Search results for: Acidic catalyst.

Authors: M. Donmez, F. Akbal

Abstract:

In this study arsenate [As(V)] removal from drinking water by coagulation process was investigated. Ferric chloride (FeCl3.6H2O) and ferrous sulfate (FeSO4.7H2O) were used as coagulant. The effects of major operating variables such as coagulant dose (1–30 mg/L) and pH (5.5–9.5) were investigated. Ferric chloride and ferrous sulfate were found as effective and reliable coagulant due to required dose, residual arsenate and coagulant concentration. Optimum pH values for maximum arsenate removal for ferrous sulfate and ferric chloride were found as 8 and 7.5. The arsenate removal efficiency decreased at neutral and acidic pH values for Fe(II) and at the high acidic and high alkaline pH for Fe(III). It was found that the increase of coagulant dose caused a substantial increase in the arsenate removal. But above a certain ferric chloride and ferrous sulfate dosage, the increase in arsenate removal was not significant. Ferric chloride and ferrous sulfate dose above 8 mg/L slightly increased arsenate removal.

Keywords: Arsenic removal, coagulation, ıron salts, drinking water.

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Authors: Noor S. Nasri, Eric C. A. Tatt, Usman D. Hamza, Jibril Mohammed, Husna M. Zain

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Catalytic combustion of methane is imperative due to stability of methane at low temperature. Methane (CH4), therefore, remains unconverted in vehicle exhausts thereby causing greenhouse gas GHG emission problem. In this study, heterogeneous catalysts of palladium with bio-char (2 wt% Pd/Bc) and Al2O3 (2wt% Pd/ Al2O3) supports were prepared by incipient wetness impregnation and then subsequently tested for catalytic combustion of CH4. Support-porous heterogeneous catalytic combustion (HCC) material were selected based on factors such as surface area, porosity, thermal stability, thermal conductivity, reactivity with reactants or products, chemical stability, catalytic activity, and catalyst life. Sustainable and renewable support-material of bio-mass char derived from palm shell waste material was compared with those from the conventional support-porous materials. Kinetic rate of reaction was determined for combustion of methane on Palladium (Pd) based catalyst with Al2O3 support and bio-char (Bc). Material characterization was done using TGA, SEM, and BET surface area. The performance test was accomplished using tubular quartz reactor with gas mixture ratio of 3% methane and 97% air. The methane porous-HCC conversion was carried out using online gas analyzer connected to the reactor that performed porous-HCC. BET surface area for prepared 2 wt% Pd/Bc is smaller than prepared 2wt% Pd/ Al2O3 due to its low porosity between particles. The order of catalyst activity based on kinetic rate on reaction of catalysts in low temperature was 2wt% Pd/Bc>calcined 2wt% Pd/ Al2O3> 2wt% Pd/ Al2O3>calcined 2wt% Pd/Bc. Hence agro waste material can successfully be utilized as an inexpensive catalyst support material for enhanced CH4 catalytic combustion.

Keywords: Catalytic-combustion, Environmental, Support-bio-char material, Sustainable, Renewable material.

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Authors: Phuong T. Dang, Hy G. Le, Giang T. Pham, Hong T. M. Vu, Kien T, Nguyen, Canh D. Dao, Giang H. Le, Hoa T. K. Tran, Quang K. Nguyen, Tuan A. Vu

Abstract:

Nanostructured catalysts were successfully prepared by acidification of diatomite and regeneration of FCC spent catalysts. The obtained samples were characterized by IR, XRD, SEM, EDX, MAS-NMR (27Al and 29Si), NH3-TPD and tested in catalytic pyrolysis of biomass (rice straw). The results showed that the similar bio-oil yield of 41.4% can be obtained by pyrolysis with catalysts at 450oC as compared to that of the pyrolysis without catalyst at 550oC. The bio-oil yield reached a maximum of 42.55% at the pyrolysis temperature of 500oC with catalytic content of 20%. Moreover, by catalytic pyrolysis, bio-oil quality was better as reflected in higher ratio of H/C, lower ratio of O/C. This clearly indicated high application potential of these new nanostructured catalysts in the production of bio-oil with low oxygenated compounds.

Keywords: Acidified diatomite, biomass, catalytic pyrolysis, bio-oil, nanostructured catalysts, regenerated FCC catalyst.

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Authors: Mohammad Asif

Abstract:

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.

Keywords: Finite hollow cylinder, Catalyst pellet, Effectiveness factor, Thiele Modulus, Conversion

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Authors: Hsien T. Hsieh, Chao R. Chen, Li C. Chuang, Chin C. Shen

Abstract:

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.

Keywords: Fenton, oxidation, heterogeneous catalyst, wastewater.

