A PROCEDURE FOR EVALUATION OF COMMERCIAL FCC CATALYSTS

Based on the correlations between laboratory units and commercial plants, a procedure has been developed to guide commercial FCC (Fluid Catalytic Cracking) catalysts selection. Examining the operability of catalyst mixtures during catalyst transition period is emphasized. The testing procedure is simple and reliable. A commercially available catalyst and the catalyst currently in use have been compared to demonstrate the applicability of this procedure. The commercial testing has confirmed the reliability of laboratory results. The use of the catalyst evaluated led to a 30% saving in catalyst cost.     

Activities of MFI-Supported Rhenium Catalysts for the Aromatization of Methane: Effect of Cationic Form of the Inorganic Carrier

MFI type inorganic carrier was used in two different cationic forms, hydrogen and calcium respectively. MFI-supported molybdenum and rhenium catalysts were prepared. The activities of the catalysts were compared for the aromatization reaction of methane. Higher activity values were attained with the catalysts supported on HZSM-5. Aromatics were also observed with the catalysts supported on CaZSM-5, despite their deficiency in acid sites. Highly dispersed rhenium is expected to be formed with the use of the inorganic carrier in calcium form. On the other hand, lower reaction rates were observed with rhenium supported on CaZSM-5, in spite of the improved dispersion of the active rhenium species on this catalyst. This was interpreted in terms of the critical role of the acid sites in the conversion of methane to aromatics, compared to the improved dispersion of the active metal.     

Łukasiewicz logic and Riesz spaces

We initiate a deep study of Riesz MV-algebras which are MV-algebras endowed with a scalar multiplication with scalars from \([0,1]\) . Extending Mundici’s equivalence between MV-algebras and \(\ell \) -groups, we prove that Riesz MV-algebras are categorically equivalent to unit intervals in Riesz spaces with strong unit. Moreover, the subclass of norm-complete Riesz MV-algebras is equivalent to the class of commutative unital C \(^*\) -algebras. The propositional calculus \({\mathbb R}{\mathcal L}\) that has Riesz MV-algebras as models is a conservative extension of ?ukasiewicz \(\infty \) -valued propositional calculus and is complete with respect to evaluations in the standard model \([0,1]\) . We prove a normal form theorem for this logic, extending McNaughton theorem for ? ukasiewicz logic. We define the notions of quasi-linear combination and quasi-linear span for formulas in \({\mathbb R}{\mathcal L},\) and relate them with the analogue of de Finetti’s coherence criterion for \({\mathbb R}{\mathcal L}\) .     

A theoretical study of solvent effects on Kolbe-Schmitt reaction kinetics

A theoretical DFT study was employed to confirm the Kolbe-Schmitt reaction mechanism and investigate solvent effects on this reaction. The use of a solvent in the Kolbe-Schmitt reaction is desirable to facilitate a homogeneous reaction mixture and potentially improve the reaction rate. The candidate solvents were designed using computer aided molecular design (CAMD) and tested using DFT solvation calculations. The results from the quantum mechanical calculations were then used to determine the rate constants for each elementary step, the overall reaction yields and the corresponding residence time. The methodology was tested on the reaction without solvent, with solvents reported in the literature, and with the designed solvents. The study revealed that in the presence of solvents with high dielectric constant the reaction becomes reversible, leading to low product yields.     

