In this study nanocrystalline TiO2 was synthesized by a sol-gel process. The effect of praseodymium (Pr) doping and calcination conditions on the textural properties of nano structured particles and photocatalytic activity were examined. Samples were synthesized by hydrolyzation of titanium tetra iso-propoxide (TTIP) and calcination at different temperatures. Characterizations of the samples were carried out using XRD, BET, XPS, TEM, and EDAX analyses. It was observed that anatase to rutile transformation is favored by higher calcination temperatures. The XRD analysis indicated that the anatase structure is stabilized by Pr doping and rutile phase formation at higher calcination temperatures is inhibited by the addition of Pr. It was also observed that Pr doping enhances the surface area and inhibit crystal growth. Phase stabilization effect of Pr doping was also confirmed by XPS results. EDAX analysis revealed that Pr is dispersed atomically in the crystal structure. The Photoluminescence analysis by 325 nm excitation indicated the emissions at 608 and 621 nm which can be attributed by photon up-conversion. The photocatalytic activities of the samples were measured by methylene blue degradation and phenol mineralization reactions. The photocatalytic activities of the Pr doped samples were also found higher than undoped TiO2 samples.

Boron nitride nanotubes (BNNTs), which are structurally similar to carbon nanotubes (CNTs), were synthesized in 1995 for the first time. They are made up by folding atom sheets which consist of boron and nitrogen atoms into cylindrical form. After their discovery, BNNTs have been attracting great attention due to their extraordinary mechanical, thermal, electrical, and optical properties. In this study, BNNTs were synthesized from the reaction of ammonia gas with the boron and iron powder mixture in a tubular reactor which was connected to a mass spectrometer for on-line chemical analysis of the reactor effluent stream. The synthesized materials were purified with acid treatment. Chemical analysis results showed that nitrogen and hydrogen gases were present in addition to ammonia gas. XRD results revealed that the solid phases in the synthesized material were hexagonal boron nitride, rhombohedral boron nitride, iron, and boron-iron compounds (FeB49 and Fe3B). Reactions taking place in BNNT synthesis were proposed as the decomposition of ammonia gas which was the only gas phase reaction, the formation of boron-iron compounds from the reaction of boron with iron, and boron nitride formation from the reaction of nitrogen with boron-iron compounds. Agglomerated, hollow, multi-walled nanotubes were synthesized with an outer diameter range of 10-550 nm. Both open and close-ended nanotubes were observed. The interlayer distance between BN sheets was measured about 0.33 nm and this distance indicated the d002 plane of hexagonal boron nitride. BNNTs exhibited Type II isotherms with a Type B hysteresis. A decrease in the surface area of the synthesized BNNTs was observed with an increase in temperature. The highest surface area was 147.6 m2/g. Average pore diameter of BNNTs synthesized at different temperatures was around 38 &Aring / . Deposition rate of boron nitride increased with an increase in temperature. After a certain temperature, deposition rate decreased with temperature due to the sintering effect. The highest deposition rate was observed when BNNTs were synthesized with the B/Fe weight ratio of 15/1 at 1300 &deg / C.

Ru/C type ammonia synthesis catalysts are known to be poisoned by hydrogen. In order to elucidate a mechanism for hydrogen poisoning, H2 adsorption and spillover on Ru based ammonia synthesis catalysts were investigated. Supported Ru catalysts and Na promoted Ru catalyst were prepared by incipient wetness impregnation of Ru(NO)(NO3)3 on SiO2, SBA-15, CNT and Vulcan supports. Dispersion value of the catalysts was determined via H2 chemisorption and Transmission Electron Microscopy (TEM) characterization techniques. Over SBA-15 support, the dispersion of the catalyst determined by two different characterization techniques were in agreement. On the other hand, over CNT and SiO2 supports dispersion measured by TEM characterization method was higher than H2 chemisorption method. H2 chemisorption measurements performed over extended periods of time were used to determine the spilled over hydrogen amounts over Ru/Vulcan and Na-Ru/Vulcan catalysts at 375 torr and 10 torr H2 pressure at room temperature. By using H2 uptake data measured for extended periods of 6 &ndash / 24 hours, diffusion coefficient of hydrogen species over Vulcan support was calculated assuming a point source diffusion mechanism. Coefficient of diffusion for Ru/Vulcan and Na-Ru/Vulcan was found as 1.39 x 10-14 cm2/sec and 1.23 x 10-14 cm2/sec, respectively at 375 torr. Similarly, at 10 torr, diffusion coefficients of Ru/Vulcan and Na-Ru/Vulcan catalysts were determined as 1.51 x 10-15 cm2/sec and 1.81 x 10-15 cm2/sec, respectively.

