Master Degree / Yüksek Lisans Tezleri
Permanent URI for this collectionhttps://hdl.handle.net/11147/3008
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Master Thesis L[+]-Lactic Acid Purification From Fermentation Broth Using Ion Exchange Resins(Izmir Institute of Technology, 2002) Polat, Zelal; Harsa, Hayriye ŞebnemLactic acid exists in two optically active form, D(-) and L(+)-lactic acid. It has been used in food, leather, textile, pharmaceutical and cosmetic industries. Moreover, L(+)-lactic acid constitutes the raw material for the production of poly-L-lactic acid which is used in biomedical applications.The aim of this study was to recover and purify the microbially produced L(+)-lactic acid from the fermentation media efficiently and economically. Among the various downstream operations, ion exchange chromatography was used since it is highly selective and yields a low cost product recovery within a short period of time. The additional goals were to investigate the end product purity, to obtain new data on the adsorption/desorption behaviours of lactic acid and to investigate the applicability of the system for industrial usage. In this project, Lactobacillus casei NRRL B-441 was used for the production of L(+)-lactic acid from whey by a 12 hours fermentation process at pH 5.5 and 37 oC. The product concentration was 50 g/l with 100% L(+)-lactic acid content. Then, a suitable resin with high sorption capacity and rapid equilibrium behavior was selected. The selected resin was Dowex marathon WBA, a weakly basic anion exchanger in OH form. It reached the equilibrium state in 15 minutes. The batch sorption experiments were done at pH 7.0 and 30 oC and sampling was continued for 20 hours. Furthermore, the effect of temperature and pH was investigated and their influence was found to be unimportant. All the adsorption/desorption experiments were applied both to model lactic acid and to biomass free fermentation broth. The ion exchange equilibria of lactic acid and L(+)-lactic acid in fermentation broth on Dowex marathon WBA were explained by the Langmuir isotherm. The maximum exchange capacity (qm) for model lactic acid was 0.25 g La/g wet resin, while L(+)-lactic acid in fermentation broth has a qm value of 0.04 g La/g wet resin. The equilibrium loading and exchange efficiency of L(+)-lactic acid in fermentation broth were reduced as a result of competition by other ionic species. The competing ions inhibit the binding of L(+)-lactic acid to the free sites of ion exchanger. Moreover, column operations were applied to recover sorbed lactic acid from the ion exchanger. 2.0 M HCl was found to be a suitable eluting agent to recover the bound L(+)-lactic acid with a flowrate of 1 ml/min at ambient temperature. About 95 % of bound L(+)-lactic acid was recovered from Dowex marathon WBA.Master Thesis Cation Exchange in Zeolites Structure Modification by Using a Microwave(Izmir Institute of Technology, 1999) Akdeniz, Yelda; Ülkü, SemraIn this research, characterization and modification of clinoptilolite minerals from different deposits have been studied to determine its utility for different Clinoptilolite minerals obtained from the source located in Western (FTIR) to determine the structural properties. The FTIR spectra of the samples showed the characteristic vibrations of the clinoptilolite framework. Thermal properties were determined using Differential Thermal Analyzer (DTA), Thermal Gravimetric Analyzer (TGA), and Differential Scanning Calorimetry (DSC). The analysis showed that the structure of the samples were stable up to 650 DC and due to the Fe203 present in the tuff, phase inversion was observed. Accelerated Surface Area and Porosimeter (ASAP 2010) used to determine the adsorptionrelated properties using N2 and Ar adsorption isotherms. The samples showed different adsorption behaviour toward each gas. The pore size distribution of clinoptilolite samples showed that they have mesaporous structure.The clinoptilolite was modified by ion exchange using 1N NaCI salt solution in waterbath, and in microwave maintained at 80 DC for 10 min, 60 min and 120 min. The efficiency of each method on ion exchange was compared. The Na+ amount in the zeolite was found to be 2.25 and 3.24 % by weight after 2 hours of exchange in waterbath and microwave, respectively. The results showed that microwave method used for modification was more efficient.