The aim of this research was the production of beta-galactosidase from thermophilic fungi for use in low lactose milk production or other possible applications. For this purpose, three thermophilic fungi Humicola insolens, Torula thermophila and Thermomyces lanuginosus were screened for lactase production. Highest lactase activity was observed in Thermomyces lanuginosus. The carbon source inducing highest extracellular lactase production in Thermomyces lanuginosus was determined as arabinose. When grown on arabinose T. lanuginosus produced two major lactase activity peaks, one being at day 4 (beta-galactosidase-A) and second starting following the initiation of biomass degradation at day 3 suggesting the existence of a cell wall-bound beta-galactosidase (beta-galactosidase-B). Maximum activity of the second enzyme was at day 10. Crude enzyme stored at 4&ordm / C and -20&ordm / C was stable over a period of one month. Optimum pH and temperature of crude enzyme were found as pH 6.8 and 65&ordm / C. For concentration of extracellular enzyme, fractional ammonium sulfate precipitation with 60-85% salt was applied. Comparisons with commercial lactase obtained from Kluyveromyces lactis revealed that partially purified lactase from Thermomyces lanuginosus was 1.3 times more efficient in hydrolysis of lactose even at 30&ordm / C which is optimum for Kluyveromyces lactis. Lactose hydrolysis was enhanced at higher temperatures and reached maximum at 50-60&ordm / C giving 4.7 fold higher hydrolysis than Kluyveromyces lactis beta-galactosidase. Molecular weight of the second enzyme was determined as 156 kDa by gel filtration. Being an extracellular enzyme with optimum pH suitable for dairy processes, high thermotolerance and stability, this enzyme has a potential for commercial use.

Magnesium oxychloride cement (MOC) based grinding and polishing bricks developed for polishing of granite based ceramic tiles were produced and characterized. For surface grinding 46 and 180 grit size SiO2 powder embedded MOC based abrasive bricks / for polishing 600 and 1200 grit size SiC powder embedded MOC based abrasive bricks followed by neat (unreinforced) MOC pastes were applied on ceramic tiles. Three different neat MOC pastes depending on MgO/MgCl2 molar ratio in the paste e.g. 6/1, 7/1, and 8/1, were formed and evaluated. Grinding bricks were formed by adding 30 weight percentage, wt%, of both SiO2 powders. Polishing bricks were formed by adding 20, 25, and 30 wt% of both SiC powders. X-Ray diffraction analyses revealed that MOC F5 was the main crystalline phase in the neat MOC pastes. Additions of both SiO2 and SiC powders enhanced mechanical properties namely / compressive strength and abrasion resistance, chemical durability in water and polishing ability of MOC paste. More than 25 wt% addition of SiC powders had a tendency to decrease the compressive strength and water resistance of MOC paste. Polishing performance of abrasive bricks was evaluated in terms of mean surface roughness of ceramic tiles and abrasive brick consumption upon polishing. Scanning Electron Microscope examinations revealed the evidences of the reasons that 25 wt% SiC powder embedded abrasive bricks has the best qualifications in terms of abrasion resistance and polishing performance.

Strontium pyrophosphate is a promising phosphate that is used widely in the industry as a result of its luminescent, fluorescent, dielectric, semi-conductor, catalyst, magnetic and ion exchange properties. Thermoluminescent dosimetry (TLD) is one of such areas. Recent researches in METU on thermoluminescence property of strontium pyrophosphate showed that strontium pyrophosphate could give enough intensity for radiation dosimetry when doped with oxides of some rare-earth elements. In this study strontium pyrophosphate was synthesized and the product was doped with copper-silver, copper-indium and manganese-praseodymium ions by solid-state reaction. In addition to these processes, characterization and the investigation of thermoluminescence properties of strontium pyrophosphate with and without dopants was conducted. Stoichiometric quantities of strontium carbonate and ammonium dihydrogen phosphate were weighed, mixed and ground by agate mortar. Afterwards, the mixture was heated at 900&amp / #730 / C for 14.5 hours. For doping process, synthesized strontium pyrophosphate and different amounts of copper oxide, indium oxide, silver nitrate, manganese oxide and praseodymium oxide were weighed and powdered together. Then, mixture was heated at 950&amp / #730 / C for 11 hours. For characterization of strontium pyrophosphate samples with and without dopants / X-ray Diffraction (XRD) was implemented. Fourier Transform Infrared Spectroscopy (FTIR) was used to determine whether the bond structures were affected from doping or not. Thermal properties of the samples were investigated with the help of Differential Thermal Analysis (DTA). Morphology of compounds was observed by Scanning Electron Microscope (SEM). Afterwards thermoluminescence (TLD) studies were carried out. XRD pattern of samples showed that the intensity of hkl-310 peak of strontium pyrophosphate increased with the inclusion of metal oxides, however none of the characteristic peaks of metal oxides was observed. Addition of metal oxides caused no change in FTIR meaning that the anionic part of matrix compound, which is strontium pyrophosphate, has structural stability. Thermal analysis and morphological investigation of this material were performed. TLD results were different for each sample, which has different content. The most significant peak, which is suitable for radiation dosimetry was observed at 160&amp / #730 / C in the glow curve with the sample doped with 7% manganese oxide and 1% praseodymium oxide.