In this study, it was aimed to investigate the effects of different co-carbon sources on therapeutically important glycoprotein, recombinant human erythropoietin (rHuEPO) production by Pichia pastoris by designing feeding strategies which were applied in the production phase of the bioprocess. During the experiments, the cell growth, sorbitol, mannitol, and methanol consumptions, recombinant human EPO production, alcohol oxidase activity, total protease concentrations and the by-products organic acid concentrations were analyzed. In this context, firstly, laboratory scale air filtered shake bioreactor experiments were performed by P. pastoris Mut+ strain to investigate the effects of mannitol and sorbitol. 50 gL-1 initial concentration of co-substrates was found more affordable and appropriate for cell concentration and recombinant protein production. Thereafter, six pilot scale bioreactor operations were designed and performed. In the first designed strategy (named as SSM strategy), batch-wise 50 g L-1 sorbitol was fed at t=0 h of the production phase and then sorbitol concentration was kept constant at 50 g L-1 by fed-batch feeding with a pre-determined specific growth rate of &mu / Srb0=0.025 h-1 within t=0-15 h of the production phase together with fed-batch methanol feeding with a pre-determined specific growth rate of &mu / M0=0.03 h-1. In the following bioreactor experiments co-substrate mannitol was fed to the system with different feeding strategies together with fed-batch methanol feeding with a pre-determined specific growth rate of &mu / M0=0.03 h-1. In the second strategy (MM), only 40 g L-1 mannitol was added to the system at t=0 h of the production phase. In the third strategy (MMM), after adding 50 g L-1 mannitol at t=0 h, mannitol concentration was kept constant at 50 g L-1 by fed-batch feeding with a pre-determined specific growth rate of &mu / Man0=0.11 h-1 within t=0-9 h of the production phase when the same cell concentration was attained in SSM strategy. In the fourth one (MLM), limiting amount of mannitol, 3 g L-1, was added at t=0 h and then mannitol concentration was kept constant at 3 g L-1 by fed-batch feeding with a pre-determined specific growth rate of &mu / Man0=0.005 h-1 within t=0-10 h of the production phase. After these strategies, several pulses, batch-wise, mannitol feeding strategies were performed. In the fifth strategy (MPM), besides 50 g L-1 initial mannitol feeding at t=0 h, adding second batch-wise mannitol at t=6 h, and third one at t=12 h were applied. In the last strategy (MPMG), four 50 g L-1 pulse feeding of mannitol were performed at t=0 h, 7 h, 14 h, and 24 h, containing glycerol, with an initial concentration in the fermentation medium being 8 g L-1. The highest extracellular rHuEPO production was achieved in the fifth strategy MPM as CrHuEPO=645 mg L-1 at t=9 h while the highest cell concentration was achieved in the first strategy SSM as Cx=109 gL-1 at t=48 h. The overall cell and product yields on total substrate were calculated as YX/St=0.22 g g-1 and YP/St=2.23 mg g-1 in the highest rHuEPO production case.