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Authors: Chandrashekar, R. T. Radhika, B. M. Venkatesha, S. Ananda, Shivalingegowda, T. S. Shashikumar, H. Ramachandra

Abstract:

The kinetics of the oxidation of amitriptyline (AT) by sodium N-bromotoluene sulphonamide (C₆H₅SO₂NBrNa) has been studied in an acidic buffer medium of pH 1.2 at 303 K. The oxidation reaction of AT was followed spectrophotometrically at maximum wavelength, 410 nm. The reaction rate shows a first order dependence each on concentration of AT and concentration of sodium N-bromotoluene sulphonamide. The reaction also shows an inverse fractional order dependence at low or high concentration of HCl. The dielectric constant of the solvent shows negative effect on the rate of reaction. The addition of halide ions and the reduction product of BAT have no significant effect on the rate. The rate is unchanged with the variation in the ionic strength (NaClO₄) of the medium. Addition of reaction mixtures to be aqueous acrylamide solution did not initiate polymerization, indicating the absence of free radical species. The stoichiometry of the reaction was found to be 1:1 and oxidation product of AT is identified. The Michaelis-Menton type of kinetics has been proposed. The CH₃C₆H₅SO₂NHBr has been assumed to be the reactive oxidizing species. Thermodynamical parameters were computed by studying the reactions at different temperatures. A mechanism consistent with observed kinetics is presented.

Keywords: Amitriptyline, bromamine-T, kinetics, oxidation.

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Authors: Leila Vafajoo, Farhad Khorasheh, Mehrnoosh Hamzezadeh Nakhjavani, Moslem Fattahi

Abstract:

In the present study, a procedure was developed to determine the optimum reaction rate constants in generalized Arrhenius form and optimized through the Nelder-Mead method. For this purpose, a comprehensive mathematical model of a fixed bed reactor for dehydrogenation of heavy paraffins over Pt–Sn/Al2O3 catalyst was developed. Utilizing appropriate kinetic rate expressions for the main dehydrogenation reaction as well as side reactions and catalyst deactivation, a detailed model for the radial flow reactor was obtained. The reactor model composed of a set of partial differential equations (PDE), ordinary differential equations (ODE) as well as algebraic equations all of which were solved numerically to determine variations in components- concentrations in term of mole percents as a function of time and reactor radius. It was demonstrated that most significant variations observed at the entrance of the bed and the initial olefin production obtained was rather high. The aforementioned method utilized a direct-search optimization algorithm along with the numerical solution of the governing differential equations. The usefulness and validity of the method was demonstrated by comparing the predicted values of the kinetic constants using the proposed method with a series of experimental values reported in the literature for different systems.

Keywords: Dehydrogenation, Pt-Sn/Al2O3 Catalyst, Modeling, Nelder-Mead, Optimization

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Authors: Seyed Hamed Mahdaviani, Davood Soudbar, Matin Parvari

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In the present research, the titanium-catalyzed ethylene dimerization and more specifically, the concomitant byproducts and polymer formation have been studied in the presence of 2,5-dimethoxytetrahydrofuran as an electron donor compound in the combination with triethylaluminium (TEA) as activator. Then, we added ethylene chlorobromide as a new efficient promoter to the relevant catalyst system. Finally, the behavior of novel homogeneous [Titanium tetrabutoxide (Ti(OC4H9)4)/2,5-dimethoxytetrahydrofuran/ TEA/ethylene chlorobromide] was investigated in the various operating conditions for the optimum production of 1-butene. In the optimum conditions, a very high ethylene conversion (almost 90.77 %), a relative high selectivity to 1-butene (79.00 %), yield of reaction equal to 71.70 % and a significant productivity (turnover frequency equal to 1370 h-1) were achieved.

Keywords: Ethylene dimerization, 2, 5-dimethoxytetrahydrofuran, ethylene chlorobromide, polymeric compounds

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Authors: J. Bolobajev, M. Trapido, A. Goi

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The practical application of the Fenton-based treatment method for organic compounds-contaminated water purification is limited mainly because of the large amount of ferric sludge formed during the treatment, where ferrous iron (Fe(II)) is used as the activator of the hydrogen peroxide oxidation processes. Reuse of ferric sludge collected from clarifiers to substitute Fe(II) salts allows reducing the total cost of Fenton-type treatment technologies and minimizing the accumulation of hazardous ferric waste. Dissolution of ferric iron (Fe(III)) from the sludge to liquid phase at acidic pH and autocatalytic transformation of Fe(III) to Fe(II) by phenolic compounds (tannic acid, lignin, phenol, catechol, pyrogallol and hydroquinone) added or present as water/wastewater constituents were found to be essentially involved in the Fenton-based oxidation mechanism. Observed enhanced formation of highly reactive species, hydroxyl radicals, resulted in a substantial organic contaminant degradation increase. Sludge reuse at acidic pH and in the presence of ferric iron reductants is a novel strategy in the Fenton-based treatment application for organic compounds-contaminated water purification.

