Perchlorate is known to adversely affect the thyroid gland functions including iodide take up, thus perchlorate should be removed from drinking water. Bituminous coal-based activated carbon (AC) has been used for perchlorate removal in past years. Virgin carbon and carbon modified by oxidation with HNO3, NaOH and H2O2 were examined in this study for their ability to remove perchlorate by reduction or adsorption mechanisms. Surface functional groups formed on the modified AC (MAC) were examined with diffuse reflectance infrared spectrometry. Inhibition of perchlorate removal onto MAC by various anions ( - Cl , - 3 NO , and - 2 4 SO ) and solution pH (4.5, 7.2 and 10.5) were examined to characterize the MACs before an electrochemical reaction was performed. Surface functional groups were increased by oxidation. Groups that were found on the carbon include, but are not limited to lactone, quinine, carboxylate, and nitrogenoxygen groups. The effect of pH on removal of perchlorate by MAC was greatly affected by the change in the zero point charge (ZPC) induced on the carbon by modification. Virgin carbon also experienced difficulty in removing perchlorate when solution pH was above the ZPC. Anion inhibition varied with the modification process. - 3 NO inhibited perchlorate removal only by the virgin carbon. The other anions showed no major effects on the removal efficiency of perchlorate by the carbons. Electrochemical processes did not show favorable results in removal of perchlorate. The dominant mechanism of perchlorate removal during desorption tests was adsorption onto the carbon surfaces via ion exchange.

Chloramines are used for disinfection in many water treatment facilities because of their ability to provide residual protection of water supplies while minimizing the formation of disinfection-by-products. However, chloramines can impart taste and odor to the water, which can lead to customer complaints. Furthermore, the removal of monochloramine from water is essential for certain industries. Previous research at the University of Texas at Austin has demonstrated the potential of several granular activated carbons (GAC) for removal of monochloramine under conditions typical of water treatment plants. The goal of this research project is to further quantify steady-state monochloramine reduction in fixed bed reactors (FBR) with three commercially available GACs, and improve the understanding of the physical and chemical properties that influence removal. The research was divided into 3 phases: 1. A laboratory scale fixed bed reactor experiment was used to quantify steady state monochloramine removal over time. City of Austin tap water viii was used for three GAC types (Jacobi CAT, Norit CAT, Nority CNS) at pH 8 and 9. 2. Physical characterization of each GAC was performed using analysis of nitrogen adsorption isotherms. Specific surface area, pore volume, and pore distribution were determined. Chemical characterization was performed quantitatively using Boehm titrations. Qualitative analysis was performed by analyzing FTIR spectra of untreated activated carbon samples. 3. The Monochloramine Catalysis (MCAT) model was calibrated using results from the Phase 1 and 2 experiments. Simulations of full scale point of use drinking water filters were run for various empty bed contact times and influent monochloramine concentrations. These results were compared against National Sanitation Foundation monochloramine reduction certification criteria. Results show that steady state removal was achieved for all of the activated carbons tested and this removal efficiency can reach nearly 90% using a 0.75-minute empty bed contact time. This steady state performance indicated that catalysis of the monochloramine was occurring, and removal could theoretically occur for very long periods of time. The second stage of the research shows correlation between chemical characteristics (acidity and basicity) and removal efficiency. Furthermore, physical characteristics, mainly micro-porosity, were shown to largely impact performance. Finally, the MCAT model provides a reasonable estimate of steady state removal, and is used to predict full scale point of use performance. / text

