was found. The chemical composition strongly influenced catalytic properties. This influence was quite variable with regards to the different processes.

Isolation and Screening of Fungal Strains for β-Galactosidase Production

Enzymes are the biocatalysts which catalyze the biochemical processes and thus have a wide variety of applications in the industrial sector. β-Galactosidase (E.C. 3.2.1.23) also known as lactase, is one of the prime enzymes, which has significant potential in the dairy and food processing industries. It has the capability to catalyze both the hydrolytic reaction for the production of lactose hydrolyzed milk and transgalactosylation reaction for the synthesis of prebiotics such as lactulose and galactooligosaccharides. These prebiotics have various nutritional and technological benefits. Although, the enzyme is naturally present in almonds, peaches, apricots and other variety of fruits and animals, the extraction of enzyme from these sources increases the cost of enzyme. Therefore, focus has been shifted towards the production of low cost enzyme from the microorganisms such as bacteria, yeast and fungi. As compared to yeast and bacteria, fungal β-galactosidase is generally preferred as being extracellular and thermostable in nature. Keeping the above in view, the present study was carried out for the isolation of the β-galactosidase producing fungal strain from the food as well as the agricultural wastes. A total of more than 100 fungal cultures were examined for their potential in enzyme production. All the fungal strains were screened using X-gal and IPTG as inducers in the modified Czapek Dox Agar medium. Among the various isolated fungal strains, the strain exhibiting the highest enzyme activity was chosen for further phenotypic and genotypic characterization. The strain was identified as Rhizomucor pusillus on the basis of 5.8s RNA gene sequencing data.

Reaction Kinetics of Biodiesel Production from Refined Cottonseed Oil Using Calcium Oxide

Power law approximation was used in this study to evaluate the reaction orders of calcium oxide, CaO catalyzed transesterification of refined cottonseed oil and methanol. The kinetics study was carried out at temperatures of 45, 55 and 65 oC. The kinetic parameters such as reaction order 2.02 and rate constant 2.8 hr-1g-1cat, obtained at the temperature of 65 oC best fitted the kinetic model. The activation energy, Ea obtained was 127.744 KJ/mol. The results indicate that the transesterification reaction of the refined cottonseed oil using calcium oxide catalyst is approximately second order reaction.

NiO-CeO2 Nano-Catalyst for the Removal of Priority Organic Pollutants from Wastewater through Catalytic Wet Air Oxidation at Mild Conditions

Catalytic wet air oxidation (CWAO) is normally carried out at elevated temperature and pressure. This work investigates the potential of NiO-CeO2 nano-catalyst in CWAO of paper industry wastewater under milder operating conditions of 90 °C and 1 atm. The NiO-CeO2 nano-catalysts were synthesized by a simple co-precipitation method and characterized by X-ray diffraction (XRD), before and after use, in order to study any crystallographic change during experiment. The extent of metal-leaching from the catalyst was determined using the inductively coupled plasma optical emission spectrometry (ICP-OES). The catalytic activity of nano-catalysts was studied in terms of total organic carbon (TOC), adsorbable organic halides (AOX) and chlorophenolics (CHPs) removal. Interestingly, mixed oxide catalysts exhibited higher activity than the corresponding single-metal oxides. The maximum removal efficiency was achieved with Ce40Ni60 catalyst. The results indicate that the CWAO process is efficient in removing the priority organic pollutants from wastewater, as it exhibited up to 59% TOC, 55% AOX, and 54 % CHPs removal.

Preparation of Heterogeneous Ferrite Catalysts and Their Application for Fenton-Like Oxidation of Radioactive Organic Wastewater

Fenton oxidation technology is the general strategy for the treatment of organic compounds-contained wastewater. However, a considerable amount of ferric sludge was produced during the Fenton process as secondary wastes, which were needed to be further removed from the effluent and treated. In this study, heterogeneous catalysts based on ferrite oxide (Cu-Fe-Ce-O) were synthesized and characterized, and their application for Fenton-like oxidation of simulated and actual radioactive organic wastewater was investigated. The results of TOC decomposition efficiency around 54% ~ 99% were obtained when the catalyst loading, H2O2 loading, pH, temperature, and reaction time were controlled. In this case, no secondary wastes formed and the given catalysts were able to be separated by magnetic devices and reused again.

