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Thesis (MScEng)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: Can salts present in an aqueous industrial effluent be retained by the [me ash that is produced as a by-product of gasification or by power stations utilising coal as the raw material? In order to answer this question, the actual chemistry that occurs during the mixing and settling process, needs to be understood. At the Sasol Secunda petrochemical plants in South Africa, ash is produced as a byproduct from the gasification of coal, and by the coal-fired power stations (steam plants). The [me portion of the ash (± 50J.lm in diameter) is disposed of through the use of a closed loop wet ash disposal system. The ash is transported as a slurry to the disposal sites (ash darns). The industrial effluent used to transport the ash consists mainly of the recycled ash effluent, known as clear ash effluent (CAE), as well as a variety of process waste streams containing high concentrations of salts. This mixture of ash and water is pumped to ash dams, where the ash is allowed to settle and is therefore separated from the effluent. From the ash darns the effluent flows into evaporation dams, and finally into CAE dams before being returned to the ash plant in Sasol 2 and 3 to be mixed once again with the ash. During this contact time of the ash with the water certain chemical reactions may occur. If one understands what chemical reactions occur during this process, and under what conditions they occur, then it will be possible to utilise the ash disposal system to its full potential, possibly enhancing the salt retention ability. An investigation was thus conducted into what processes actually occurs during the entire ash water contact period. The overall aim of the project was to obtain an understanding of the functioning of the [me ash disposal system so that its efficiency can be improved upon, and furthermore, so that the ash darns can be utilised more effectively in retaining salts. This investigation focussed on the chemical reactions that occur when an industrial effluent is mixed with fine ash, and consisted of four main aspects: • A literature survey on related issues. • An analysis and evaluation of the changes that occur in the actual disposal system. • Laboratory column experiments to investigate, in more detail, the different chemical reactions, which occur during the different stages of the disposal process. • The drilling of boreholes into the ash dams to obtain core material at a variety of depths and locations for analysis purposes. From this investigation it was concluded that salts are retained in the ash dams; based on the results obtained from the laboratory column experiments and the production rate of the fine ash from Sasol 2 and Sasol 3, the potential amount of salts that can be removed from the system (either due to precipitation or water retention in the ash dams) is approximately 95 tons/day. The salts that were found to be most pertinent to the wet ash disposal system utilised at Sasol, Secunda, are Ca, S04, Na, and Cl. Of these, Ca, S04 and Na were identified in literature to be the components most commonly associated with fly ash leachate. The Ca chemistry, which occurs in the ash disposal system, was explored extensively. Is was found that Ca, which is initially present in the fresh fine ash as lime, is leached from the ash into the effluent, where it reacts with carbon dioxide in the atmosphere, and is therefore removed from the system due to the precipitation of calcite. Sodium, S04, and Cl were all found to be retained in the ash; the S04 appears to be retained in a stable form within the ash, not merely due to hydraulic retention, which suggests that the ash system has the potential to act as a salt sink for S04 ions. The mechanism of salt retention in the ash darns was found to be predominantly by means of hydraulic retention, and therefore the salts have the potential to be flushed out of the ash dams into the underlying soil material. However, results from the core drilling exercise revealed that there doesn't appear to be a significant seepage of elements from the ash fill material into the underlying vertisol material. Some components (AI, Fe, Na, K, Mg, Cr, P, Ti and V) from the older, and inactive ash dam, do appear to have percolated into the underlying material. However, a significant amount of water, and therefore salts, are still retained in the ash dam. In terms of the mineralogical composition of the ash dams, a significant difference was observed