In this thesis, characterization of two class F fly ashes (FA) from &Ccedil / atalagzi and Sug&ouml / z&uuml / thermal power plants were carried out and their utilization potentials in three different fields were examined. Characterization of sintered samples and determination of their utilization potentials in ceramic industry is the first research area in this thesis. For this purpose, the class F fly ash samples were first pressed into cylindrical specimen without the addition of any organic binders or inorganic additives, and then sintered to form ceramic materials. Effects of sintering temperature and time on sintering characteristics were investigated. In the experiments, the cylindrical specimens were first preheated to 300oC for 1 h to remove moisture and any other gases. The specimens were then fired at the temperatures of 1000oC, 1050oC, 1100oC and 1150oC for the sintering times of 0.5, 1.0, 1.5 and 2.0 hours. Heating rate of 10oC/min was kept constant throughout the experiments. Quality of sintered samples was evaluated in terms of ceramic specifications such as density, water absorption, porosity, shrinkage and splitting tensile strength. In addition, mineralogical and microstructural changes during sintering were determined with X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses. According to literature data, better microstructure, the highest density and strength with the lowest porosity, water absorption and shrinkage values are the indications of the optimum sintering conditions. Based on these specifications, Sug&ouml / z&uuml / fly ash gave better results compared to &Ccedil / atalagzi fly ash, and the optimum conditions were achieved at the sintering temperature of 1150oC for the sintering time of 1.5 hours for both samples. Pozzolanic reactivity of the fly ashes and their utilization potentials in civil engineering applications were also examined in detail during this study. For this purpose, &Ccedil / atalagzi (CFA) and Sug&ouml / z&uuml / (SFA) fly ashes were first subjected to a specific hydraulic classification process developed at CAER (University of Kentucky, Center for Applied Energy Research) to recover ultrafine fly ash particles. The overflow products with average particle sizes of 5.2 &mu / m for CFA and 4.4 &mu / m for SFA were separated from the respective as-received samples with average particle sizes of 39 &mu / m and 21 &mu / m. After the classification stage, the pozzolanic activities of these ultrafine fly ash fractions (UFA) and as-received samples were examined by preparing a number of mortar (mixture of Portland cement (PC), FA or UFA as partial cement replacement, sand and water) and paste (mixture of PC, FA or UFA as partial cement replacement and water) specimens. Control samples containing only PC were also prepared and tested through the experiments for the comparison of the results. In the mortar experiments, three different PC replacement ratios by FA and UFA (10%, 20% and 30%) were used to examine the effects of FA and UFA samples on the fresh and hardened mortar properties such as water requirement, compressive strength, drying shrinkage and water expansion. These mortar tests indicated that ultrafine fractions of &Ccedil / atalagzi (CUFA) and Sug&ouml / z&uuml / (SUFA) fly ashes provided more than 10% reduction in water demand compared to the control sample for 30% PC replacement. The mortar cubes containing CUFA and SUFA samples exhibited also higher strength development rates after 14 days compared to the ones with as-received samples and PC only. At the end of the curing age of 112 days, both CUFA and SUFA provided more than 40% increase in compressive strength compared to the control sample for the PC replacement ratios higher than 20%. As a comparison, SUFA gave better results than CUFA in both water demand and compressive strength tests. The mortar bars prepared with the both FA and UFA samples exhibited very low shrinkage and expansion values. These values decreased generally with increasing PC replacement ratio especially after 14 days. In the paste experiments, thermogravimetric analyses (TGA) of the paste specimens prepared by using only with 20% PC replacement were carried out to determine pozzolanic reactivity of the samples. The difference between the remaining Ca(OH)2 (portlandite) contents