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 Cation Exchange (ag+, Zn2+, Cu2+) Behavior of Natural Zeolites(01. Izmir Institute of Technology, 2001) Top, Ayben; Ülkü, SemraIn this study, clinoptilolite, most abundant zeolite present in nature, was proposed as a low cost antibacterial material. As a preliminary work, antibacterial activities of the original, Ag, and Zn forms of the clinoptilolite were investigated against several strains and compared to the commercial antibiotics. No antibacterial action was observed for the original clinoptilolite. Ag loaded clinoptilolite was found to be superior to the Zn-form against Proteus spp. and Pseudomonas aeruginosa.The original, Na, Ag, Zn, and Cu forms of the clinoptilolite samples were characterized by FTIR spectroscopy, thermal analyses (TGA, DTA, and DSC), and N2 physisorption studies. Specific attention was given in to the chemical analysis of the clinoptilolite by ICP-AES. Using the standard addition method, the respective idealized formulas of the original and Na-clinoptilolite based on 72 oxygen atoms in the unit cell were calculated as:(Na0.816 K2.070) (Ca1.060 Mg0.264) (Al5.653 Fe0.390) (Si30.084) O72. 20.023 H2O, and (Na4.763 K1.057) (Ca0.076 Mg0.094) (Al5.843 Fe0.221) (Si29.911) O72.17.049 H2O.In the FTIR spectra of the original and exchanged forms of the clinoptilolite, considerable shifts (from 3460 to 3494.8 cm-1) were observed in the band, which is formed due to the interactions of water molecules with the framework via hydrogen bonds. The positions of the other bands were not affected by cation exchange significantly. From the TGA curves, the water contents ranged between 14.31 and 11.00 % for the original and the cation-exchanged forms of the clinoptilolite. Mainly, two endotherms and one exotherm were obtained in the DTA curves. The first endotherm occurred up to about 150 oC, the second endotherm lied between 200 and 700 oC, and the exotherm was obtained at about 850 oC. Significant differences observed between the shapes of the DSC curves indicated that the cations control the dehydration behavior of the samples. N2 physisorption isotherms of five samples were all, Type IV with BET surface areas ranging between 34.97 and 46.76 m2/g.Ag, Zn and Cu ion exchange equilibria were investigated at 25 oC for both the original clinoptilolite and Na-clinoptilolite. In the former case, from the plateau of the isotherms cation exchange capacities were determined as 1.184, 0.439, 0.539 meq/g clinoptilolite for Ag+, Zn2+, and Cu2+ respectively. The major portion of the exchanges was contributed by Na+ and Ca2+. Distribution coefficient values indicated that at Ag, Zn and Cu ion exchange equilibria were investigated at 25 oC for both the original clinoptilolite and Na-clinoptilolite. In the former case, from the plateau of the isotherms cation exchange capacities were determined as 1.184, 0.439, 0.539 meq/g clinoptilolite for Ag+, Zn2+, and Cu2+ respectively. The major portion of the exchanges was contributed by Na+ and Ca2+. Distribution coefficient values indicated that at relatively low initial concentrations, the preference of the clinoptilolite for Zn2+ and Cu2+ was significant. At higher concentrations, higher distribution coefficients were obtained for Ag+ compared to Zn2+ and Cu2+. Langmuir and Freundlich models were applied for each equilibrium data. For Zn2+ and Cu2+ exchanges, Langmuir model gave better correlation and Freundlich model fitted experimental data slightly better in the case of Ag+ exchange.Equilibrium isotherms for Ag+-Na+, Zn2+-Na+, and Cu2+-Na+ pairs were investigated. Silver exchange isotherm lied above the diagonal over the whole composition range. For zinc and copper exchanges, the isotherms were above the diagonal up to equivalent fractions of exchanging ion in solution phase (As) at about 0.2. While full exchange was attained for silver, partial exchanges were obtained in the case of zinc and copper. The standard free energy of exchange values were found as .6.0, 2.03 and 3.09 kj/equiv for Ag+-Na+, Zn2+-Na+, and Cu2+-Na+ pairs respectively. From these values selectivity sequence was obtained as Ag+ > Na+ > Zn2+ > Cu2+.Consequently, by considering the preliminary antibacterial activity results, specific cation exchange capacities, and selectivity sequence of the clinoptilolite, Ag-clinoptilolite seemed to be promising antibacterial material. The results of the current study compared to the literature data pointed out that cation exchange behavior of the clinoptilolite is dependent on its original cationic composition. Therefore, it is necessary to carry out specific studies on representative samples from the deposit before any practical application.