Granular Activated Carbon (GAC) is used in packed beds to treat trace quantities of icropollutants. Many years of research and industrial use has ensured that it is highly effective as a water treatment process. However, GAC is expensive and economic considerations mean it has to be recovered and re-used Powdered Activated Carbon (PAC; is a cheaper alternative but the particle size range means it is unsuitable for packed bed applications. This thesis describes a novel method for utilising PAC to treat micropollutants. By contacting carbon paracles with air bubbles, under conditions o.lrotational shear and a binding agent, oleyl alcohol, carbon-coated air bubbles form which remain stable while agitated byflowing water. A stabilised air bubble can be visualised as a phere with an impervious core (the air bubble), surrounded by a thin layer of porous matehal (PAC). Theory dictates that all these stabilised air bubbles can be moved counter-currently to a contaminated stream, higher throughputs than conventional packed beds are possible. Several aspects of this process are investigated. Bubble generation is critical and so the literature was reviewed to explain the mechanisms involved Practical use was made of this knowledge in designing a larger bubble generator. Transferring the coated-bubbles to a contacting column was difficult. Problems associated with the various methods employed are described and recommendations are made for improvement. The contacting column was used to assess the stability and adsorptive capacity of the bubbles. The possibility of counter-current flow using stabilised air bubbles was also evaluated and found to be incompatible with the current column design. The stabilised bubbles collected in the column resembled an inverted fluidised bed. Experiments were performed to test Richardson and Zaki's hydrodynamic laws for conventional fluidised beds were applicable to inverted beds. The adsorptive capacity of the bubbles was assessed by dosing the water with trace levels of phenol and p-chlorophenol. Samples taken from before and after the fluidised bed were analysed and compared. The results were inconclusive, although the concentration profile produced indicated that flow through the bubble bed was piston-flow.

Iodine number, BET surface area, taste and odour compound isotherms, and trace capacity number tests were used to rank five different granular activated carbons according to thermodynamic adsorption performance. These tests were compared to expected activated carbon service life and loading results of rapid small-scale column tests (RSSCTs) run with water from two lake sources spiked with geosmin and 2-methylisoborneol (MIB). Trace capacity number, used to specifically identify high adsorption energy sites on activated carbon, was hypothesized to be correlated to geosmin/MIB breakthrough and loading performance of different activated carbons. This study found no such clear correlation. However, when only bituminous coal activated carbons were considered, correlations to MIB breakthrough were strengthened. Natural organic matter (NOM) adversely affected adsorption, resulting in decreased RSSCT throughput to breakthrough in surface water with higher total organic carbon (TOC). Methods for improving characterization tests and RSSCTs when NOM is present are discussed.

Biogas, produced from anaerobic digestion of cattle manure, is an attractive alternative energy source as it is rich in methane. However, it is necessary to remove hydrogen sulfide from the biogas before it can be used in engines for electricity generation. Currently, large scale biogas systems employ physical adsorbing solvents to upgrade and purify biogas which is not economically feasible for small scale biogas systems. Activated carbon made from anaerobic digestate proves to be an effective adsorbent of hydrogen sulfide because it has minimal operating costs and essentially zero raw material cost. A model is developed to predict the adsorption capacity, carbon bed life span, and breakthrough time for this carbon material. By analyzing the reaction constant, adsorption constant, and degradation constant, adsorption behavior under different operating conditions were studied. The model can be scaled-up to model adsorption for biogas loading rates for small to large scale cattle farms.

Iodine number, BET surface area, taste and odour compound isotherms, and trace capacity number tests were used to rank five different granular activated carbons according to thermodynamic adsorption performance. These tests were compared to expected activated carbon service life and loading results of rapid small-scale column tests (RSSCTs) run with water from two lake sources spiked with geosmin and 2-methylisoborneol (MIB). Trace capacity number, used to specifically identify high adsorption energy sites on activated carbon, was hypothesized to be correlated to geosmin/MIB breakthrough and loading performance of different activated carbons. This study found no such clear correlation. However, when only bituminous coal activated carbons were considered, correlations to MIB breakthrough were strengthened. Natural organic matter (NOM) adversely affected adsorption, resulting in decreased RSSCT throughput to breakthrough in surface water with higher total organic carbon (TOC). Methods for improving characterization tests and RSSCTs when NOM is present are discussed.