Heavy Metal Removal and Neutralization of Acid Mine Waste Water ‐ Kinetic Study

The influence of the apatite on the efficiency of neutralization and on heavy metal removal of acid mine waste water has been studied. The analysis of the treated waste water samples with apatite has shown an advanced purification, the concentration of the heavy metals after the treatment of the waste water with apatite being 25 to 1000 times less than the Maximum Concentration Limits admitted by European Norms (NTPA 001/2005). In order to establish the macro‐kinetic mechanism in the neutralization process, the activation energy, Ea, and the kinetic parameters, rate coefficient of reaction, k_r, and k_t were determined from the experimental results obtained in “ceramic ball‐mill” reactor. The obtained values of the activation energy Ea >> 42 kJ mol^?1 (e.g. Ea = 115.50 ± 7.50 kJ mol^?1 for a conversion of sulphuric acid η_H2SO4 = 0.05, Ea = 60.90 ± 9.50 kJ mol^?1 for η ^H2SO4 = 0.10 and Ea = 55.75 ± 10.45 kJ mol^‐1 for η ^H2SO4 = 0.15) suggest that up to a conversion of H2SO4 equal 0.15 the global process is controlled by the transformation process, adsorption followed by reaction, which means surface‐controlled reactions. At a conversion of sulphuric acid η ^H2SO4 > 0.15, the obtained values of activation energy Ea < 42 kJ mol^‐1 (e.g. Ea = 37.55 ± 4.05 kJ mol^‐1 for η ^H2SO4 = 0.2, Ea = 37.54 ± 2.54 kJ mol^‐1 for η ^H2SO4 = 0.3 and Ea = 37.44 ± 2.90 kJ mol^‐1 for η ^H2SO4 = 0.4) indicate diffusion‐controlled processes. This means a combined process model, which involves the transfer in the liquid phase followed by the chemical reaction at the surface of the solid. Kinetic parameters as rate coefficient of reaction, kr with values ranging from (5.02 ± 1.62) 10‐4 to (8.00 ± 1.55) 10‐4 (s^‐1) and transfer coefficient, kt, ranging from (8.40 ± 0.50) 10‐5 to (10.42 ± 0.65) 10‐5 (m s^‐1) were determined.     

Synthesis and properties of chitosan-modified poly(vinyl butyrate)

Modification of chitosan by grafting of vinyl butyrate was carried out in homogeneous phase using potassium persulfate as redox initator and 1.5% acetic acid as solvent. The percent grafting and grafting efficiency were analysed and the high grafting efficiency up to 94% was observed. The effects of reaction variables such as monomer concentration, initiator concentration, temperature and reaction time were investigated. It was observed that the solubility of chitosan was markedly reduced after grafting with vinyl butyrate. The grafted product is insoluble in common organic solvents as well in dilute organic and inorganic acids. Characterization of the graft copolymers were carried out by using Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) technics. Characteristic signal of carbonyl group was observed at 1,731 cm⁻¹ which belongs to the poly vinyl butyrate segments in the graft copolymer. The melting transition of the chitosan main chain in the copolymer shifted to 124°C from its original value 101°C. In addition to these, we have also studied topology of the graft copolymer and the SEM micrograph showed continuous homogenous matrix which means there is no phase separation.     

Toughening of epoxy thermosets with nano-sized or micron-sized domains of poly(ethylene oxide)-b-poly(butadiene-co-acrylonitrile)-b-poly(ethylene oxide) triblock copolymers synthesized using room temperature ester coupling reaction

Poly(ethylene oxide)-b-poly(butadiene-co-acrylonitrile)-b-poly(ethylene oxide) (PEO-b-PBN-b–PEO) triblock copolymers with three different compositions were synthesized from poly(ethylene glycol) methyl ethers and carboxylic acid-terminated poly(butadiene-co-acrylonitrile) (CTBN) by ester coupling reaction at room temperature. The PEO-b-PBN-b-PEO was incorporated into anhydride cured epoxy thermosets to improve the fracture toughness by the formation of either nano-sized spherical micelles or micron-sized vesicles. The polymer chemical structure was confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance, and gel permeation chromatography. The morphology of PEO-b-PBN-b–PEO within the epoxy thermosets was investigated using a transmission electron microscope, an atomic force microscope, and a scanning electron microscope. Also, we conducted impact testing and plane-strain fracture toughness testing to evaluate the fracture toughness in terms of the impact strength and the critical stress intensity factors (K_IC) for the modified epoxy thermosets. The results revealed that all the PEO-b-PBN-b-PEO triblock copolymers are more effective in the toughening of epoxy thermoset compare to CTBN. We found that the 5 wt% PEO-b-PBN-b-PEO modified epoxy thermoset containing micron-sized vesicles exhibited the highest K_IC, which was 3.23 times as high as the K_IC of pristine epoxy thermoset. Besides, the glass transition temperature remained and the tensile modulus did not reduce remarkably when the amount of PEO-b-PBN-b-PEO added into epoxy was 5 wt%.     

