Master Degree / Yüksek Lisans Tezleri
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Master Thesis Preparation of Natural Zeolite Supported Tio2 Composites for Removal of Terephthalic Acid(Izmir Institute of Technology, 2014) Deliismail, Özgün; Çakicioğlu Özkan, Seher Fehime; Helvacı, Şerife ŞerefThis study focuses on the preparation of natural zeolite supported TiO2 composites for the removal of model pollutant, terepththalic acid (TPA) via sorption. Natural zeolite was purified and used to prepare natural zeolite supported TiO2 adsorbents. Prior to sorption, the adsorbents were characterized by Scanning Electron Microscopy, Volumetric Adsorption Instrument, X-ray Diffractometer, Fourier Transformer Infrared, Induced Coupled Plasma Atomic Emmision Spectroscopy, and Thermal Gravimetric Analyzer. It was deduced that natural zeolite was clinoptilolite rich low (Ca) silicate. The sorption studies of TPA on adsorbents were applied in dark conditions at room temperature by altering adsorbent amount (0.2-1.5 g/l) and initial TPA concentration (20-60 ppm). It was observed that the amount of adsorbed TPA per unit mass of adsorbent decreased with increasing adsorbent amount, and sorption percent was unchanged (about 72%). This can be explained by the affinity of adsorbents to water molecules more than TPA molecules. Much more number of TPA molecules was allocated on the clinoptilolite than TiO2 composites. Sorption mechanism was identified by fitting the kinetic data to diffusion (Weber-Morris model, intraparticle/external diffusion) and reaction models (First order and pseudo second order model). First order reaction model was well correlated to experimental data for sorption process. Comparing pore size of the adsorbents to molecular size of TPA indicates that main contribution to intraparticle diffusion was the intercrystalline diffusion. Intraparticle diffusion was not the sole rate-limiting step due to the existence of external resistance. Biot and Weber-Morris calculations corroborated these results. In the future, photocatalytic performance of these adsorbents will also be tested.Master Thesis Ion exchange in natural zeolite packed column(Izmir Institute of Technology, 2004) Can, Özge; Ülkü, SemraTurkish natural clinoptilolites were examined to evaluate their ion exchange performance for the removal of copper, nickel and cobalt ions by performing both batch and packed column experiments.Initial metal solutions were prepared using metal nitrate solutions at various concentrations.All of the experiments were carried out at 29oC.Before performing the ion exchange experiments zeolites were characterized and their clinoptilolite contents were determined quantitatively as 80 and 64 % for zeolites named as CP1 and CP2, respectively.The copper exchange capacities of CP1 and CP2 were determined from equilibrium studies as 10.01 mg (0.32 meq) Cu2+ / g CP1 and 8.33 mg (0.262 meq) Cu2+ / g CP2. Ion exchange capacity of CP2 zeolite was determined as 6.64 mg (0.226 meq) Ni2+ / g and 4.55 mg (0.154 meq) Co2+ / g.The equilibrium behaviour of the system was best described by Langmuir model.Experiments were designed to investigate the optimum parameters and significance of the interactions between these parameters.In column studies, the parameters such as packing height, inlet metal concentration and flow rate were investigated.The concentration of the metals in the sample solutions which were taken from the exit of the ion exchange column at specific time intervals were analyzed by using Optical Emission Spectrometry (ICP-OES).Afterwards, by making use of the data obtained from ICP-OES, breakthrough curves were constructed.By the help of these curves, breakthrough capacity and ion exchange capacity of natural zeolites were calculated.The ion exchange capacity of CP2 zeolite was calculated as 8.04 mg Cu2+/g CP2, which was consistent with the capacity calculated from batch experiments, 8.33 mg Cu2+/g CP2.Also, breakthrough points were determined. Furthermore, solid phase was also analysed for determining its crystal structure and chemical composition using Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray (EDX) devices (Philips XL 30S FEG).In addition to these, natural zeolite particles which have been ion exchanged throughout this process were regenerated using 0.2M and 1.7M of NaCl solutions.According to regeneration studies, it was determined that 94 and 95% of copper were recovered within the first 100 minutes for both experiments.After the experiments were performed, model equations were applied to the system in order to be able to investigate the dynamic behavior of the system.As a result of this simulation, breakthrough was well predicted.Master Thesis Preparation and Characterization of Polymer-Zeolite Composite Membranes(01. Izmir Institute of Technology, 1999) Ebil, Özgenç; Çiftçioğlu, MuhsinThis thesis is on the investigation of polymer-zeolite composite membranes for gas separation and the effects of a number of