Thesis (Master)--İzmir Institute of Technology,İzmir, 2005 / Includes bibliographical references (leaves. 84-89).

M.Sc. / The metallurgical industrial losses of base metals with waste solutions are an environmental threat to water sources, hence these metal ions must be removed prior to discharge into receiving bodies. In this study, Southern African clinoptilolite’s capability as an ion-exchanger with respect to Cu2+ and Co2+ was investigated in order to consider its application in metal cation removal from aqueous solutions. The clinoptilolite was characterised with X-ray powder diffraction (XRD), X-ray fluorescence (XRF), FTIR, thermogravimetric analyser (TGA) and SEM-EDS. The clinoptilolite was found to be a thermally stable alumino-silicate with calcite, dolomite and quartz as the main minerals. Investigations of Co2+ and Cu2+ uptake were first performed on non-mixed solutions of these cations. It was found that Cu2+ was removed faster than Co2+ with removal efficiencies of 79% and 63% respectively. The column method was used in the cation-exchange processes with synthetic solutions of 0.0020 M, 0.0698 M and 0.2000 M of Co2+ and Cu2+ concentrations which were measured using atomic absorption spectroscopy (AAS). The effects of Co2+ and Cu2+ ions on one another’s removal efficiency were investigated on Co/Cu mixed synthetic solutions by varying their concentration ratios in solution. The Cu2+ was generally found to be removed at lower rates than the Co2+. Investigations on added impurities in the form of Si4+ and Fe2+ in the mixed Co/Cu synthetic solutions were carried out to determine their effect on the removal efficiencies of the targeted metals. It was found that both Si4+ and Fe2+ greatly reduced the removal efficiency of Cu2+, especially with increased amounts of Si4+ in the Co/Cu solution.

Slow rate sand filtration (SSF) amended with a 20 em surface layer of clinoptilolite, a natural zeolite, was compared to SSF with no amendment in a field scale SSF facility treating 85 m3/d of water. Parameters examined included turbidity, coliforms, and ammonium removal. The control filter with sand and the experimental filter amended with the zeolite were also compared with respect to duration of filter cycle, cold weather operation, and economics. Amended and unamended filters were appr oximately equivalent with respect to ammonium and coliform removal at 10° C. The zeolite amended cell was superior to the unamended cell with respect to coliform and turbidity removal at 3° C. The zeolite amended cell had filter cycle durations four times longer and operation and maintenance costs 25% lower than the unamended cell. Laboratory column studies were also conducted to compare a control column of construction sand to a homogeneous sand-zeolite mixture. and to SSF amended with zeolite or coarse sand. Construction sand and clinoptilolite were very similar in metal removal efficiency. Head loss developed most rapidly in the SSF column with construction sand only. Head loss developed more slowly resulting in longer filter cycles when the SSF was amended with a zeolite or coarse sand surface layer. A homogeneous sand-clinoptilolite mixture had filter cycles longer than construction sand, but shorter than SSF amended with a coarse surface medium. Batch reactor tests were utilized to compare adsorption of reovirus to sand and clinoptilolite. Reovirus adsorption was approximately equivalent for the two media.

No description available.

Clinoptilolite is the most abundant zeolite mineral in nature. In this study a reproducible synthesis recipe for clinoptilolite was established and the limits of the crystallization field were developed by changing synthesis parameters such as temperature, composition and the nature of reactants. Clinoptilolite was reproducibly synthesized as a pure phase and in high yield at 140oC using a benchmark batch composition of 2.1 Na2O:Al2O3:10SiO2:110.1 H2O. Clinoptilolite was crystallized from 10wt% or 28wt% seeded systems while it was not formed if no seeds were present. Clinoptilolite was also crystallized as a pure phase when the cation in the benchmark batch composition was Na,K mixture, or when alkali salts such as carbonates or chlorides were used besides alkali hydroxides, or when the SiO2/Al2O3 ratio was in the range of 10-12. Clinoptilolite was still crystallized as a single phase when alkali hydroxides in the batch were reduced by 20%. With the benchmark batch composition, clinoptilolite was crystallized in pure phase form at 100oC, 120oC, 140oC and 160oC while synthesis at 175oC resulted in the formation of pure mordenite. At 140oC clinoptilolite was crystallized together with Linde L when cation in the benchmark composition is only potassium. Phillipsite crystallized together with clinoptilolite at SiO2/Al2O3 ratio of 8 to 9. At SiO2/Al2O3 ratios of 6 or 4, phillipsite or analcime was formed as pure phase respectively. When the alkali hydroxides in the batch was increased by 20%, sanidine was formed. Use of reactive aluminosilicate gels enhanced the formation of clinoptilolite while attempts to use mineral raw materials were unsuccessful. For both Na and (Na,K)-clinoptilolite, Si/Al ratio of products were greater than four. Thermal stability of synthetic clinoptilolites were comparable with natural clinoptilolite and potassium ion increased thermal stability of clinoptilolite.