Keywords: Ferric sludge reuse, ferric iron reductant, water treatment, organic pollutant.

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Authors: Maksudur Rahman Khan, Kar Min Chan, Huei Ruey Ong, Chin Kui Cheng, Wasikur Rahman

Abstract:

Microbial fuel cells (MFCs) represent a promising technology for simultaneous bioelectricity generation and wastewater treatment. Catalysts are significant portions of the cost of microbial fuel cell cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. The sluggish oxygen reduction reaction (ORR) rate at air cathode necessitates efficient electrocatalyst such as carbon supported platinum catalyst (Pt/C) which is very costly. Manganese oxide (MnO2) was a representative metal oxide which has been studied as a promising alternative electrocatalyst for ORR and has been tested in air-cathode MFCs. However the single MnO2 has poor electric conductivity and low stability. In the present work, the MnO2 catalyst has been modified by doping Pt nanoparticle. The goal of the work was to improve the performance of the MFC with minimum Pt loading. MnO2 and Pt nanoparticles were prepared by hydrothermal and sol gel methods, respectively. Wet impregnation method was used to synthesize Pt/MnO2 catalyst. The catalysts were further used as cathode catalysts in air-cathode cubic MFCs, in which anaerobic sludge was inoculated as biocatalysts and palm oil mill effluent (POME) was used as the substrate in the anode chamber. The asprepared Pt/MnO2 was characterized comprehensively through field emission scanning electron microscope (FESEM), X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) where its surface morphology, crystallinity, oxidation state and electrochemical activity were examined, respectively. XPS revealed Mn (IV) oxidation state and Pt (0) nanoparticle metal, indicating the presence of MnO2 and Pt. Morphology of Pt/MnO2 observed from FESEM shows that the doping of Pt did not cause change in needle-like shape of MnO2 which provides large contacting surface area. The electrochemical active area of the Pt/MnO2 catalysts has been increased from 276 to 617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The CV results in O2 saturated neutral Na2SO4 solution showed that MnO2 and Pt/MnO2 catalysts could catalyze ORR with different catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode catalyst generates a maximum power density of 165 mW/m3, which is higher than that of MFC with MnO2 catalyst (95 mW/m3). The open circuit voltage (OCV) of the MFC operated with MnO2 cathode gradually decreased during 14 days of operation, whereas the MFC with Pt/MnO2 cathode remained almost constant throughout the operation suggesting the higher stability of the Pt/MnO2 catalyst. Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced performance.

Keywords: Microbial fuel cell, oxygen reduction reaction, Pt/MnO2, palm oil mill effluent, polarization curve.

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Authors: Rawichar Chaipojjana, Suttipong Phosuksirikul, Arunsri Leejeerajumnean

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The objective of the study was to select the survival of probiotic strains when exposed to acidic and bile salts condition. Four probiotic strains Lactobacillus casei subsp. rhamnosus TISTR 047, Lactobacillus casei TISTR 1500, Lactobacillus acidophilus TISTR 1338 and Lactobacillus plantarum TISTR 1465 were cultured in MRS broth and incubated at 35ºC for 15 hours before being inoculated into acidic condition 5 M HCl, pH 2 for 2 hours and bile salt 0.3%, pH 5.8 for 8 hour. The survived probiotics were counted in MRS agar. Among four stains, Lactobacillus casei subsp. rhamnosus TISTR 047 was the highest tolerance specie. Lactobacillus casei subsp. rhamnosus TISTR 047 reduced 6.74±0.07 log CFU/ml after growing in acid and 5.52±0.05 log CFU/ml after growing in bile salt. Then, double emulsion of microorganisms was chosen to encapsulate before spray drying. Spray drying was done with the inlet temperature 170ºC and outlet temperature 80ºC. The results showed that the survival of encapsulated Lactobacillus casei subsp. rhamnosus TISTR 047 after spray drying decreased from 9.63 ± 0.32 to 8.31 ± 0.11 log CFU/ml comparing with non-encapsulated, 9.63 ± 0.32 to 4.06 ± 0.08 log CFU/ml. Therefore, Lactobacillus casei subsp. rhamnosus TISTR 047 would be able to survive in gastrointestinal and spray drying condition.

Keywords: Probiotic, acid, bile salt, spray drying.