in the paste specimens containing the fly ashes and the reference PC paste was used as a measure of pozzolanic reactivity. After 112 days, 68.56% and 62.68% Ca(OH)2 content of PC only pastes were obtained with the pastes containing CUFA and SUFA samples, respectively, corresponding to 11% and 13% more Ca(OH)2 consumptions in reference to the respective as-received samples. X-ray diffraction (XRD) analyses were also performed for comparison of main portlandite peak intensities in the paste specimens containing FA or UFA with those in the PC only paste during cement hydration. According to these XRD analyses, portlandite content in PC/UFA pastes decreased significantly after 14 days compared to the PC only paste. All of these tests and analyses showed that a highly reactive lower cost pozzolan with very fine particle size and higher surface area compared to regular fly ash pozzolans can be produced from both &Ccedil / atalagzi and Sug&ouml / z&uuml / fly ashes using a relatively simple hydraulic classification technology. Cenosphere recovery potentials from &Ccedil / atalagzi and Sug&ouml / z&uuml / fly ashes were also studied in this thesis. Determination of cenosphere content was done under optical microscope by particle counting on the basis of point and area. Based on the point-counting data, CFA and SFA samples originally contain 11.30% and 4.50% cenospheres, respectively. Variations of cenosphere contents in the fly ash samples were examined by using float-sink, screening and air classification tests. The results pointed out that cenosphere contents decreased with decreasing size and increasing density for both samples. According to the float-sink tests, &Ccedil / atalagzi fly ash has much more floating products and more cenospheres than Sug&ouml / z&uuml / fly ash for the same density interval. Based on the air classification results, cenospheres were concentrated in the underflow products, and cenosphere contents increased with increasing air pressure and decreasing motor speed for both samples. The most efficient cenosphere separation technique among the examined methods was screening. Cenosphere contents of CFA and SFA increased to 21.65% and 11.83%, respectively by only using simple screening through 38 &mu / m.

One way to reduce the amount of CO2 in the atmosphere for the mitigation of climate change is to capture the CO2 and inject it into geological formations. The most important public concern about carbon capture and storage (CCS) is whether stored CO2 will leak into groundwater sources and finally into the atmosphere. To prevent the leakage, the possible leakage paths and the mechanisms triggering the paths must be examined and identified. It is known that the leakage paths can be due to CO2 - rock interaction and CO2 &ndash / well interaction. The objective of this research is to identify the geochemical reactions of the dissolved CO2 in the synthetic formation water with the rock minerals of the Sayindere cap rock by laboratory experiments. It is also aimed to model and simulate the experiments using ToughReact software. Sayindere formation is the cap rock of the Caylarbasi, a southeastern petroleum field in Turkey. The mineralogical investigation and fluid chemistry analysis of the experiments show that calcite was dissolved from the cap rock core as a result of CO2- water- rock interaction. Using the reactive transport code TOUGHREACT, the modeling of the dynamic experiment is performed. Calcite, the main primary mineral in the Sayindere is dissolved first and then re-precipitated during the simulation process. The decreases of 0.01 % in the porosity and 0.03% in permeability of the packed core of the Sayindere cap rock are observed in the simulation. The simulation was continued for 25 years without CO2 injection. However, the results of this simulation show that the porosity and permeability are increased by 0.001 % and 0.004 %, respectively due to the CO2-water-rock mineral interaction. This shows that the Sayindere cap rock integrity must be monitored in the field if application is planned.