Recent developments have confirmed that in the future hydrogen demand in industrial applications will arise because of the growing requirements for H2 in chemical manufacturing, petroleum refining, and the newly emerging clean energy concepts. Hydrogen is mainly produced from the steam reforming of natural gas and water gas shift reactions. The major products of these processes are hydrogen and carbon dioxide. The selective removal of CO2 from the product gas is important because it poisons catalysts in the reactor and it is highly corrosive. Membrane separation processes for hydrogen purification may be employed as alternative for conventional methods such as adsorption, cryogenic distillation. Mixed matrix membranes (MMMs) are composed of an insoluble phase dispersed homogeneously in a continuous polymer matrix. They have potential in gas separation applications by combining the advantageous properties of both phases. The objective of this study is to produce neat polybenzimidazole (PBI) membranes and PBI based mixed matrix membranes for separation of H2/CO2. Furthermore, to test the gas permeation performance of the prepared membranes at permeation temperatures of 35oC to 90oC. Commercial PBI supplied from both Celanese and FumaTech were used as polymer matrix. PBI was selected based on its thermal, chemical stabilities and mechanical properties and its performance as a fuel-cell membrane produced by PBI. Micro-sized Zeolite 3A and nano-sized SAPO-34 are zeolites with 0.30 nm and 0.38 nm pore size respectively have attracted considerable interest and employed as fillers in this study. Commercial Zeolite 3A and synthesized SAPO-34 by our group was used throughout the study. Membranes were prepared using N,N-dimethylacetamide as the solvent. Prepared membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The effect of annealing procedure and operating temperature on gas separation performance of resultant neat PBI, PBI/Zeolite 3A and PBI/SAPO-34 membranes were investigated by gas permeation tests. Hydrogen and carbon dioxide gases were used for single gas permeation measurements. Two different annealing strategies were utilized namely in-line annealing and in-oven annealing. In-oven annealing was performed in an oven in nitrogen atmosphere at 120oC, 0.7 atm while in-line annealing was performed in the gas permeation set-up by feeding helium as permeating gas at 90oC and 3 bar. Neat PBI and PBI/ Zeolite 3A membranes were in-oven annealed. The in-oven annealed membranes showed better selectivities with lower permeabilities, but the performance results of these membranes had low repeatability. On the other hand, in-line annealed membranes showed much higher permeabilities and lower selectivities with stable performance. By changing the annealing method hydrogen permeability increased from 5.16 Barrer to almost 7.77 barrer for neat membranes and for PBI/Zeolite 3A mixed matrix membranes increased from 5.55 to to 7.69 Barrer at 35oC. The selectivities were decreased from 6.21 to 2.31 for neat membranes and for PBI/Zeolite 3A from 5.55 to 2.63. Effect of increasing operating temperature was investigated by using in-line annealed membranes. Increasing temperature from 35oC to 90o improved the performance of the both types of membranes and repeatable results were obtained. Besides neat PBI and PBI/Zeolite 3A, PBI/SAPO-34 membranes were prepared only via in-line annealing. The addition of nano-sized filer to the membranes provided homogeneous distribution in polymer matrix for PBI/SAPO-34 membranes. For this type of membrane hydrogen permeability increased from 8.01 to 26.73 Barrer and with no change in H2/CO2 selectivities via rising temperature. Consequently, it is better to study hydrogen and carbon dioxide separation at high temperature. For all types of membranes hydrogen showed higher activation energies. In between all membranes magnitude of activation energies were the highest for PBI/SAPO-34 membrane which is an indication of good interaction between polymer and zeolite interface. In-line annealed membranes gave the best gas permeation results by providing repeatability of measurements. Among all studied membranes in-line annealed PBI/SAPO-34 membrane exhibited the best gas permeation results.