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Authors: Wai Keng Teng, Gek Cheng Ngoh, Rozita Yusoff, Mohamed Kheireddine Aroua, Joe Shen Heng

Abstract:

As a by-product of the biodiesel industries, glycerol has been vastly generated which surpasses the market demand. It is imperative to develop an efficient glycerol valorization processes in minimizing the net energy requirement and intensifying the biodiesel production. In this study, base-catalyzed transesterification of glycerol with dimethyl carbonate using microwave irradiation as heating method to produce glycerol carbonate was conducted by varying grades of glycerol, i.e. 70%, 86% and 99% purity, that is obtained from biodiesel plant. Metal oxide catalysts were used with varying operating parameters including reaction time, DMC/glycerol molar ratio, catalyst weight %, temperature and stirring speed. From the study on the effect of different operating parameters it was found that the type of catalyst used has the most significant effect on the transesterification reaction. Amidst the metal oxide catalysts examined, CaO gave the best performance. This study indicates the feasibility of producing glycerol carbonate using different grade of glycerol in both conventional thermal activation and microwave irradiation with CaO as catalyst. Microwave assisted transesterification (MAT) of glycerol into glycerol carbonate has demonstrated itself as an energy efficient route by achieving 94.2% yield of GC at 65°C, 5 minutes reaction time, 1 wt% CaO and DMC/glycerol molar ratio of 2. The advantages of MAT transesterification route has made the direct utilization of bioglycerol from biodiesel production without the need of purification. This has marked a more economical and less-energy intensive glycerol carbonate synthesis route.

Keywords: Biodiesel, glycerol, glycerol carbonate, microwave irradiation.

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Authors: M. AlSawalha, F. Roessner, L. Novikova, L. Bel'chinskaya

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The acidity of different raw Jordanian clays containing zeolite, bentonite, red and white kaolinite and diatomite was characterized by means of temperature programmed desorption (TPD) of ammonia, conversion of 2-methyl-3-butyn-2-ol (MBOH), FTIR and BET-measurements. FTIR spectra proved presence of silanol and bridged hydroxyls on the clay surface. The number of acidic sites was calculated from experimental TPD-profiles. We observed the decrease of surface acidity correlates with the decrease of Si/Al ratio except for diatomite. On the TPD-plot for zeolite two maxima were registered due to different strength of surface acidic sites. Values of MBOH conversion, product yields and selectivity were calculated for the catalysis on Jordanian clays. We obtained that all clay samples are able to convert MBOH into a major product which is 3-methyl-3-buten-1-yne (MBYNE) catalyzed by acid surface sites with the selectivity close to 70%. There was found a correlation between MBOH conversion and acidity of clays determined by TPD-NH3, i.e. the higher the acidity the higher the conversion of MBOH. However, diatomite provided the lowest conversion of MBOH as result of poor polarization of silanol groups. Comparison of surface areas and conversions revealed the highest density of active sites for red kaolinite and the lowest for zeolite and diatomite.

Keywords: Acidity, Jordanian clay, Methylbutynol conversion, Temperature programmed desorption of ammonia

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Authors: Malee Santikunaporn, Tattep Techopittayakul, Channarong Asavatesanupap

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Biofuel production especially that of biodiesel has gained tremendous attention during the last decade due to environmental concerns and shortage in petroleum oil reservoir. This research aims to investigate the influences of operating parameters, such as the alcohol-to-oil molar ratio (4:1, 6:1, and 9:1) and the amount of catalyst (1, 1.5, and 2 wt.%) on the trans esterification of refined palm oil (RPO) in a medium-scale oscillatory baffle reactor.  It has been shown that an increase in the methanol-to-oil ratio resulted in an increase in fatty acid methyl esters (FAMEs) content. The amount of catalyst has an insignificant effect on the FAMEs content. Engine testing was performed on B0 (100 v/v% diesel) and blended fuel or B50 (50 v/v% diesel). Combustion of B50 was found to give lower torque compared to pure diesel. Exhaust gas from B50 was found to contain lower concentration of CO and CO₂.

Keywords: Biodiesel, oscillatory baffled reactor, palm oil, transesterification, fatty acid methyl esters.

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Authors: Umpawan Satitthai, Apanee Luengnaruemitchai, Erdogan Gulari

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In this study, oxidative steam reforming of methanol (OSRM) over a Au/CeO2–Fe2O3 catalyst prepared by a depositionprecipitation (DP) method was studied to produce hydrogen in order to feed a Proton Exchange Membrane Fuel Cell (PEMFC). The support (CeO2, Fe2O3, and CeO2–Fe2O3) were prepared by precipitation and co-precipitation methods. The impact of the support composition on the catalytic performance was studied by varying the Ce/(Ce+Fe) atomic ratio, it was found that the 1%Au/CF(0.25) calcined at 300 °C exhibited the highest catalytic activity in the whole temperature studied. In addition, the effect of Au content was investigated and 3%Au/CF(0.25) exhibited the highest activity under the optimum condition in the temperature range of 200 °C to 400 °C. The catalysts were characterized by various techniques: XRD, TPR, XRF, and UV-vis.