parameters such as solvent and zeolite type, zeolite content, polymer/solvent ratio and preparation temperature on the microstructure of the final membrane. Although there is an increasing interest in polymeric composite membranes, most of the previous work concentrated on the synthesis and performance measurements of new membrane materials rather than the effects of different methods and parameters on processmg.In this study polymer-zeolite composite membranes were prepared by a phase inversion technique. Polysulfone, natural zeolite and synthetic zeolite 13X were used as polymer and second phases respectively. Dichloromethane and dimethylformamide were used as solvents. Four experimental sets of membranes containing the same polymer but different solvents and zeolites with increasing zeolite loadings were prepared and characterized by thermo gravimetric analysis, infrared spectroscopy, optical microscopy and scanning electron microscopy.It has been found that the types of the solvent and zeolite directly affect the final microstructure of the membranes. Solvent removal rate and distribution of zeolite particles are important and have strong effects on the mechanical performance of the membranes.Membranes prepared by using synthetic zeolite 13X and dichloromethane were determined to be the best zeolite distributions in the microstructure by optical microscopy and thermogravimetric analysis. Uniform and mechanically strong membranes with 20-60 % synthetic zeolite contents were prepared. Mechanically weak and relatively nonuniform membranes were prepared by using natural zeolite clinoptilolite. The incorporation of an ultrasonic treatment of the zeolite dispersion most likely contributed in the successful deagglomeration of the second phase in the polymer matrix.Master Thesis A Chromatographicstudy of Carbon Monoxide Adsorption in Clinoptilolite(Izmir Institute of Technology, 2001) Narin, Güler; Ülkü, SemraAdsorption equilibrium and kinetic parameters for CO/clinoptilolite adsorbate/adsorbent pair were determined by perturbation gas chromatography. Chromatographic experiments were performed at temperatures in the 60-120°C range and at carrier gas flow rates in the range of 10.31-24.36 em/sec. The chromatographic response peaks were obtained by concentration pulse method. A packed column of 10 em length and 0.46 em inlet diameter which was packed with clinoptilolite particles with narrow size distribution (500-850 §) around mean diameter of301.9 § was used. The clinopti10lite particles were excavated from Gordes, Western Anatolia. The moments of the response peaks were calculated by integration of experimental chromatographic data and matched to the .model parameters in order to determine the equilibrium constants and diffusion coefficients. The dynamic model (Haynes and Sarma, 1973) was applied to describe the adsorption and diffusion processes in the packed column. This model includes axial dispersion, external mass transfer resistance, micropore and mesopore diffusion resistances. The equilibrium constants (Henry's law constants, K) were calculated in the range of 40 - 952 and were found to be in good agreement with the results in the literature. These constants were found to decrease with increasing temperature. The heats of adsorption were obtained in the range of 54.15 - 57.14 kl/mol from the slope of van't Hoff plots and compared with those in the literature. The heats of adsorption were found to be lower than those reported in the literature obtained for the same adsorbate/adsorbent pair. The higher heats of adsorption were explained by the smaller pore size, higher cation content of the clinoptilolite and more accessibility of the cations in the clinoptilolite framework by CO molecules. Heats of adsorption remained almost constant over the carrier gas velocity range studied. The contributions of axial dispersion and other mass transfer resistances Indiffusion of CO in clinoptilolite were also determined. The total dispersion exhibited slight change (average 0.035 see) with temperature implying that the micropore diffusional resistance was not dominant for diffusion of CO in clinoptilolite under the experimental conditions studied. The axial dispersion coefficient was determined in the range of 1.149.88 cm2/sec and the total mass transfer resistances were found between 0,02-0.06 sec. The results showed that the mesopore diffusion resistance was the controlling mechanism in CO diffusion in clinoptilolite. Mesopore diffusion coefficient was estimated as 2.98xlO-3 cm2/sec. This value was in good agreement with the theoretically determined value.Master Thesis Removal of Heavy Metals From Wastewaters by Use of Natural Zeolites(Izmir Institute of Technology, 2001) Türkmen, Müşerref; Ülkü, SemraIn the present study, clinoptilolite rich local natural zeolite was proposed as an ion-exchanger for the removal of heavy metals (Pb2+, Cu2+, Zn2+) from wastewaters.Natural zeolite samples were exposed to a simple pretreatment process