between the mineral phases present in the ash fill material of an active and an inactive ash dam. Ettringite was detected throughout the borehole drilled into the inactive ash darn, and was not evident at all in the core material from the two boreholes drilled into the active dam, which suggests that this mineral is formed in the ash darns over a long time period. The minerals quartz and mullite were found in the fresh [me ash as well as in most of the core material obtained from the drilling exercise. The mineralogical composition of the ash fill samples, from the boreholes drilled into the centre of the active and inactive ash darns, was found to be very consistent with depth. This finding, combined with the fact that the chemical composition of the core samples varied more significantly in the borehole located near the edge of the active fine ash darn, indicated that the lateral position of the ash in the ash dam influences the chemical reactions that occur. Overall, from this investigation it was concluded that although the chemistry, involved in the mixing of an industrial effluent with fine ash, is extremely complex and site-specific, it is possible to determine the most significant changes which occur within a wet ash disposal system. Besides providing one with a better understanding of the working of the Secunda ash disposal system, the results of this investigation have also provided the framework for future research on this topic and related issues, i.e. the construction of a pilot scale ash darn set-up; further column experiments to investigate the extent to which S04 ions can be removed from the system; the influence of the addition of CO2 to the system; and more extensive core drilling in the vicinity of the ash darns. / AFRIKAANSE OPSOMMING: Kan soute teenwoordig in 'n industriële uitvloeisel teruggehou word in fynas geproduseer as neweproduk van steenkoolkragsentrales? Om 'n antwoord op hierdie vraag te kry, moet die chemiese reaksies wat gebeur tydens die meng en wegdoening van die as en aswater verstaan word. By die Sasol petrochemiese aanlegte in Secunda, Suid Afrika, word fynas geproduseer as 'n neweproduk in die vergassing en die stoomopwekkingprosesse. Die fynas (50)lm diameter) word weggedoen deur 'n geslote nat asstelsel. Die industriële uitvloeisel wat gebruik word vir die vervoer van die as bestaan hoofsaaklik uit hergebruikte aswater (genoem CAE - clear ash effluent), asook 'n verskeidenheid ander prosesafvalstrome wat hoë konsentrasies soute bevat. Die mengsel van as en aswater word in 'n asflodder gepomp na die asdamme, waar die as besink en sodoende geskei word van die waterfase (aswater). Vanaf die asdamme vloei die aswater na verdampingsdamme, en daarna na die CAE damme, vanwaar die CAE weer na die Sasol aanleg teruggepomp word om weer met as gemeng te word. Gedurende die kontak tussen die CAE en as gebeur sekere chemiese reaksies. Indien hierdie reaksies verstaan word, en onder watter toestande dit plaasvind, kan die asdamstelsel tot volle kapasiteit benut word deur moontlik die soutretensie binne die asdam te verhoog. 'n Ondersoek is gedoen om te bepaal watter prosesse plaasvind gedurende kontak tussen die as en water. Die doel van die ondersoek was om 'n beter begrip te kry oor die funksionering van die fynas-wegdoeningstelsel en om te bepaal of die asdamme meer effektiefbedryfkan word om moontlik meer soute te akkommodeer. Die ondersoek het uit vier hoofaspekte bestaan: • Literatuuroorsig, • 'n Analise en evaluering van die veranderinge wat plaasvind oor die asdamstelsel, • Laboratoriumskaal kolomeksperimente om in meer besonderhede die chemiese reaksies wat 'n rol in die aswaterstelsel speel, te bepaal, en • Die boor van toetsgate op die bestaande asdamme om boorkerne te ontleed by bepaalde dieptes en liggings. Uit die ondersoek is bevind dat soute wel in die asdamme behou word. As die kolomtoetse as basis gebruik word, en die produksietempo van fynas vanaf Sasol 2 en 3, dan kan daar 'n potensiële 95 ton soute per dag deur die asstelsel verwyder word (deur hoofsaaklik waterretensie en presipitasie van soute). Die mees prominente soute wat in die Sasol asstelsel voorkom is Ca, S04, Na, en Cl. Vanhierdie soute, is Ca, S04, en Na deur die literatuur geïdentifiseer as komponente wat met vliegas loog geassosieer word. Die Ca chemie, wat in die asstelsel plaasvind, is in besonderhede ontleed. Dit is bevind dat Ca, teenwoordig in die vars fynas as kalk, vanuit die as in die aswater geloog word, waar dit dan met atmosferiese CO2 reageer en dan vanuit die stelselverwyder