An investigation on wear behavior of UHMWPE/carbide composites at elevated temperatures

Ultra-high molecular weight polyethylene (UHMWPE) is extensively used in frictional applications due to its advanced wear resistance. This advanced polymer is reinforced with hard particulate fillers for further developments against wear conditions. Since elevated temperatures prevail in the service conditions, wear behavior of UHMWPE composites is an important issue for the engineering applications. In the present work, UHMWPE-based composites including silicon carbide (SiC) fillers were fabricated in a compression molding chamber. In the specimen preparation stage, molding pressure, filler amount, and filler particle size were varied to investigate the influence of these variables. Upon deciding the optimum parameters from the wear tests conducted at room temperature, the wear experiments were repeated for the optimum specimen at elevated temperatures, such as 40 and 60°C. According to the results, the wear behavior of the SiC/UHMWPE composites is heavily changed by the effect of elevated temperature. Adhesive effect is pronounced at elevated temperatures while the wear characteristics possess the abrasive effect in the sliding path. In addition, the composites exhibit an accelerated material loss as temperature increases during the frictional system.     

Improvements of the structural,thermal, and mechanical properties of structural adhesive with functionalized boron nitride nanoparticles

Investigations on the production and development of nanoparticle-reinforced polymer materials have been attracted attention by researchers. Various nanoparticles have been used to improve the mechanical, chemical, thermal, and physical properties of polymer matrix composites. Boron compounds come to the fore to improve the mechanical and thermal properties of polymers. In this study, mechanical, thermal, and structural properties of structural adhesive have been examined by adding nano hexagonal boron nitride (h-BN) to epoxy matrix at different percentages (0.5, 1, 2, 3, 4, and 5%). For this purpose, nano h-BN particles were functionalized with 3-aminopropyltriethoxysilane (APTES) to disperse the h-BN nanoparticles homogeneously in epoxy matrix and to form a strong bond at the matrix interface. Two-component structural epoxy adhesive was modified by using functionalized h-BN nanoparticles. The structural and thermal properties of the modified adhesives were investigated by scanning electron microscopy and energy dispersion X-ray spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis techniques. Tensile test and dynamic mechanical analysis were performed to determine the mechanical properties of the adhesives. When the results obtained from analysis were examined, it was seen that the nano h-BN particles functionalized with APTES were homogeneously dispersed in the epoxy matrix and formed a strong bond. In addition that, it was concluded from the experimental results that the thermal and mechanical properties of adhesives were improved by adding functionalized nano h-BN particles into epoxy at different ratios.     

Structural,thermal, and mechanical properties of silanized boron carbide doped epoxy nanocomposites

In the presented study, the structural, thermal, and mechanical properties of the nanocomposites were investigated by doping silanized hexagonal boron carbide (h-B₄C) nanoparticles in varying proportions (0.5%, 1%, 2%, 3%, 4%, and 5%) into the epoxy resin by weight. For this purpose, the surfaces of h-B₄C nanoparticles were silanized by using 3-(glycidyloxypropyl) trimethoxysilane (GPS) to improve adhesion between h-B₄C nanoparticles and epoxy matrix. Then, the silanized nanoparticles were added to the resin by ultrasonication and mechanical stirring techniques to produce nanocomposites. The bond structure differences of silanized B₄C nanoparticles (s-B₄C) and nanoparticle doped composites were investigated by using Fourier transform infrared spectroscopy. Scanning electron microscopy and energy dispersion X-ray spectroscopy (SEM-EDS) technique was used to examine the distribution of nanoparticles in the modified nanocomposites. Differential scanning calorimetry and thermogravimetric analysis techniques were used to determine the thermal properties of the neat and s-B₄C doped nanocomposites. The tensile test and dynamic mechanical analysis were performed to determine the mechanical properties. When the experimental results were examined, changes in the bonding structure of the s-B₄C nanoparticles doped nanocomposites and significant improvements in the mechanical and thermal properties were observed. The optimum doping ratio was determined as 2% by weight. At this doping ratio, the T_g, tensile strength and storage modulus increased approximately 18%, 35%, and 44% compared to the neat composite, respectively.