which included washing and drying to remove impurities and dust.Thermal and adsorption related properties of washed and original zeolite samples were determined by TGA and N2 adsorption analyses. In TGA analyses, average water content for washed and original samples were found as 9.44 and 10.13 % respectively. In N2 adsorption studies, both washed and original samples showed the characteristic Type IIb isotherm. BET surface areas of the samples were calculated as 39.73 and 47.72 m2/g for washed and original samples respectively.Pretreatment process was found to improve the adsorption capacity of clinoptilolite due to the removal of impurities and dust.In ion-exchange studies, efficiency of natural zeolite in removal of heavy metals from the solutions was investigated based on some physical and chemical variables. For this purpose, particle size and the amount of zeolite in the solution, contact time of the metal containing solution with zeolite were selected as physical variables and pH, metal concentration of the solution, and the presence of other ions were selected as chemical variables. The chemical analyses of all exchange solutions were performed by using ICP-AES. Removal % of the metal ions from the solutions were obtained. Based on the experimental results, zeolite exhibited a significant affinity to Pb2+, followed by Cu2+ and Zn2+ even in the presence of competing cations.To test the applicability of natural zeolite for the treatment of Acid Mine Drainage (AMD), zeolite samples were allowed to contact with simulated AMD solutions.Consequently, natural zeolite was found to be an efficient ion exchanger for removing lead, copper and zinc ions from aqueous solutions.Master Thesis Synergistic Effect of Zinc Stearate and Natural Zeolite on Pvc Thermal Stability(Izmir Institute of Technology, 2004) Atakul, Sevdiye; Balköse, DevrimAt high temperatures (about 100 °C), PVC decomposes by the removal of hydrogen chloride (HCl) gas and the decomposition is accompanied by polymer discoloration going from yellow to orange, brown and black. In order to prevent decomposition of PVC, thermal stabilizers are added to PVC. The synergistic effect of zinc stearate (ZnSt2) and/or natural zeolite (clinoptilolite) on PVC thermal stability was investigated in this project. For this purpose PVC plastisol was prepared by mixing poly(vinyl chloride) (PVC) and dioctyphthalate (DOP) and stabilized with different amounts of metal soaps and zeolite.The materials and the prepared PVC plastisols were characterized by spectroscopic and thermal analysis techniques. The gelation of the plastisols was observed by optical microscopy and the photographs were taken by a digital camera. The complete gelation was observed at 185 °C. The morphology of PVC plastigel films were studied by scanning electron microscope (SEM). SEM with energy dispersive X-ray (EDX) analysis was used to obtain elemental compositions in polymer and particle phases. The thermal stability of PVC plastigels in terms of color were obtained by heating them in a static vaccum oven. When zeolite was used as a primary stabilizer it prevented the early blackening of the film. Kinetic study of dehydrochlorination was determined by 763 PVC Thermomat equipment for unstabilized and stabilized PVC plastigels. When PVC plastigels were heated in PVC Thermomat in the presence of nitrogen gas, the conductivity of water which nitrogen gas was passed due to the evolved HCl, changed with respect to time. The period when conductivity starts to increase is called as induction time, and the period when the conductivity value reaches to 50 uS/cm is called as stability time. The induction and stability time values of unstabilized and stabilized PVC plastigel films were obtained at 140 and 160 °C. The stabilizing effect of zeolite on the increase in the induction period of the sample was considered the result from the absorption of HCl which was thought to reduce the autocatalytic effect of HCl evolved at the initial stages of dehydrochlorination. Since the induction time of the sample having 0.53% ZnSt2 and 0.53% zeolite was higher than the PVC plastigels having only ZnSt2 or zeolite the synergistic effect on thermal stability was observed at low levels of them.Master Thesis Investigation of Fuel Oxygenate Adsorption on Clinoptilolite Rich Natural Zeolite(Izmir Institute of Technology, 2006) Yetgin, Senem; İnal, FikretThe wide use of fuel oxygenates in gasoline as anti-knocking and emission reduction agent have recently led to serious environmental concerns due to their detection in groundwater and surface water. Among the various gasoline additives, methyl tertiary butyl ether (MTBE) and ethyl tertiary butyl ether (ETBE) are the most frequently used fuel oxygenates worldwide. Due to the physical and chemical properties of fuel oxygenates, the conventional treatment technologies are generally ineffective for their removal from contaminated water. Adsorption is a common process frequently used to remove