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Future work will focus on optimizing operating conditions, oxidation of real electroplating wastewaters, and investigation of the oxidation of PFOS replacements e. Work has begun on determining the reactivity of PFOS replacements e. Initial work focused on investigating the potential dependent reactivity of these compounds using density functional theory DFT modeling. A summary of these results is shown in Fig. The direct oxidation reaction was modeled, as it has been shown to be the rate limiting step for PFOS oxidation.
According to the results shown in Fig. These results suggest that FTS should react readily via electrochemical oxidation. The laboratories were shut down on March 15, , and reopened on June 15, at limited capacity. For obvious reasons, the project period was extended by one year. A schematic of the tubular reactor is shown in Fig. It is comprised of a tubular Ti 4 O 7 reactive electrochemical membrane REM and a centrally located stainless steel rod. The NaClO 4 background electrolyte was chosen as a non-electroactive electrolyte that could mimic the solution conductivity of electroplating wastewater. The results are shown in Fig. The data fit a second-order model, with a R2 value of 0.
Further work is underway to investigate PFAS oxidation in synthetic wastewater samples. Laboratory work this quarter continued to focus on the development of a tubular reactor to test PFAS oxidation. Work was specifically focused on overcoming challenges related to current collector corrosion. It was found that plugging the pores on the ends of the membrane using a sol-gel method and utilizing niobium as a current collector overcame problems with corrosion. Since the electrode is porous, the current collector was in direct contact with the electrolyte as it permeated through the pores. To overcome the corrosion of the current collector, two strategies were utilized. First, different metals were investigated as suitable current collectors.
Second, the pores on the edge of the REM were sealed to provide an area for connection of the current collector where the electrolyte was not present. For the first task, we tested several metals e. It was found that both Nb and Ta were the most resistant to corrosion, and ultimately Nb was chosen because it is cheaper than Ta. The second task i. Sealing of the pores was accomplished using a dip coating procedure, that is shown schematically in Fig. The hydrolysis step allowed for the growth of the TiO 2 coating, and the heat treatment provided adhesion and reduction of the TiO 2 coating to Ti 4 O 7.
The procedure shown in Fig. The oxidation experiments were performed in synthetic solutions, using a crossflow setup in full recycle mode. The synthetic solutions were prepared by spiking perfluorooctanoic acid PFOA into a background electrolyte that has an ionic strength that is representative of industrial electroplating wastewaters i. The reaction rate constants were found to be approximately second-order with respect to total PFAS concentration, indicating that interactions between adsorbed intermediates is likely involved in the reaction mechanism. Additionally, shorter-chain PFASs were observed to form and degrade throughout the experiment. Therefore, future work will focus on improving electrocatalytic activity to minimize the production of these compounds.
The operating conditions for the electrochemical oxidation experiments are shown in Table 2 above and results are shown in Fig. Three initial PFAS concentrations were investigated i. It was found that rapid removal was observed for the initial two hours of the experiment i. All three concentrations showed the production of short chain compounds, which is in line with the literature. Currently, researchers are studying ways to make ethanol from cellulose that is extracted from biomass, such as corn cobs, corn stover stalks and leaves , straw from wheat or rice, perennial grasses, such as Miscanthus and switchgrass, and wood waste from the forestry and paper industries. Truck and rail transportation are the major modes of moving ethanol to the blending terminals, where ethanol is mixed with gasoline to form the E or E blends for consumer engine use.
Currently ethanol is not transported by pipelines that are designed and used for petroleum-based products, however a few companies are testing shipping ethanol this way. Using the more expensive truck, rail and barge transportation increases the costs to the markets most distant from the ethanol plants. Ethanol is a good fuel for use in spark-ignition engines. It has a high octane number, making it attractive as an antiknock additive in gasoline.
It can be used as an additive for diesel biodiesel. Ethanol is also an important feedstock for the chemical industry. Ethanol production results in a net energy gain— according to some authoritative life-cycle analyses— producing about 67 percent more energy than it takes to grow and process the corn into ethanol. Liska, Haishun S. Yang, Virgil R. Bremer, Terry J. Klopfenstein, Daniel T. Walters, Galen E. Erickson, and Kenneth G.
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