Keywords: CeO2, Fe2O3, Gold catalyst, Hydrogen production, Methanol, Oxidative steam reforming.

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Authors: K. Pipitthapan, S. Maksasithorn, P. Praserthdam, J. Panpranot, K. Suriye, S. Kunjara Na Ayudhya

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WO3/SiO2 catalysts were modified by an ion exchange method with sodium hydroxide or potassium hydroxide solution. The performance of the modified catalysts was tested in the metathesis of ethylene and trans-2-butene to propylene. During ion exchange, sodium and potassium ions played different roles. Sodium modified catalysts revealed constant trans-2-butene conversion and propylene selectivity when the concentrations of sodium in the solution were varied. In contrast, potassium modified catalysts showed reduction of the conversion and increase of the selectivity. From these results, potassium hydroxide may affect the transformation of tungsten oxide active species, resulting in the decrease in conversion whereas sodium hydroxide did not. Moreover, the modification of catalysts by this method improved the catalyst stability by lowering the amount of coke deposited on the catalyst surface.

Keywords: Acid sites, alkali metals, isomerization, metathesis.

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Authors: Akan C. Offong, E. J. Anthony, Vasilije Manovic

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A modified steady-state numerical model is developed for the electrochemical reduction of CO₂ to formic acid. The numerical model achieves a CD (current density) (~60 mA/cm²), FE-faradaic efficiency (~98%) and conversion (~80%) for CO₂ electro-reduction to formic acid in a microfluidic cell. The model integrates charge and species transport, mass conservation, and momentum with electrochemistry. Specifically, the influences of Bi-Sn based nanoparticle catalyst (on the cathode surface) at different mole fractions and 1-ethyl-3-methyl imidazolium tetra-fluoroborate ([EMIM][BF₄]) electrolyte, on CD, FE and CO₂ conversion to formic acid is studied. The reaction is carried out at a constant concentration of electrolyte (85% v/v., [EMIM][BF₄]). Based on the mass transfer characteristics analysis (concentration contours), mole ratio 0.5:0.5 Bi-Sn catalyst displays the highest CO₂ mole consumption in the cathode gas channel. After validating with experimental data (polarisation curves) from literature, extensive simulations reveal performance measure: CD, FE and CO₂ conversion. Increasing the negative cathode potential increases the current densities for both formic acid and H₂ formations. However, H₂ formations are minimal as a result of insufficient hydrogen ions in the ionic liquid electrolyte. Moreover, the limited hydrogen ions have a negative effect on formic acid CD. As CO₂ flow rate increases, CD, FE and CO₂ conversion increases.

Keywords: Carbon dioxide, electro-chemical reduction, microfluidics, ionic liquids, modelling.

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Authors: T. J. Jamaleddine

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Purge columns or degasser vessels are widely used in the polyolefin process for removing trapped hydrocarbons and in-excess catalyst residues from the polymer particles. A uniform distribution of purged gases coupled with a plug-flow characteristic inside the column system is desirable to obtain optimum desorption characteristics of trapped hydrocarbon and catalyst residues. Computational Fluid Dynamics (CFD) approach is a promising tool for design optimization of these vessels. The success of this approach is profoundly dependent on the solution strategy and the choice of geometrical layout at the vessel outlet. Filling the column with solids and initially solving for the solids flow minimized numerical diffusion substantially. Adopting a cylindrical configuration at the vessel outlet resulted in less numerical instability and resembled the hydrodynamics flow of solids in the hopper segment reasonably well.

Keywords: CFD, gas-solids flow, gas purging, species transport, purge column, degasser vessel.

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Authors: Ali Zaker, Zhi Chen

Abstract:

Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contain four obvious stages and the main decomposition reaction occurred in the range of 200-600 °C. Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2 and 3 were in the range of 6.67-20.37 kJ/mol for SS; 1.51-6.87 kJ/mol for HZSM5; and 2.29-9.17 kJ/mol for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1 and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with HZSM5 and AC were in the total range of C4-C17 with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds while the presence of HZSM5 and AC dropped to 7.3% and 13.02%, respectively. Meanwhile, generation of value-added chemicals such as light aromatic compounds were significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR and TGA techniques. Overall, this research demonstrated that AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.