fuel oxygenates from water. The use of natural zeolites as adsorbent have increased significantly because of their availability and low cost. Clinoptilolite is one of the most abundant zeolites in nature, and Turkey has very large clinoptilolite reserves. In this project the adsorption properties of clinoptilolite rich natural zeolites for use in the removal of MTBE and ETBE from water have been investigated using batch equilibrium and fixed-bed column experiments. The adsorption properties have been compared with those of two activated carbons (i.e., Powdered Activated Carbon (PAC) and Granulated Activated Carbon (GAC)). In addition, bisolute (i.e., benzene and oxygenate) adsorption experiments were also carried out to determine the effectiveness of these adsorbents in the presence of other gasoline hydrocarbons. All the experiments were performed at 25 °C with initial oxygenate and benzene concentrations of 2000 ppb and 400 ppb, respectively. In batch equilibrium experiments, it has been found that the powdered and granulated activated carbons had higher adsorption capacities for MTBE and ETBE than clinoptilolite. The highest capacity for the amount of MTBE adsorbed per unit mass of adsorbent was achieved using GAC while that of ETBE was obtained using PAC. The presence of benzene decreased the adsorption capacities of GAC and PAC. However, the effect of benzene was not clear and was dependent on the adsorbent loading for clinoptilolite. In fixed-bed column experiments, GAC and clinoptilolite were tested as adsorbents. The column breakthrough curves for clinoptilolite were steep indicating fast adsorption and narrow mass transfer region. For GAC, mass transfer regions were wider due to the relatively flat breakthrough curves. There was no significant effect of benzene on the breakthrough curves for GAC and clinoptilolite.Master Thesis Preparation and Characterization of Polypropylene Based Composite Films(Izmir Institute of Technology, 2001) Pehlivan, Hilal; Tıhmınlıoğlu, FundaIn the scope of this study, preparation of silver . natural zeolite reinforced polypropylene (PP) composite system possessing antibacterial properties via ion exchange process and characterization by means of different techniques (FTIR, TGA, DSC, mechanical tests, optical microscopy) were aimed. It has been established that zeolites are suitable for removing Ag ions from silver containing solutions and that silver zeolites are increasingly investigated as germicidal, bactericidal, antifungal, and antiseptic components in different compositions (Hagiwara 1990, Kawahara 2000, Klasen 2000).In the present study, prior to the ion exchange studies, water sorption behavior of PP . clinoptilolite rich natural zeolite composites was investigated, since the ion exchange process was to be conducted in aqueous media. It was observed that a hydrophobic polymer, PP attained the property of water sorption due to the porous structure of the composite films. The effective diffusivity of liquid water in the PP-zeolite composites prepared by hot press and extrusion techniques varied in the range of 0.3- 9.9 x10-10 and 0.1 - 3.3 x10-12 cm2/s, respectively. Silver loading to PP - zeolite composites was provided by means of two different methods. In Method I, PP - zeolite composite films were treated with a variety of silver ion containing solutions (5 to 50 ppm AgNO3 solution), whereas in Method II silver exchanged zeolite minerals (prepared with initial AgNO3 concentrations of 50, 500, and 5000 ppm) were molded with PP in the presence of DOP (Dioctyl Phthalate). The amounts of Ag+ loaded per gram of zeolite for initial AgNO3 concentrations of 50, 500, and 5000 ppm were determined as 4.36, 27.85, and 183.78 mg, respectively. Antibacterial activity tests against E.coli indicated that the samples obtained in Method II were superior to those prepared by Method I since the penetration of silver ions to the zeolite phase was limited by the PP phase in the case of Method I. However, the discoloring effect of silver ion was readily observed for the samples prepared by Method II as indicated by the discoloration parameters. The release of Ag+ to water was found to be negligible as reported in literature leading to long . term antibacterial activity.The thermal characterization studies showed that the addition of the zeolite increased the crystallinity of the structure acting as a nucleating agent in PP crystallization as well as retarded the degradation temperature of PP. At low silver concentrations, the zeolite behaved as a decelerating agent in PP, however at higher silver concentrations, the composites degraded at a faster rate than pure PP. Yet the activation energy values for the thermal decomposition reactions of Method II was considerably lower indicating that the decomposition has been accelerated by the presence of silver.It was found that the addition of the zeolite into the PP matrix decreased the density of pure PP (0.89 g/cm3) due to the formation of voids. However, a