Clinoptilolite zeolite has a theoretical cation exchange capacity of 2.25 moles of charge kg⁻¹, and a rigid three-dimensional lattice riddled with angstrom-sized tunnels, and interconnected voids, in which water and exchangable cations are held. The hypothesis was that clinoptilolite had the facility to preferentially and internally sorb NH₄⁺, where it would be physically protected from microbial nitrification. Hence nitrification rates would be decreased and plant N-fertilizer use efficiency increased. Exchange capacities of clinoptilolite determined at 30°C by saturation/desorption for NH₄⁺, K⁺ and Na⁺ were approximately 2.00 moles of charge kg⁻¹, while capacities for Ca²⁺ and Mg²⁺ were 1.53 and 0.97 respectively. On this basis three site groups were identified: those accessible to all cations studied, sites accessible to all cations but Mg²⁺ and sites only accessible to NH₄⁺, K⁺ and Na⁺. Equilibrium isotherms were used to determine selectivity of site groups at 30°C. Consideration of site accessibilities and selectivities indicate an overall preference of clinoptilolite of: K⁺ > NH₄⁺ > Na⁺ = Ca²⁺ > Mg²⁺. Notably, the plant macronutrient cations, K⁺ and NH₄⁺, are preferentially sorbed. Nitrification of NH₄⁺ on clinoptilolite amended sands incubated at 20% volumetric moisture capacities, was studied in the laboratory. Treatments were washed mortar sand amended with 0, 5 and 10% clinoptilolite by volume and 2.38 and 3.57 moles of NH₄⁺ m⁻³ of sand-clinoptilolite mix. Nitrification was evaluated by monitoring NH₄⁺ loss. Rates of nitrification decreased with increasing clinoptilolite amendment and decreased with N-fertilizer initially applied. The effect of clinoptilolite in slowing nitrification was more pronounced at higher initial NH₄⁺-fertilizer application. The hypothesis that internally sorbed NH₄⁺ in clinoptilolite is physically protected from microbes resulting in decreased nitrification rates was confirmed. The effect of clinoptilolite on N-use efficiency of creeping bentgrass was studied in a field trial. Factorial treatments included washed mortar sand amended with 0, 5 and 10% clinoptilolite by volume and 25, 50 and 75 kg of N ha⁻¹ growing month⁻¹. Approximately 45% of applied N was harvested in clippings from 10% clinoptilolite amended sand in contrast to 36% N recovery on 100 % sand. This supports the hypothesis of improved plant N-fertilizer use efficiency on clinoptilolite amended sand.

Crops grown in sandy soils require frequent irrigation. As a result, nitrogen (N) fertilizers. such as ammonium sulfate((NH4)2SO4), are leached from the rooting zone of crops. This loss of N increases N fertilizer use and the potential for nitrate (NO3-) contamination of water. Ammonium-loaded clinoptilolite (NH4+-Cp) may reduce this N leaching, increase N fertilizer use-efficiency, and prevent NO3- contamination of water while sustaining normal crop growth. The potential of NH4+-Cp as a N fertilizer was assessed in three leaching experiments without plants and two leaching experiments with plants. Pots containing rounded quartz sand were amended with (NH4)2SO4 and one of three NH4+-Cp size fractions: small ( Finally, in two leaching studies, pots containing the sandy soil were planted with sweet corn and grown for 35 d and 42 d, respectively. No differences were found among N sources in corn relative growth rates, leaf area ratios, and net assimilation rates, even though the corn plants that were fertilized with NH4+-Cp assimilated significantly more N than the (NH4)2SO4-fertilized plants. The pots fertilized with NH5+-Cp leached In the greenhouse, NH4+-Cp is a slow-release fertilizer that will reduce N leaching while maintaining normal plant growth. However, field studies are needed to confirm the suitability of NH4+-Cp as a slow-release fertilizer under field conditions.