Keywords: Activated char, bio-oil, catalytic pyrolysis, HZSM5, sewage sludge.

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Authors: Mahmoud A. Rabah

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Preparation of size controlled nano-particles of silver catalyst on carbon substrate from e-waste has been investigated. Chemical route was developed by extraction of the metals available in nitric acid followed by treatment with hydrofluoric acid. Silver metal particles deposited with an average size 4-10 nm. A stabilizer concentration of 10- 40 g/l was used. The average size of the prepared silver decreased with increase of the anode current density. Size uniformity of the silver nano-particles was improved distinctly at higher current density no more than 20mA... Grain size increased with EK time whereby aggregation of particles was observed after 6 h of reaction.. The chemical method involves adsorption of silver nitrate on the carbon substrate. Adsorbed silver ions were directly reduced to metal particles using hydrazine hydrate. Another alternative method is by treatment with ammonia followed by heating the carbon loaded-silver hydroxide at 980°C. The product was characterized with the help of XRD, XRF, ICP, SEM and TEM techniques.

Keywords: e-waste, silver catalyst, metals recovery, electrokinetic process.

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Authors: Hafizuddin W. Yussof, Syamsutajri S. Bahri, Adam P. Harvey

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Strong anion exchange resins with QN+OH-, have the potential to be developed and employed as heterogeneous catalyst for transesterification, as they are chemically stable to leaching of the functional group. Nine different SIERs (SIER1-9) with QN+OH-were prepared by suspension polymerization of vinylbenzyl chloridedivinylbenzene (VBC-DVB) copolymers in the presence of n-heptane (pore-forming agent). The amine group was successfully grafted into the polymeric resin beads through functionalization with trimethylamine. These SIERs are then used as a catalyst for the transesterification of triacetin with methanol. A set of differential equations that represents the Langmuir-Hinshelwood-Hougen- Watson (LHHW) and Eley-Rideal (ER) models for the transesterification reaction were developed. These kinetic models of LHHW and ER were fitted to the experimental data. Overall, the synthesized ion exchange resin-catalyzed reaction were welldescribed by the Eley-Rideal model compared to LHHW models, with sum of square error (SSE) of 0.742 and 0.996, respectively.

Keywords: Anion exchange resin, Eley-Rideal, Langmuir-Hinshelwood-Hougen-Watson, transesterification.

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Authors: Bita Bayatsarmadi, Shi-Zhang Qiao

Abstract:

Oxygen Reduction Reaction (ORR) performance of iron and nitrogen co-doped porous carbon nanoparticles (Fe-NPC) with various physical and (electro) chemical properties have been investigated. Fe-NPC nanoparticles are synthesized via a facile soft-templating procedure by using Iron (III) chloride hexa-hydrate as iron precursor and aminophenol-formaldehyde resin as both carbon and nitrogen precursor. Fe-NPC nanoparticles shows high surface area (443.83 m2g-1), high pore volume (0.52 m3g-1), narrow mesopore size distribution (ca. 3.8 nm), high conductivity (IG/ID=1.04), high kinetic limiting current (11.71 mAcm-2) and more positive onset potential (-0.106 V) compared to metal-free NPC nanoparticles (-0.295V) which make it high efficient ORR metal-free catalysts in alkaline solution. This study may pave the way of feasibly designing iron and nitrogen containing carbon materials (Fe-N-C) for highly efficient oxygen reduction electro-catalysis.

Keywords: Electro-catalyst, mesopore structure, oxygen reduction reaction, soft-template.

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Authors: V. Georgiev

Abstract:

Catalytic oxidation of benzene assisted by ozone, on alumina, silica, and boehmite-supported Ni/Pd catalysts was investigated at 353 K to assess the influence of the support on the reaction. Three bimetallic Ni/Pd nanosized samples with loading 4.7% of Ni and 0.17% of Pd supported on SiO₂, AlOOH and Al₂O₃ were synthesized by the extractive-pyrolytic method. The phase composition was characterized by means of XRD and the surface area and pore size were estimated using Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH) methods. At the beginning of the reaction, catalysts were significantly deactivated due to the accumulation of intermediates on the catalyst surface and after 60 minutes it turned stable. Ni/Pd/AlOOH catalyst showed the highest steady-state activity in comparison with the Ni/Pd/SiO₂ and Ni/Pd/Al₂O₃ catalysts. Their activity depends on the ozone decomposition potential of the catalysts because of generating oxidizing active species. The sample with the highest ozone decomposition ability which correlated to the surface area of the support oxidizes benzene to the highest extent.

Keywords: Ozone, catalysts, oxidation, Volatile organic compounds, VOCs.