systematic approach was not observed with the increasing zeolite content as a consequence of the uneven zeolite distribution. On the other hand, a considerable enhancement was noticed for the tensile tested film densities changing between 0.58 - 0.78 g/cm3, which are in a better agreement with the commercially desired range (0.6 - 0.65 g/cm3) for packaging applications of PP composites. Mechanical tests indicated that the addition of the zeolite tended to decrease the yield stress values while a slight decrease was observed for Young moduli. The effect of silver on the Young Modulus values of the composites is not quite significant, however the yield stress values increased from 23.6 to 29.5 MPa with the increasing silver concentration.Consequently, of all the composite films prepared by Method II, the ones loaded with 4.36 (mg Ag+/g zeolite) containing 2, and 4 % wt zeolite were selected to be the most appropriate, considering the thermal, mechanical, and structural characteristics as well as the discoloring actions.Master Thesis Co2, N2 and Ar Adsorption on Modified Zeolites(Izmir Institute of Technology, 2004) Ertan, Aslı; Özkan, Seher FehimeIn this study, CO2 and N2 adsorption on synthetic zeolites namely, 5A and 13X, and acid treated natural zeolites was investigated by using volumetric adsorption device, ASAP 2010. The natural zeolites and its acid treated forms with HCl (1M, 3M and 5M), HNO3 (2 M), and H3PO4 (1.1 M) solutions at 60 oC for 6 or 3 hours were used as adsorbent. The effect of the acid treatment and temperature on the adsorption properties of the zeolites for the CO2 and N2 gases at 5 and 25 oC was studied. Langmuir, Sips, Vrial and Dubinin-Astakhov model equations were applied to the adsorption data in order to determine the affinity and the heterogeneity of the adsorbents.Calorimetric properties of the zeolites were also studied using CO2, N2 and Ar gases through a Tian-Calvet calorimeter, Setaram C80 at 25 oC. Isosteric heat of adsorption of the gases adsorbed on the adsorbents under investigation was determined at 5 oC and 25 oC using Clasius- Clapeyron equation. These results were compared with the heat of adsorptions obtained from the calorimetric studies directly.The zeolite treated with 1.1 M H3PO4, P1 has the highest adsorption capacity (2.24 mmol/g and 0.67 mmol/g) for CO2 and N2 while the natural zeolite has only 2.08 mmol/g and 0.51 mmol/g respectively at 5 oC. Synthetic zeolites 13X and 5A have higher CO2 (6.82 mmol/g and 5.46 mmol/g respectively) and N2 adsorption capacities (0.31mmol/g and 0.91 mmol/g respectively) than natural zeolites at 5 oC. Langmuir b parameter called the affinity constant decreased as adsorption temperature increased for CO2 and N2 adsorption. The Sips model t parameter characterizing the system heterogeneity is higher for CO2 adsorption than N2 adsorption and decreases with increasing temperature. This indicates that the CO2 molecules give more specific interactions than N2 molecules. The pure component selectivities of CO2 over N2 calculated from Langmuir equation, are the highest for NCW zeolite as 408 at 25 oC. This value follows by P1 zeolite which is 151 at the same temperature.The highest differential heat of adsorption value (80.29 kJ/mol) at zero coverage for CO2 also belongs to P1 sample. The heterogeneity parameters of the model equations applied also indicated that P1 sample is more heterogeneous when compared to other acid treated natural zeolites. Finally as expected, for both N2 and CO2 as temperature increased from 5 to 25 oC, the adsorbed amounts decreased when fresh samples were used at each run in the experiments. The temperature difference had a greater effect on N2 adsorption rather than CO2.Master Thesis Acylation of 2-Methoxynaphthalene Over Ion-Exchanged Beta Zeolite(Izmir Institute of Technology, 2002) Kantarlı, İsmail Cem; Artok, LeventFriedel Crafts acylation of 2-Methoxynaphthalene was carried out over various ion-exchanged . zeolites (Mn+., where Mn+: In3+, Zn2+, Al3+, Fe3+, La3+) with various anhydride (acetic, propionic and benzoic anhydrides), or acyl chloride (acetyl, propionyl and benzoyl chlorides) acylating reagents. The results suggested that selectivity towards the 6-substituted products was higher with the larger size anhydrides, propionic and benzoic anhydrides. The metal cation type within the zeolite significantly influenced the extent of conversion and product distribution. That La3+ exchanged zeolite displayed higher selectivity for the 6-position acylated product with anhydrides ascribed mainly to narrowing of channels by the presence of La(OH)2+ ions that leave no room for the formation of more bulky isomeric forms and to enhanced Bronsted acidity of the zeolite. With acyl chlorides, the recovery of ketone products was found to be remarkably low. 1-Acyl-2-methoxynaphthalenes actively underwent deacylation when acyl chlorides were used as the acylation reagent.
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