The scope of this thesis was to study thermodynamics of lead oxide and cobalt oxide as the chemical looping agent for oxygen. Furthermore, the theoretical results were verified experimentally. Ellingham diagrams were constructed for the selected oxides. Then, detailed thermodynamic analysis was conducted for stability analysis at different temperatures and pressures. Equilibrium product compositions for various reactions involving these oxides were calculated via Gibbs free energy minimization analysis. Finally, it was shown that cobalt, lead and their oxide forms can be used for syngas production. In the experimental part PbOx, CoOx, Pt-doped CoOx and Pt-doped cobalt alumina, and mixed lead cobalt oxides were synthesized. In addition, technical grade cobalt oxide and lead rods were also used. XRD analysis indicated that Co3O4, Pb2O3 and &alpha / -PbO were the main crystal structures. Oxygen evolution from mixed oxides was monitored by TPD in a home built system. Re-oxidation of the reduced metals was successfully conducted using CO2 and H2O as oxidizing agents. Oxygen TPD studies indicated that oxygen evolution rates and amounts were higher and started at lower temperatures when two oxides were together. These observations were consistent with the predictions obtained from thermodynamics. In a series packed bed reactor, evolved oxygen from the mixed oxides were used to react with coal packed upstream of the oxides. It was found that coal oxidation can be achieved around 400oC and 600oC by using Pb/Co=3 (wt./wt.) looping media with almost no CO2 formation. It was also found that desired product selectivity (CO) can be increased by controlling reactive agent (O2) concentration in reaction environment.

Tartaric acid is a dicarboxylic acid naturally present in grapes, and has many application areas with its salts. It can be produced synthetically, manufactured as a by-product in wine industry, or can be recovered by electrodialysis and solvent extraction methods. Since, ion exchange is one of the oldest processing techniques for the recovery and purification of valuable materials, it can be applied to obtain this valuable organic acid. In this study it is aimed to investigate the effects of resin basicity, initial concentration, and initial pH of the solution on ion exchange equilibrium. The model tartaric acid solutions were prepared for the equilibrium analysis with two different anion exchange resins in a batch type system. A shaker bath at 28 oC with 300-rpm agitation rate was used. The weakly basic resin Lewatit MP62, and strongly basic resin Lewatit M511, which are in polystyrene structure, was obtained from the producer Bayer AG. In the analysis, Shimadzu PDA Detector at 210 nm with Waters Atlantis dC18 column was used. 20 mM NaH2PO4 at pH = 2.7 was introduced to the HPLC as the mobile phase at 0.5 ml/min flow rate. In the investigation of the resin basicity, MP62 presented better performance than M511. The equilibrium experiments were performed at three different initial acid concentrations (0.01, 0.02, and 0.10 M) for both resin, and in the pH ranges pH &lt / pKa1, pKa1 &lt / pH &lt / pKa2, and pKa2 &lt / pH for weakly basic resin, and in the pH ranges pH &lt / pKa1, pKa1 &lt / pH &lt / pKa2 for strongly basic resin at each concentration. Results show that the pH of the solution is a more important parameter than the initial concentration that affects the ion exchange equilibrium. Also, Langmuir and Freundlich isotherms were plotted, and it was shown that they were in good agreement with the experimental data especially for the systems that are at low total ion concentrations.

In this study, a methodology for separation of chiral molecules, by using enhanced ultrafiltration system was developed. Benzoin was the model chiral molecule studied. In the scope of developing this methodology, some parameters were investigated in the preliminary ultrafiltration experiments in order to set the operation conditions for enhanced ultrafiltration experiments. Due to the slight solubility of benzoin in pure water, 15% (v/v) Polyethylene glycol (PEG 400) and 30 % (v/v) Dimethyl sulfoxide (DMSO) were selected as cosolvents. Because of the high retention capacity of RC-10000 Da membranes for benzoin, a membrane saturation strategy was developed. In polymer enhanced ultrafiltration (PEUF) experiments bovine serum albumin (BSA) was used as ligand. Effects of ligand concentration and pH on total benzoin retention and on enantiomeric excess (ee %) were investigated. Benzoin concentration was almost kept constant at ~10 ppm and ~50 ppm for 15% (v/v) PEG 400 and 30 % (v/v) DMSO cosolvents, respectively. It was observed that the increase either in pH or in BSA concentration yielded an increase in total benzoin retention. In 15% (v/v) PEG 400-water, with BSA concentration of 10000 ppm, at pH 10, total benzoin retention reached to 48.7%. For this cosolvent, at different pH values and at different BSA concentrations, all ee % values were about or less than 10%. When 50000 ppm BSA was dissolved in 30 % (v/v) DMSO-water, total benzoin retention increased to 41.3% at pH 10 and ee % reached 16.7 % at pH 11. In enzyme enhanced ultrafiltration (EEUF) experiments, specific to benzoin, apo form of Benzaldehyde Lyase (BAL, E.C. 4.1.2.38) was used as ligand. These experiments were performed with constant ~ 10 ppm benzoin concentration in only 15% (v/v) PEG 400 &ndash / water solvent. Effect of BAL concentration on total benzoin retention and ee% was investigated. It was found that / for all the studied BAL concentrations in the range of 650- 1936 ppm total benzoin retention and ee % were kept almost constant at ~75% and ~60%, respectively.