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Authors: Wanyu Mao, Hongfang Ma, Haitao Zhang, WeixinQian, Weiyong Ying

Abstract:

The nature of adsorbed species on catalytic surface over an industrial precipitated iron-based high temperature catalyst during FTS was investigated by in-situ DRIFTS and chemical trapping. The formulation of the mechanism of oxygenates formation and key intermediates were also discussed. Numerous oxygenated precursors and crucial intermediates were found by in-situ DRIFTS, such as surface acetate, acetyl and methoxide. The results showed that adsorbed molecules on surface such as methanol or acetaldehyde could react with basic sites such as lattice oxygen or free surface hydroxyls. Adsorbed molecules also had reactivity of oxidizing. Moreover, acetyl as a key intermediate for oxygenates was observed by investigation of CH3OH + CO and CH3I + CO + H2. Based on the nature of surface properties, the mechanism of oxygenates formation on precipitated iron-based high temperature catalyst was discussed.

Keywords: Iron-based catalysts, intermediates, oxygenates, in-situ DRIFTS, chemical trapping.

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Authors: Farooq A. Al-Sheikh, Ali Elkamel, William A. Anderson

Abstract:

A fluidized catalytic cracking unit (FCCU) is one of the effective units in many refineries. Modeling and optimization of FCCU were done by many researchers in past decades, but in this research, comparison between post- and oxy-combustion was studied in the regenerator-FCCU. Therefore, a simplified mathematical model was derived by doing mass/heat balances around both reactor and regenerator. A state space analysis was employed to show effects of the flow rates variables such as air, feed, spent catalyst, regenerated catalyst and flue gas on the output variables. The main aim of studying dynamic responses is to figure out the most influencing variables that affect both reactor/regenerator temperatures; also, finding the upper/lower limits of the influencing variables to ensure that temperatures of the reactors and regenerator work within normal operating conditions. Therefore, those values will be used as side constraints in the optimization technique to find appropriate operating regimes. The objective functions were modeled to be maximizing the energy in the reactor while minimizing the energy consumption in the regenerator. In conclusion, an oxy-combustion process can be used instead of a post-combustion one.

Keywords: FCCU modeling, optimization, oxy-combustion post-combustion.

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Authors: SeungKyu Shin, Jeong Hyub Ha, Sung Han, JiHyeon Song

Abstract:

Silver nano-particles have been used for antibacterial purpose and it is also believed to have removal of odorous compounds, oxidation capacity as a metal catalyst. In this study, silver nano-particles in nano sizes (5-30 nm) were prepared on the surface of NaHCO3, the supporting material, using a sputtering method that provided high silver content and minimized conglomerating problems observed in the common AgNO3 photo-deposition method. The silver nano-particles were dispersed by dissolving Ag-NaHCO3 into water, and the dispersed silver nano-particles in the aqueous phase were applied to remove inorganic odor compounds, H2S, in a scrubbing reactor. Hydrogen sulfide in the gas phase was rapidly removed by the silver nano-particles, and the concentration of sulfate (SO4 2-) ion increased with time due to the oxidation reaction by silver as a catalyst. Consequently, the experimental results demonstrated that the silver nano-particles in the aqueous solution can be successfully applied to remove odorous compounds without adding additional energy sources and producing any harmful byproducts

Keywords: Silver nano-particles, Scrubbing, Oxidation, Hydrogen sulfide, Ammonia

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Authors: R. D. Kulkarni, Mayur Chaudhari, S. Mishra

Abstract:

Curing of paints by exposure to UV radiations is emerging as one of the best film forming technique as an alternative to traditional solvent borne oxidative and thermal curing coatings. The composition and chemistry of UV curable coatings and role of multifunctional and monofunctional monomers, oligomers, and photoinitiators have been discussed. The limitations imposed by thermodynamic equilibrium and tendency for acrylic double bond polymerizations during synthesis of multifunctional acrylates have been presented. Aim of present investigation was thus to explore the reaction variables associated with synthesis of multifunctional acrylates. Zirconium oxychloride was evaluated as catalyst against regular acid functional catalyst. The catalyzed synthesis of glyceryl acrylate and neopentyl glycol acrylate was conducted by variation of following reaction parameters: two different reactant molar ratios- 1:4 and 1:6; catalyst usage in % by moles on polyol- 2.5, 5.0 and 7.5 and two different reaction temperatures- 45 and 75 0C. The reaction was monitored by determination of acid value and hydroxy value at regular intervals, besides TLC, HPLC, and FTIR analysis of intermediates and products. On the basis of determination of reaction progress over 1-60 hrs, the esterification reaction was observed to follow 2nd order kinetics with rate constant varying from 1*10-4 to 7*10-4. The thermal and catalytic components of second order rate constant and energy of activation were also determined. Uses of these kinetic and thermodynamic parameters in design of reactor for manufacture of multifunctional acrylate ester have been presented. The synthesized multifunctional acrylates were used to formulate and apply UV curable clear coat followed by determination of curing characteristics and mechanical properties of cured film. The overall curing rates less than 05 min. were easily attained indicating economical viability of radiation curable system due to faster production schedules

Keywords: glyceryl acrylate, neopentyl glycol acrylate, kinetic modeling, zirconium oxychloride.