Alkaline conditions induced by algae growth in wastewater stabilization ponds create deprotonated ammonium ions that result in ammonia gas (NH3) volatilization. If algae are utilized to remediate wastewater through uptake of phosphorus, the resulting nitrogen loss will hinder this process because algae generally require a stoichiometric molar ratio of N16P1. Lower ratios of N/P due to loss of ammonia gas will limit the growth and yield of algae, and therefore will reduce phosphorus removal from the water phase into the algae phase. In order to reduce nitrogen loss through volatilization, an ammonium selective zeolite, clinoptilolite, can be used to sequester nitrogen from the water phase as ammonium ion and in a form that is bioavailable for uptake and growth of algae. A novel algae biofilm rotating photo bioreactor (RPB) with clinoptilolite integrated to the outermost surface as the substratum for algae biofilm attachment and growth has been designed, constructed, and tested for ammonium capture and algae biomass production, with simultaneous removal of the algal nutrient phosphorus from water. The clinoptilolite‐based RPB (cRPB) provides algal biomass that can serve as feedstock for biofuel production through uptake of zeolite‐based nitrogen and water phase phosphorus.

Biogas is a source of renewable energy and is produced at anaerobic conditions. The gas consists mainly of methane (55-70 %) and carbon dioxide (30-45 %). Biogas can be used as vehicle fuel after the gas has been upgraded to a methane content of approximately 97 %. There are several companies in Sweden producing biogas. Svensk biogas AB in Linköping is one of the largest. The company has two biogas production plants; one in Linköping and one in Norrköping. To meet the surge demand for biogas it is not only important to increase the volumetric capacity of the digesters, but also to optimize the process at the existing production plants in different ways. Zeolites, a clay mineral, have earlier been shown to have a positive effect on anaerobic digestion of certain substrates. The aim of this master’s thesis was to investigate if the organic loading rate could be increased and/or if the hydraulic retention time could be reduced by addition of zeolites to a reactor treating slaughterhouse waste as a substrate. The aim was further to investigate which substance/substances that zeolites possibly could affect. Addition of the zeolite clinoptilolite in a continuously stirred lab tank reactor showed a significantly lower accumulation of volatile fatty acids compared to that in a control reactor without zeolites added, when the hydraulic retention time was kept low (30 days) and the organic loading rate was high (4.8 kg VS/ (m3 × day)). The same results were observed upon zeolite addition in a batch experiment, which also showed a decreased lag phase. Neither the specific gas production nor the methane concentration was significantly affected by addition of zeolites. Furthermore, addition of a possible inhibitor, long-chain fatty acids (LCFA), increased the lag phase further when slaughterhouse waste was used as a substrate. The conclusion from the observed results is that a metabolite or metabolites produced during the anaerobic degradation is/are the reason to inhibition and an increased lag phase.

ABSTRACT LEAD(II) AND AMMONIUM EXCHANGE on Na-FORM of G&Ouml / RDES CLINOPTILOLITE ASiroglu, Sedat M.S., Department of Chemical Engineering Supervisor Prof. Dr. Hayrettin Y&uuml / cel September 2006, 89 pages Natural zeolites, especially clinoptilolite, have the ability of removing certain cations from wastewater by utilizing ion exchange and adsorption. In this study, ion exchange behaviour of G&ouml / rdes clinoptilolite at particle size range (0.5-0.25 mm) for lead and ammonium removal was investigated to establish the conditions under which clinoptilolite may be used in an economical and effective manner. Experiments were divided into two parts. Batch and continuous (column) experiments were carried out. In the batch experiments, experimental isotherms of NH4+-Na+, Pb2+-Na+ binary systems and NH4+-Pb2+-Na+ ternary system were obtained as the graphs of equivalent fractions of exchanging cation in solution versus equivalent fractions of cation in zeolite. It was determined that clinoptilolite has affinity for Pb2+ and NH4+ ions. Finally, the selectivity sequence of G&ouml / rdes clinoptilolite in the presence of Pb2+ and NH4+ together was determined as Pb2+ &gt / NH4+ &gt / Na+. In the column studies, removal of lead, ammonium and simultaneous removal of lead-ammonium solutions were investigated. The loading flow rates were selected as 8, 15, and 30 mL/min. The ion exchange capacity of clinoptilolite for lead and ammonium removal showed good performance. Flow rates at 8, 15, 30 mL/min, breakthrough capacities were found as 0.398 meq/g (Pb2+) and 0.337 meq/g (NH4+), 0.299 meq/g (Pb2+) and 0.297 meq/g (NH4+), 0.197 meq/g (Pb2+) and 0.198 meq/g (NH4+) for lead-ammonium-sodium system and corresponding column efficiencies were 63.36%, 51.38%, 34.05%, respectively.