Preparation and Characterization of Photocatalyst for the Conversion of Carbon Dioxide to Methanol

Carbon dioxide (CO2) emission to the environment is inevitable which is responsible for global warming. Photocatalytic reduction of CO2 to fuel, such as methanol, methane etc. is a promising way to reduce greenhouse gas CO2 emission. In the present work, Bi2S3/CdS was synthesized as an effective visible light responsive photocatalyst for CO2 reduction into methanol. The Bi2S3/CdS photocatalyst was prepared by hydrothermal reaction. The catalyst was characterized by X-ray diffraction (XRD) instrument. The photocatalytic activity of the catalyst has been investigated for methanol production as a function of time. Gas chromatograph flame ionization detector (GC-FID) was employed to analyze the product. The yield of methanol was found to increase with higher CdS concentration in Bi2S3/CdS and the maximum yield was obtained for 45 wt% of Bi2S3/CdS under visible light irradiation was 20 μmole/g. The result establishes that Bi2S3/CdS is favorable catalyst to reduce CO2 to methanol.

Recycling of Polymers in the Presence of Nanocatalysts: A Green Approach towards Sustainable Environment

This work involves the degradation of plastic waste in the presence of three different nanocatalysts. A thin film of LLDPE was formed with all three nanocatalysts separately in the solvent. Thermo Gravimetric Analysis (TGA) and Differential Scanning Calorimetric (DSC) analysis of polymers suggest that the presence of these catalysts lowers the degradation temperature and the change mechanism of degradation. Gas chromatographic analysis was carried out for two films. In gas chromatography (GC) analysis, it was found that degradation of pure polymer produces only 32% C3/C4 hydrocarbons and 67.6% C5/C9 hydrocarbons. In the presence of these catalysts, more than 80% of polymer by weight was converted into either liquid or gaseous hydrocarbons. Change in the mechanism of degradation of polymer was observed therefore more C3/C4 hydrocarbons along with valuable feedstock are produced. Adjustment of dose of nanocatalyst, use of nano-admixtures and recycling of catalyst can make this catalytic feedstock recycling method a good tool to get sustainable environment. The obtained products can be utilized as fuel or can be transformed into other useful products. In accordance with the principles of sustainable development, chemical recycling i.e. tertiary recycling of polymers along with the reuse (zero order recycling) of plastics can be the most appropriate and promising method in this direction. The tertiary recycling is attracting much attention from the viewpoint of the energy resource.

One-Pot Facile Synthesis of N-Doped Graphene Synthesized from Paraphenylenediamine as Metal-Free Catalysts for the Oxygen Reduction Used for Alkaline Fuel Cells

In the work presented here, nitrogen-doped graphene materials were synthesized and used as metal-free electrocatalysts for oxygen reduction reaction (ORR) under alkaline conditions. Paraphenylenediamine was used as N precursor. The N-doped graphene was synthesized under hydrothermal treatment at 200°C. All the materials have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS). Moreover, for electrochemical evaluation of samples, Rotating Disk electrode (RDE) and Cyclic Voltammetry techniques (CV) were employed. The resulting material exhibits an outstanding catalytic activity for the oxygen reduction reaction (ORR) as well as excellent resistance towards methanol crossover effects, indicating their promising potential as ORR electrocatalysts for alkaline fuel cells.

Amino Acid Coated Silver Nanoparticles: A Green Catalyst for Methylene Blue Reduction

Highly stable and homogeneously dispersed amino acid coated silver nanoparticles (ANP) of ≈ 10 nm diameter, ranging from 420 to 430 nm are prepared on AgNO3 solution addition to gum of Azadirachta indica solution at 373.15 K. The amino acids were selected based on their polarity. The synthesized nanoparticles were characterized by UV-Vis, FTIR spectroscopy, HR-TEM, XRD, SEM and 1H-NMR. The coated nanoparticles were used as catalyst for the reduction of methylene blue dye in presence of Sn(II) in aqueous, anionic and cationic micellar media. The rate of reduction of dye was determined by measuring the absorbance at 660 nm, spectrophotometrically and followed the order: Kcationic > Kanionic > Kwater. After 12 min and in absence of the ANP, only 2%, 3% and 6% of the dye reduction was completed in aqueous, anionic and cationic micellar media respectively while, in presence of ANP coated by polar neutral amino acid with non-polar -R group, the reduction completed to 84%, 95% and 98% respectively. The ANP coated with polar neutral amino acid having non-polar -R group, increased the rate of reduction of the dye by 94, 3205 and 6370 folds in aqueous, anionic and cationic micellar media respectively. Also, the rate of reduction of the dye increased by three folds when the micellar media was changed from anionic to cationic when the ANP is coated by a polar neutral amino acid having a non-polar -R group.