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.Master Thesis Use of Ion Exchange Resins Modified With Zero-Valent Iron for the Sorption/Speciation of Inorganic As(iii) and As(v) in Waters(Izmir Institute of Technology, 2012) Bölek, Deniz; Eroğlu, Ahmet EminArsenic is a cumulative toxic element and according to Environmental Protection Agency its maximum admissible concentration is established as 10.0 μgL-1 in drinking water. The consumption of arsenic via drinking contaminated water causes chronic and acute poisoning which result in different cancer types. Therefore, determination, speciation and removal of arsenic compounds from waters are important. This study aims to develop a novel sorbent for removal of inorganic arsenic species from contaminated waters. For this purpose a strong anion exchange resin (Amberlite IRA 458) was modified with zero valent iron (ZVI). In the first part of the study, various commercial anion exchange resins and novel resins prepared in the study were used for sorption and speciation of inorganic arsenic. For all the sorbents, the optimized sorption parameters were determined to be 25 ËšC for sorption temperature, 50.0 mg for sorbent amount, 60 min for shaking time for 20.0 mL of 100.0 μgL-1 of arsenic species. The release of As(III) and As(V) from the sorbents was realized using two eluents, 2% (m/v) NaOH + 3% (m/v) NaCl and 5% (m/v) NaOH + 3% (m/v) NaCl, respectively. The accuracy of the proposed methodology was verified with sorption studies for various water types spiked with 100.0 μgL-1 As(III) and As(V). Sorption values of ZVI-IRA 458 were determined to range between 59.1% and 100% for As(III) and between 61.5% and 100% for As(V). Moreover, the sorption efficiencies of the novel sorbents were compared with those of the commercial sorbents.In the final part of the study, the sorption results demonstrated that the most effective immobilization method was NaBH4 reduction and the most efficient resin to be modified was Amberlite IRA 458. Also, the sorption characteristic of ZVI-modified resins showed that the removal efficiency depended on the type of resins and arsenic species in water.Master Thesis Chemical Behaviour of Clinoptilolite Rich Natural Zeolite in Aqueous Medium(Izmir Institute of Technology, 2005) Polatoğlu, İlker; Özkan, Seher FehimeIn this study the chemical behavior of natural zeolite from Gördes Türkey and its Na2CO3 treated form was investigated in acid (hydrochloric acid, lactic acid, acetic acid) and basic (sodium hydroxide) solutions. Synthetic gastric juice (hydrochloric acid and 0.4 % pepsin at pHi.2) was also prepared in order to examine the neutralizing capacity of zeolite for high acid concentration of stomach. The change in proton and hydroxyl concentration with time was studied by putting the different amount of zeolites into the various concentrations of acid and base solutions.It was found that natural zeolite tended to increase the pH of acidic solution while decreased the pH of basic solution depending on the concentration of proton or hydroxyl ions in solution and zeolite amount. The proton or hydroxide ions entered to the zeolite could not balance the cations released from zeolite structure. Therefore not only ion exchange, but also adsorption, cation hydrolysis, dissolution of Al and Si, complex formation and precipitation can be occurred. The neutralizing capacity of modified zeolite with sodium carbonate was higher than untreated ones. In the study conducted with synthetic gastric juice, 0.5 g modified zeolite did not significantly affect the pepsin activity of the medium and increased the pH to 2.9 which was between the normal ranges of stomach acid (2.9-3.1). In all aqueous studies conducted by using natural zeolite there was no change observed at the surface charge of the zeolite. According to characterizations performed it is understood that there was no significant change and the structure was stable. For these reason zeolite can be used as solid buffer in aqueous medium.