ABSTRACT VANADIUM AND MOLYBDENUM INCORPORATED MCM-41 CATALYSTS FOR SELECTIVE OXIDATION OF ETHANOL G&uuml / &ccedil / bilmez, YeSim Ph.D., Department of Chemical Engineering Supervisor : Prof. Dr. Timur Dogu Co-Supervisor: Prof. Dr. Suna Balci June 2005, 144 pages In this study, V-MCM-41, MCM-41 and Mo-MCM-41 catalysts were synthesized by the one-pot alkaline and acidic synthesis methods. The as-synthesized catalysts were found to have high BET surface areas (430-1450 m2/g), homogeneous pore size distributions (2-4 nm), good crystalline patterns and high metal loading levels (Metal/Si atomic ratio in the solid = 0.01-0.16) as determined by the characterization studies. MCM-41 and Mo-MCM-41 catalysts were highly active in the selective oxidation of ethanol with conversion levels of 56% and 71%, respectively, at 400oC for an O2/EtOH feed ratio of 0.5. Both catalysts had very high selectivities to acetaldehyde at temperatures below 300oC. Conversions exceeded 95% with the V-MCM-41 catalyst having a V/Si molar ratio (in the solid) of 0.04 in the temperature range of 300oC-375oC for the O2/EtOH feed ratios of 0.5-2.0. Acetaldehyde selectivities changed between 0.82-1.00 at the temperature range of 150oC-250oC. Ethylene, which is listed as a minor side product of the selective oxidation of ethanol in literature, was produced with a maximum yield of 0.66 at 400oC at the O2/EtOH feed ratio of 0.5. This yield is higher than the yields obtained in the industrial ethylene production methods such as thermal cracking and oxidative dehydrogenation of ethane. Besides, the feedstock used in this work is a non-petroleum chemical, namely ethanol, which can be produced from sugar and crop wastes by fermentation. Thus, the findings of this study are also proposed as an alternative ethylene production method from a non-petroleum reactant at lower temperatures with higher yields. &Ouml / Z ETANOL&Uuml / N SE&Ccedil / iCi OKSiDASYONUNDA KULLANILMAK &Uuml / ZERE VANADYUM VE MOLiBDEN i&Ccedil / EREN MCM-41 KATALiZ&Ouml / RLERiNiN &Uuml / RETiMi G&uuml / &ccedil / bilmez, YeSim Doktora, Kimya M&uuml / hendisligi B&ouml / l&uuml / m&uuml / Tez Y&ouml / neticisi : Prof. Dr. Timur Dogu Ortak Tez Y&ouml / neticisi: Prof. Dr. Suna Balci Haziran 2005, 144 sayfa Bu &ccedil / aliSma kapsaminda, dogrudan sentez metoduyla, alkali ve asit ortamlarinda, V-MCM-41, MCM-41 ve Mo-MCM-41 kataliz&ouml / rleri sentezlenmiStir. Bu Sekilde sentezlenen kataliz&ouml / rlerin y&uuml / ksek BET y&uuml / zey alanlarina (430-1450 m2/g), homojen g&ouml / zenek boyutu dagilimlarina (2-4 nm), iyi kristal yapilarina ve y&uuml / ksek metal y&uuml / kleme oranlarina (Metal/Si katidaki molar orani =0.01-0.16) sahip olduklari karakterizasyon &ccedil / aliSmalari sonucunda g&ouml / r&uuml / lm&uuml / St&uuml / r. MCM-41 ve Mo-MCM-41 kataliz&ouml / rleri etanol&uuml / n se&ccedil / ici oksidasyonunda, 400oC&amp / #8217 / de ve reakt&ouml / r giriSinde 0.5&amp / #8217 / lik O2/EtOH oraninda, sirasiyla, 56% ve 71% d&ouml / n&uuml / S&uuml / m seviyeleriyle, y&uuml / ksek aktivite g&ouml / stermiSlerdir. Her iki kataliz&ouml / r de 300oC&amp / #8217 / nin altinda &ccedil / ok y&uuml / ksek asetaldehit se&ccedil / iciligi g&ouml / stermiStir. D&ouml / n&uuml / S&uuml / m degerleri, V/Si katidaki molar orani 0.04 olan V-MCM-41 kataliz&ouml / r&uuml / i&ccedil / in / 300oC-375oC araliginda ve 0.5-0.2 O2/EtOH reakt&ouml / r giriSi oranlarinda, 95%&amp / #8217 / i ge&ccedil / miStir. Asetaldehit se&ccedil / icilikleri, 150oC-250oC araliginda, 0.82-1.00 arasinda degiSmiStir. Literat&uuml / rde, etil alkol&uuml / n se&ccedil / ici oksidasyonunda &ouml / nemsiz bir yan &uuml / r&uuml / n olarak s&ouml / z&uuml / ge&ccedil / en etilen, 400oC&amp / #8217 / de ve 0.5&amp / #8217 / lik O2/EtOH reakt&ouml / r giriS oraninda 0.66 maksimum verimle &uuml / retilmiStir. Bu verim degeri isil par&ccedil / alanma ve etanin kismi oksidasyonu gibi end&uuml / striyel etilen &uuml / retim yollariyla elde edilen verimlerden daha y&uuml / ksektir. Ayrica, bu &ccedil / aliSmada kullanilan etanol petrol-bazli olmayan bir hammaddedir ve Seker pancari atiklarindan fermentasyonla &uuml / retilebilmektedir. Bu sebeple, bu &ccedil / aliSmadaki bulgular, petrol-bazli olmayan bir hammaddeden, daha d&uuml / S&uuml / k sicaklikta, daha y&uuml / ksek verimle etilen elde etmek i&ccedil / in alternatif bir &uuml / retim metodu olarak da &ouml / nerilmiStir. Anahtar Kelimeler: Etilen, Etil alkol, Se&ccedil / ici Oksidasyon, MCM-41, V-MCM-41, Mo-MCM-41, Oksidatif Dihidrojenasyon, Kismi Oksidasyon