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Authors: B. Aydinli, A. Caglar

Abstract:

Renewable energy sources have gained ultimate urgency due to the need of the preservation of the environment for a sustainable development. Pyrolysis is an ultimate promising process in the recycling and acquisition of precious chemicals from wastes. Here, the co-pyrolysis of hazelnut shell with ultra-high molecular weight polyethylene was carried out catalytically and noncatalytically at 500 and 650 ºC. Potassium dichromate was added in certain amounts to act as a catalyst. The liquid, solid and gas products quantities were determined by gravimetry. As a main result, remarkable increases in gasification were observed by using this catalyst for pure components and their blends especially at 650 ºC. The increase in gas product quantity was compensated mainly with the decreases in the solid products and additionally in some cases liquid products quantities. These observations may stem from mainly the activation of carbon-carbon bonds rather than carbon-hydrogen bonds via potassium dichromate. Also, the catalytic effect of potassium dichromate on HS: PEO and HS: UHMWPE co-pyrolysis was compared.

Keywords: Hazelnut shell, Polyethylene oxide, Potassium Dichromate, Pyrolysis, UHMWPE

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Authors: Ibrahim F. Elbaba, Paul T. Williams

Abstract:

Hydrogen is regarded to play an important role in future energy systems because it can be produced from abundant resources and its combustion only generates water. The disposal of waste tyres is a major problem in environmental management throughout the world. The use of waste materials as a source of hydrogen is particularly of interest in that it would also solve a waste treatment problem. There is much interest in the use of alternative feedstocks for the production of hydrogen since more than 95% of current production is from fossil fuels. The pyrolysis of waste tyres for the production of liquid fuels, activated carbons and gases has been extensively researched. However, combining pyrolysis with gasification is a novel process that can gasify the gaseous products from pyrolysis. In this paper, an experimental investigation into the production of hydrogen and other gases from the bench scale pyrolysis-gasification of tyres has been investigated. Experiments were carried using a two stage system consisting of pyrolysis of the waste tyres followed by catalytic steam gasification of the evolved gases and vapours in a second reactor. Experiments were conducted at a pyrolysis temperature of 500 °C using Ni/Al2O3 as a catalyst. The results showed that there was a dramatic increase in gas yield and the potential H2 production when the gasification temperature was increased from 600 to 900 oC. Overall, the process showed that high yields of hydrogen can be produced from waste tyres.

Keywords: Catalyst, Hydrogen, Pyrolysis, Gasification, Tyre, Waste

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Authors: Francis Bukola Dada, Samuel Ojo Ajayi, Babatunde Sunday Ewulo, Kehinde Oseni Saani

Abstract:

A key element in the sustainability of the soil-plant relationship in crop yield and performance is the soil's capacity to support tree crops prior to establishment. With the intention of determining the suitability and limitations of the soils of the locations, the northern and southern portions of Akure, a rainforest in Nigeria, were chosen for the suitability evaluation of land for tree crops. In the study area, 16 pedons were established with the help of the Global Positioning System (GPS), the locations were georeferenced and samples were taken from the pedons. The samples were subjected to standard physical and chemical testing. The findings revealed that soils in the research locations were deep to extremely deep, with pH ranging from highly acidic to slightly acidic (4.94 to 6.71). and that sand predominated. The soils had low levels of organic carbon, effective cation exchange capacity (ECEC), total nitrogen, and available phosphorus, whereas exchangeable cations were evaluated as low to moderate. The suitability result indicated that only Pedon 2 and Pedon 14 are currently highly suitable (S1) for the production of oil palms, while others ranged from moderately suitable to marginally suitable. Pedons 4, 12, and 16 were not suitable (N1), respectively, but other Pedons were moderately suitable (S2) and marginally suitable (S3) for the cultivation of cocoa. None of the study areas are currently highly suitable for the production of oil palms. The poor soil texture and low fertility status were the two main drawbacks found. Finally, sound management practices and soil conservation are essential for fertility sustainability.

Keywords: Cashew, cocoa, land evaluation, oil palm, soil fertility suitability.

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