Fly ashes generated from fluidized bed combustion of low calorific value, high ash content Turkish lignites are characterized by high content of acidic oxides, such as SiO2, Al2O3 and Fe2O3, varying in the range 50-70%. However, there exists no study for the investigation of the possibility of using these ashes as concrete admixture. Therefore, in this study, characterization of fly ashes from fluidized bed combustion of a Turkish lignite and evaluation of these fly ashes as a substitute for Portland cement in production of pastes and mortars were carried out. The samples were subjected to chemical, physical, mineralogical and morphological analyses. Results of chemical and physical analyses of three fly ash samples show that they satisfy the requirements of EN 197-1, EN 450 and ASTM C 618, except for CaO and SO3, owing to high content of acidic oxides of these ashes contrary to majority of FBC fly ashes reported in the literature. In addition to characterization studies, water requirement, compressive strength, setting time and soundness tests were also performed for 10%, 20% and 30% fly ash-cement blends and the reference cement. Results of these tests reveal that the blends meet compressive strength, setting time and soundness requirements of ASTM C 595 without any pre-hydration treatment, and that fly ashes from fluidized bed combustion of Turkish lignites have significant potential for utilization as an admixture in manufacture of blended cements.

The investigation of CO oxidation with supported noble metal catalysts to develop a fundamental understanding of the nature of the active sites, adsorbate-surface interactions, surface reaction pathways and the role of promoters is of prime importance for development of highly active and selective catalyst formulations for low temperature oxidation of carbon monoxide. Low temperature CO oxidation catalysts find applications in monitoring and elimination of CO in chemical process exhaust gases, in on-board control and diagnostics devices, automobile exhaust gas treatment systems for the development of zero-emission vehicles and, in closed-cycle CO2 lasers for remote sensing. Moreover, the investigation of the interaction of CO with noble metals and noble metals catalyzed oxidation of CO have important outcomes for upstream fuel processing systems and for the development of more CO tolerant anode materials for hydrogen fuel cell. Palladized tin dioxide is a well-known and highly active catalyst for CO oxidation which possesses the potential to satisfy the need for CO oxidation catalysts in the abovementioned areas however, research on this material is concentrated mostly around empirical studies which focus solely on CO sensing applications. This current research is undertaken to investigate both the mechanism of CO oxidation with Pd/SnO2 at the molecular scale and the possibility of promoting the CO activity of this catalyst by the application alkali-metal modifiers. Alkali-metal modified PdO/SnO2 catalysts were characterized by XPS, XRD and SEM and, tested with regard to their oxidation/reduction and CO oxidation behavior by in-situ dynamic methods such as, temperature-programmed reaction/reduction/desorption and impulse techniques. Modification of PdO/SnO2 by alkali-metals, namely Li, Na and K, resulted in catalyst formulations with different surface characteristics and reduction/oxidation behaviors that lead to superior activity in low temperature CO oxidation and selectivity towards CO in the presence of hydrogen. Studies have shown that these catalysts are potential candidates for CO oxidation catalysts in a wide range of areas.