word deur die presipitasie van kalsiet. Natrium, S04 en Cl word in die as teruggehou. Dit wil voorkom asof die S04 in 'n stabiele vorm in die as teruugehou word, nie net deur die hidrouliese retensie nie en dat die asstelsel dalk as 'n potensiële sink vir S04 kan optree. Die meganisme van soutretensie in die asdamme is hoofsaaklik deur hidrouliese retensie, met die gevolg dat die soute potensieel in die onderliggende grond uitgewas kan word. Die resultate van die boorkernondersoek wys egter dat daar nie beduidende uitwassing van hierdie soute in die grond is nie. Dit wil voorkom of sekere komponente (Al, Fe, Na, K, Mg, Cr, P, Ti en V) van die ou en onaktiewe asdam in die grond geloog is. 'n Beduidende verskil was gevind tussen die minerale fases in die asmateriaal van die aktiewe en onaktiewe asdamme. Ettringiet was teenwoordig deur die hele diepte van die boorkern van die onaktiewe dam, maar was nie teenwoordig in beide boorkerns van die gate op die aktiewe asdam nie. Dit impliseer dat hierdie mineraaloor 'n langer tyd gevorm word. Kwarts en mulliet was deurentyd in al die boorkerne teenwoordig. Die mineralogie van die boorkern van die middel van die aktiewe asdam was baie konstant met diepte (in teenstelling met dié van die boorkern op die kant van die asdam) wat daarop dui dat die laterale posisie van die as in die asdam die chemiese reaksies wat mag plaasvind kan beïnvloed. Die ondersoek bevestig dat alhoewel die chemiese reaksies betrokke in die aswaterstelsel baie kompleks en liggingspesifiek is, die mees beduidende veranderinge wat in die asstelsel plaasvind, wel bepaal kan word. Die ondersoek het benewens 'n beter begrip van hoe die asdamme reageer, ook 'n raamwerk gegee vir verdere navorsing in hierdie veld, bv. die bou van 'n loodsskaal-asdam, verdere kolomtoetse om die vermoë van die asstelsel om S04 ione te verwyder te bepaal en die invloed van gemanipuleerde kalsiet presipitasie deur die byvoeging van CO2.

This pilot plant study evaluated the pretreatment capabilities of a “Sessil” media for an undiluted high strength industrial wastewater (from a cellulose acetate manufacturing plant) over a ten-month period from May 1989. The Sessil media used consisted of 20 feet long 1.15 inch wide polyethylene strips hanging from wooden slats at the top of a 26 feet tall tower. The effects of organic and hydraulic loadings on the performance of the tower were examined. The characteristics of the influent wastewater on treatment performance were also determined. The wastewater, comprised mainly of waste acetic acid, some acetone, other organic solvents such as isopropyl alcohol, and some cellulose acetate fibers, had an average COD of 2300 mg/l, BOD of 1600 mg/l, influent suspended solids of 200 mg/l, SO₄ of 3000 mg/l, and an influent pH of 4.5, at an influent temperature of 40 C. The tower was found to consistently reduce the chemical oxygen demand (COD) of the wastewater even under adverse conditions as experienced during the shock loading phase when glacial acetic acid was added to the influent stream. During steady-state conditions, net total COD (TCOD) removals ranged from 28 to 52%, with an overall mean of 39%. For organic loads ranging from 164 to 374 lb TCOD/1000ft³day, the net removals (i.e. TCODinfluent-TCODeffluent) were between 81 to 104 lb TCOD, while biological removals (TCODinfluent-Soluble CODeffluent) ranged between 113 to 184 lb. COD removal was found to be an exponential function of the organic loading rate. The COD removals were not directly dependent on the hydraulic loadings, which ranged from 673 to 1738 gallons/day/ft². However, high hydraulic loading rates increased the rates of biomass sloughing and the variability of the tower effluent suspended solids (SS). The hydraulic retention time in the tower averaged 31 minutes and appeared insensitive to the hydraulic loading rates over the range studied. Volatile organic compounds did not appear to be a significant problem and there was insignificant volatilization of the compounds during its passage through the tower. Reductions in COD during volatilization tests were a result of biological stabilization. Tower influent organic constituents (viz. acids and alcohols) were reduced during passage through the tower. Acetic acid and acetone (the major components of the wastewater) were significantly reduced but incompletely removed. The other constituents (e.g. isopropyl and other alcohols) were more completely removed. Most of the removals appeared to have occurred in the upper one-third portion of the tower. / Master of Science