Biogas, produced from anaerobic digestion of cattle manure, is an attractive alternative energy source as it is rich in methane. However, it is necessary to remove hydrogen sulfide from the biogas before it can be used in engines for electricity generation. Currently, large scale biogas systems employ physical adsorbing solvents to upgrade and purify biogas which is not economically feasible for small scale biogas systems. Activated carbon made from anaerobic digestate proves to be an effective adsorbent of hydrogen sulfide because it has minimal operating costs and essentially zero raw material cost. A model is developed to predict the adsorption capacity, carbon bed life span, and breakthrough time for this carbon material. By analyzing the reaction constant, adsorption constant, and degradation constant, adsorption behavior under different operating conditions were studied. The model can be scaled-up to model adsorption for biogas loading rates for small to large scale cattle farms.

Mercury is a serious hazard to humans, mammals and fish, which when emitted into the atmosphere reaches back to the earth. Coal-fired plants in the U.S. emit mercury upon the burning of coal in the particulate, oxidized and elemental state. Of these, elemental mercury is the most difficult to capture. U.S. coal-fired plants emit approximately 48 tons of mercury per year. Based on the U.S. EPA Clean Air Mercury Rule, these emissions need to be capped by 90%. This project deals with the Development of Bamboo Derived Sorbents for the capture of elemental mercury in gas phase. Raw bamboo is used to process sorbents using carbonization, activation and acidulation techniques. These sorbents are tested in a Batch Test, which includes a mercury permeation assembly, sampling bags, and uses nitrogen as a carrier gas. Many tests are conducted on sorbent samples with varying masses, samples with the presence or absence of skin material found on the bamboo stem along with various treatments, and varying initial concentrations of mercury. Other studies conducted also include Three-Point Bending tests for structural integrity, Surface Area Measurements, and Scanning Electron Microscopy for microstructure studies. Results and analyses of these sorbents depict successful capture of mercury in nitrogen atmosphere. Treatments such as carbon dioxide activation and hydrochloric acid functionalization are very effective in enhancing mercury adsorption. This project acts as a stepping stone for the development of bamboo derived material. Major recommendations include the optimization of the sorbents for adsorption properties, and the scaling up of experiments. Eventually, a bamboo derived sorbent could be applied in coal-fired plants on a large scale for the capture of mercury.

M. Ing.

This thesis investigates the feasibility of producing activated carbon from polysaccharides. Activated carbons are high surface area solids with rich surface functionality and as a result, find use in a variety of industrial separation processes. The market for activated carbon is already established and growing but there is a huge push to find sustainable alternatives for the raw material used for its production, which is primarily coal. While there exists a significant amount of research on agricultural residues as potential replacements, there is minimal information on using polysaccharides as precursors for the production of activated carbon. Using the patented PGX process, two separate approaches were employed for the synthesis of activated carbon. The first method relied on the porous network of PGX materials to be maintained during pyrolysis while the second approach used a chemical agent to create porosity during the pyrolysis. Gas sorption analysis revealed that the PGX structure was not maintained during the pyrolysis stage hence losing all its pore network and extended surface area. Additionally, no significant variation between the PGX and non PGX variants of the chemically activated polymers was observed. However, it was revealed that the interaction between zinc chloride and pectin produced exceptionally high specific surface area (exceeding 2000 m2 g-1) activated carbon. The produced carbon had a high degree of microporosity (up to 100%) with some flexibility present in tuning the porosity. Elemental analysis revealed the carbon to have high surface functionality and preliminary adsorption test for removal of heavy metal ions from water (Pb2+ and Cd2+) showed promising results with the in-house carbon performing better than a representative commercial carbon. This study relies on statistical methods including multiple design of experiment studies and advanced characterization techniques to analyze the manufacturing process and the properties of carbon in an attempt to find the best conditions for producing activated carbon from polysaccharides. / Thesis / Master of Applied Science (MASc)