Thesis submitted in fulfilment of the requirements for the degree
Magister Technologiae: Chemical Engineering
in the Faculty of Engineering
at the
Cape Peninsula University of Technology
2014 / An awareness campaign on the harmful effects of Perfluorinated compounds (PFCs), especially Perfluorooctanoic acid (PFOA) and Perfluorooctane sulfonate (PFOS) has been conducted to inform the general public about the impact of these organic compounds on hu-mans and biota. These compounds have been shown to be potential carcinogens, as indi-cated by the United States Environmental Protection Agency (USEPA) and the Organization for Economic Co-operation and Development . A major concern about these chemicals is that they have been widely used in consumer products and have been detected in food and drinking water. They have been determined to be resistant to biological degradation, owing to their unique chemical and physical properties (fluorine atoms that have substituted hydrogen atoms in their chemical structure). Owing to their characteristics of being highly soluble in water, they cannot be removed from water using ordinary purification processes. Studies have been conducted to evaluate the removal of PFOA and PFOS from water using different methods. Among these methods, it has been proved that adsorption is a suitable method with the best adsorbent identified as activated carbon (AC). AC can be found in many forms, including as a fibre. The use of AC for the removal of PCFs can be augmented with sonica-tion and electro-chemical methods for rapid absorption of these compounds. The aim of this study was to remove these contaminants using a microporous AC fibre (ACF) made from an indigenous plant, Agave sisalana, which is widely available across sub-Saharan Africa, by using electro-physico-chemical methods. ACF has the following advantages when compared with granulated and/or powdered AC: it has a slightly larger reactive surface area; small quantities can be used; it is easily handled; it retains its shape under stress, thus does not require additional filtration to remove particulate residue; and can be regenerated easily.
The manufacturing process of the ACF was done in several steps: 1) harvesting of the A. sisalana leaves, stripping them to obtain wet fibre by scrapping using traditional meth-ods, 2) chemical activation using NaOH, KOH, ZnCl2 and H3PO4, employing a spraying method instead of soaking, which was followed by drying, and 3) carbonisation in a furnace at the required temperature. The use of activation reagents involved the determination of an appropriate concentration, with optimum concentrations determined as 0.54M, 0.625M, 1.59M and 0.73M for NaOH, KOH, ZnCl2 and H3PO4, respectively. Apart from the fibre acti-vation, temperature and activation time were also important parameters that were optimised. A response surface methodology was used to design a set of experiments that provided the optimum temperature and activation time. From the input variables, the Expert design soft-
ware generated experimental runs (n = 13) for each fibre activation reagent used with a tem-perature range of 450°C to 933°C being assessed for carbonisation time of between 17 to 208 minutes. ACF activated with KOH (0.54 M) and characterised by micropores with the highest surface area achieved being 1285.8 m2/g in comparison with Granular activated car-bon (Ounas et al., 2009) with an average surface area range of 1000 to 1100 m2/g. This sur-face area was measured using Dubinin-Astakhov isotherm with CO2 at 273 K. The physical characteristics of the ACF were analysed using a Scanning Electron Microscope to ascertain the integrity of the fibres.
PFOA and PFOS were analysed using a solid phase extraction (SPE) method fol-lowed by analysis using a liquid chromatography/tandem mass spectrometer (SPE-LC/MS/MS). The water sample volume used for extraction was 60 mL. The instrument used was an HPLC - Ultimate 3000 Dionex HPLC system and MS model - Amazon SL Ion Trap, with the following MS/MS operational conditions and ion mode: MS Interface → ESI; dry temp → 350C; nebulising pressure → 60 psi; dry gas flow → 10 L/min; ionisation mode → negative; capillary voltage → +4500V; end plate offset → −500V, while the separation col-umn was a Waters Sunfire C18, 5 μm, 4.6 × 150 mm column (supplier: Waters, Dublin, Ire-land), with an operational temperature of 30C.
Initially, adsorption studies (n = 48) using sonication (20 kHz) in batch systems indi-cated efficient removal of PFOA and PFOS within 120 min, with numerous samples (n = 14) achieving complete removal for both PFOA and PFOS. The minimum removal rates ob-served were 65.55% for PFOA and 95.92% for PFOS. From the ACF samples in which high-est removal rates were achieved, a number (n = 3) of the ACF samples were selected for surface characterisation. Based on the sonication in the previous experiments, an electro-physico-chemical adsorption regime was designed, to facilitate the rapid adsorption of PFOS and PFOA from contaminated drinking water in an electrolytic cell. In these experiments, si-multaneous sonication and electrolysis were used. A comparison was made between ACF produced in this study and the commercial activated carbon. The result revealed that adsorp-tion of PFOA and PFOS on ACF was a monolayer adsorption type phenomenon and had the best fit using a Freundlich isotherm compared with the Langmuir isotherm. Adsorption of PFOA and PFOS on the commercial AC presented a multilayer adsorption type of isotherm fit with the Langmuir isotherm having the best fit compared with the Freundlich isotherm.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:cput/oai:localhost:20.500.11838/867 |
| Date | January 2014 |
| Creators | Imwer, Serge Mapan |
| Publisher | Cape Peninsula University of Technology |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Thesis |
| Rights | http://creativecommons.org/licenses/by-nc-sa/3.0/za/ |
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