Browsing by Subject "ion exchange"
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Item Development of Pillared M(IV) Phosphate Phosphonate Inorganic Organic Hybrid Ion Exchange Materials for Applications in Separations found in the Nuclear Fuel Cycle(2012-10-02) Burns, JonathanThis dissertation focuses on key intergroup and intragroup separations found in the back end of the nuclear fuel cycle, specifically americium from lanthanides and americium from other actinides, most importantly americium from curium. Our goal is to implement a liquid-solid separation process to reduce waste and risk of contamination by the development of metal(IV) phosphate phosphonate inorganic organic hybrid ion exchange materials with the ideal formula of M(O6P2C6H4)0.5(O3POA) * nH2O, where M = Zr or Sn, A = H or Na. These materials have previously shown to have high affinity for Ln, this work will expand on the previous studies and provide methods for the above target separation, exploiting oxidation state and ion charge to drive the separation process. The optimum hydrothermal reaction conditions were determined by adjusting parameters such as reaction temperature and time, as well as the phosphonate to phosphate (pillarto-spacer) ligands ratio. Following these results four bulk syntheses were performed and their ion exchange properties were thoroughly examined. Techniques such as inductively coupled mass spectrometry and liquid scintillation counting were used to determine the affinity of the materials towards Na+, Cs+, Ca2+, Sr2+, Ni2+, Nd3+, Sm3+, Ho3+, Yb3+, NpO2+, Pu4+, PuO22+, Am3+, AmO2+, and Cm3+. Separation factors in the thousands have been observed for intergroup separations of the Ln from the alkali, alkaline earth, and low valent transition metals. A new method for Am oxidation was developed, which employed Na2S2O8 as the oxidizing agent and Ca(OCl)2 as the stabilizing agent for AmO2+ synthesis. Separation factors of 30-60 for Nd3+ and Eu3+ from AmO2+, as well as 20 for Cm3+ from AmO2+ were observed at pH 2. The work herein shows that a liquid-solid separation can be carried out for these difficult separations by means of oxidation and ion exchange.Item Ion exchange kinetics of cesium for various reaction designs using crystalline silicotitanate, UOP IONSIV IE-911(Texas A&M University, 2004-09-30) Kim, Sung HyunThrough collaborative efforts at Texas A&M University and Sandia National Laboratories, a crystalline silicotitanate (CST), which shows extremely high selectivity for radioactive cesium removal in highly concentrated sodium solutions, was synthesized. The effect of hydrogen peroxide on a CST under cesium ion exchange conditions has been investigated. The experimental results with hydrogen peroxide showed that the distribution coefficient of cesium decreased and the tetragonal phase, the major component of CST, slowly dissolved at hydrogen peroxide concentrations greater than 1 M. A simple and novel experimental apparatus for a single-layer ion exchange column was developed to generate experimental data for estimation of the intraparticle effective diffusivity. A mathematical model is presented for estimation of effective diffusivities for a single-layer column of CST granules. The intraparticle effective diffusivity for Cs was estimated as a parameter in the analytical solution. By using the least square method, the effective diffusivities of 1.56 ? 0.14 x 10-11 m2/s and 0.68 ? 0.09x 10-11 m2/s, respectively, were obtained. The difference in the two values was due to the different viscosities of the solutions. A good fit of the experimental data was obtained which supports the use of the homogeneous model for this system. A counter-current ion exchange (CCIX) process was designed to treat nuclear waste at the Savannah River Site. A numerical method based on the orthogonal collocation method was used to simulate the concentration profile of cesium in the CCIX loaded with CST granules. To maximize cesium loading onto the CST and minimize the volume of CST, two design cases of a moving bed, where the fresh CST is pulsed into the column at certain periods or at certain concentration of cesium, were investigated. Simulation results showed that cesium removal behavior in the pilot-scale test of CCIX experiment, where the column length is 22 ft and the CST is pulsed 1 ft in every 24 hours, was well predicted by using the values of the effective diffusivities of 1.0 to 6.0 ? 10-11 m2/s.Item Liquid-phase Processing of Fast Pyrolysis Bio-oil using Pt/HZSM-5 Catalyst(2013-05-01) Santos, Bjorn SanchezRecent developments in converting biomass to bio-chemicals and liquid fuels provide a promising sight to an emerging biofuels industry. Biomass can be converted to energy via thermochemical and biochemical pathways. Thermal degradation processes include liquefaction, gasification, and pyrolysis. Among these biomass technologies, pyrolysis (i.e. a thermochemical conversion process of any organic material in the absence of oxygen) has gained more attention because of its simplicity in design, construction and operation. This research study focuses on comparative assessment of two types of pyrolysis processes and catalytic upgrading of bio-oil for production of transportation fuel intermediates. Slow and fast pyrolysis processes were compared for their respective product yields and properties. Slow pyrolysis bio-oil displayed fossil fuel-like properties, although low yields limit the process making it uneconomically feasible. Fast pyrolysis, on the other hand, show high yields but produces relatively less quality bio-oil. Catalytic transformation of the high-boiling fraction (HBF) of the crude bio-oil from fast pyrolysis was therefore evaluated by performing liquid-phase reactions at moderate temperatures using Pt/HZSM-5 catalyst. High yields of upgraded bio-oils along with improved heating values and reduced oxygen contents were obtained at a reaction temperature of 200?C and ethanol/HBF ratio of 3:1. Better quality, however, was observed at 240 ?C even though reaction temperature has no significant effect on coke deposition. The addition of ethanol in the feed has greatly attenuated coke deposition in the catalyst. Major reactions observed are esterification, catalytic cracking, and reforming. Overall mass and energy balances in the conversion of energy sorghum biomass to produce a liquid fuel intermediate obtained sixteen percent (16 wt.%) of the biomass ending up as liquid fuel intermediate, while containing 26% of its initial energy.Item Perchlorate Degradation Using Partially Oxidized Titanium Ions and Ion Exchange Membrane Hybrid System(2011-08-08) Park, Sung HyukPerchlorate has entered human and environmental food chains and has received a great deal of attention because of its toxicity to humans. In this study, chemical degradation of perchlorate was investigated using partially oxidized titanium ions (Ti2+ and Ti3+) in solutions and as part of an ion exchange membrane reactor system. Aqueous titanium ions (Ti2+ and Ti3+) were applied to remove perchlorate ions and its destructive mechanism, reaction kinetics, and the effect of environmental factors were investigated. Titanium ions were able to degrade perchlorate ions very rapidly with half life less than one hour under conditions of high acid concentrations. A new reactor system with an ion exchange membrane was adapted to apply better the reactions of perchlorate destruction to water treatment practice. A novel treatment method was developed by integrating partially oxidized titanium ions with an ion exchange membrane, and it is named the Titanium and Membrane Hybrid System (TMH System). The results shown in this research demonstrate the feasibility of TMH System for perchlorate reduction. The perchlorate ions were rapidly adsorbed onto the ion exchange membrane and diffused through it, but they were reduced by titanium ions in the degradation zone relatively slowly. To enhance the overall rate of reaction, high concentrations of acid and Ti(III) are needed, but transport of hydrogen ions through the anion permeable membrane was observed and would be greater at higher acid concentrations. The proposed mathematical model predicts the performance and behavior of the TMH system for different physical and chemical conditions. It successfully described adsorption, diffusion and reduction of perchlorate in the system. This model could be used as an important tool for process design and optimization.