Vapor Phase Transesterification of Dimethyl Malonate with Phenol over Cordierite Honeycomb Coated with Zirconia and Its Modified Forms

The transesterification of dimethyl malonate (DMM) with phenol has been studied in vapour phase over cordierite honeycomb coated with solid acid catalysts such as ZrO2, Mo(VI)/ZrO2 and SO42-/ZrO2. The catalytic materials were prepared honeycomb coated, powder forms, and characterized for their total surface acidity by NH3-TPD and crystalinity by powder XRD methods. Phenyl methyl malonate (PMM) and diphenyl malonate (DPM) were obtained as the reaction products. A good conversion of DMM (up to 82%) of MPM with 95% selectivity was observed when the reactions were carried out at a catalyst bed temperature of 200 °C and flow-rate of 10 mL/h in presence of Mo(VI)/ZrO2 as catalyst. However, over SO4^2-/ZrO2 catalyst, the yield of DPM was found to be higher. The results have been interpreted based on the variation of acidic properties and powder XRD phases of zirconia on incorporation of Mo(VI) or SO42– ions. Transesterification reactions were also carried out over powder forms of the catalytic materials and the yield of the desired phenyl ester products were compared with that of the HC coated catalytic materials. The solid acids were found to be reusable when used for at least 5 reaction cycles.

Biodiesel Production from Broiler Chicken Waste

Broiler slaughter waste has become a major source of pollution throughout the world. Utilization of broiler slaughter waste by dry rendering process produced Rendered Chicken Oil (RCO), a cheap raw material for biodiesel production and Carcass Meal a feed ingredient for pets and fishes. Conversion of RCO into biodiesel may open new vistas for generating wealth from waste besides controlling the major havoc of environmental pollution. A two-step process to convert RCO to good quality Biodiesel was invented. Acid catalysed esterification of FFA followed by base catalysed transesterification of triglycerides was carried out after meticulously standardizing the methanol molar ratio, catalyst concentration, reaction temperature, and reaction time to obtain the maximum biodiesel yield of 97.62% and lowest glycerol yield of 6.96%. RCO biodiesel blend was tested in a CRDI diesel engine. The results revealed that the blending of commercial diesel with 20% RCO biodiesel (B20) lead to less engine wear, a quieter engine and better fuel economy. The better lubricating qualities of RCO B20 prevented over heating of engine, which prolongs the engine life. RCO B20 can reduce the import of crude oil and substantially reduce the engine emissions as proved by significantly lower smoke levels, thus mitigating climatic changes.

Inflating the Public: A Series of Urban Interventions

The Green Urban Lab took the form of public installations that were placed at various locations in four cities in Cyprus. These installations - through which a series of events, activities, workshops and research took place - were the main tools in regenerating a series of urban public spaces in Cyprus. The purpose of this project was to identify issues and opportunities related to public space and to offer guidelines on how design and participatory democracy improvements could strengthen civil society, while raising the quality of the urban public scene. Giant inflatable structures were injected in important urban fragments in order to accommodate series of events. The design and playful installation generated a wide community engagement. The fluid presence of the installations acted as a catalyst for social interaction. They were accessed and viewed effortlessly and surprisingly, creating opportunities to rediscover public spaces.

A Two-Step, Temperature-Staged Direct Coal Liquefaction Process

The world crude oil demand is projected to rise to 108.5 million bbl/d by the year 2035. With reserves estimated at 869 billion tonnes worldwide, coal remains an abundant resource. The aim of this work was to produce a high value hydrocarbon liquid product using a Direct Coal Liquefaction (DCL) process at, relatively mild operating conditions. Via hydrogenation, the temperature-staged approach was investigated in a dual reactor lab-scale pilot plant facility. The objectives included maximising thermal dissolution of the coal in the presence of tetralin as the hydrogen donor solvent in the first stage with 2:1 and 3:1 solvent: coal ratios. Subsequently, in the second stage, hydrogen saturation, in particular, hydrodesulphurization (HDS) performance was assessed. Two commercial hydrotreating catalysts were investigated viz. NickelMolybdenum (Ni-Mo) and Cobalt-Molybdenum (Co-Mo). GC-MS results identified 77 compounds and various functional groups present in the first and second stage liquid product. In the first stage 3:1 ratios and liquid product yields catalysed by magnetite were favoured. The second stage product distribution showed an increase in the BTX (Benzene, Toluene, Xylene) quality of the liquid product, branched chain alkanes and a reduction in the sulphur concentration. As an HDS performer and selectivity to the production of long and branched chain alkanes, Ni-Mo had an improved performance over Co-Mo. Co-Mo is selective to a higher concentration of cyclohexane. For 16 days on stream each, Ni-Mo had a higher activity than Co-Mo. The potential to cover the demand for low–sulphur, crude diesel and solvents from the production of high value hydrocarbon liquid in the said process, is thus demonstrated.