The production of both fresh water and waste streams are progressively increasing over the years due to ongoing population growth coupled with high levels of increase in water consumption. The ongoing growth of human activities, such as industry, recreation, and agriculture, are significantly contributing to the increase in both water demand and severity of degradation of natural water resources. The majority of the industrial wastewaters have a significant impact on the environment; some of which may pose a number of threats to human health and the surrounding environment. Thus, discharge of such waste streams into a surface water and/or groundwater presents a major source of water pollution in many countries. Therefore, these waste streams must be disposed of in an environmentally acceptable manner. The primary concern of the PhD thesis is to seek the most feasible and applicable freezing desalination technologies that are potentially capable to concentrate the dissolved ionic content of the liquid streams, especially for those causing severe pollution problems. Therefore, various forms of melt crystallisation processes, namely; agitated and static crystallisation processes, ice maker machines, a Sulzer falling film crystallisation process, the Sulzer suspension crystallisation process, and the Sulzer static crystallisation process, were experimentally used and investigated. The experimental investigations were carried out on the laboratory bench scale and/or straightforward pilot plant by using aqueous solutions of sodium chloride and/or process brines as feed samples. The study was focused on a number of important parameters influencing the separation performance of the investigated treatment systems. In general, the resulting experimental data for each innovative process were highly encouraging in minimising the volume of the waste stream, and substantially increasing the amount of product water. The obtained product water was ready for immediate use either as drinking water or as a saline water of near brackish water or seawater qualities. Also, relationships between the influences and the separation performance, in terms of salt rejection and water recovery ratios, were explored and determined for the investigated technologies. Based on the experimental results, the Sulzer melt crystallisation processes were scaled up and were combined into a commercial reverse osmosis membrane desalination plant. As a result, three novel treatment option configurations were proposed for minimising the waste stream, whilst increasing the production rate of drinking water and/or preserving a substantial amount of natural water resource from the RO plant's exploitation.

In this thesis we aim to provide computationally efficient methods of performing waterbarrier simulations. The innate challenge in simulations of structures such as sea or surge barriers is resolution. Because barriers tend to be long and thin compared to the surrounding landscapes they protect, one must put mesh refinement on the barrier region in order to even numerically recognize the barrier’s presence. This is a costly computation due to the CFL condition which puts a strict limit on the size of time step proportional to the spatial mesh size. Another issue is the complexity of meshing near the barrier. Since barriers are most likely slanted or have certain shapes, the grid has to reflect this in the form of a grid mapping or an unstructured grid. To mitigate the issue of resolution, we propose an approximation of the barrier with a line interface embedded on a Cartesian grid, reducing our problem to an embedded boundary problem. Then to avoid complex meshing, we develop three cut cell methods on two shapes of barriers: 1) the h-box method (HB), 2) the state redistribution method (SRD), and 3) the cell merging method (CM). Doing this two-step approach means that we can lower the resolution near the barrier region and still feel the presence of the barrier and capture its effect, which would otherwise not be the case if we relied on resolution for representation of the barrier. This does not mean that we are losing accuracy by lowering resolution, however. Rather, we are maintaining about the same accuracy while also lowering resolution (and thus cutting computational cost), which we show by comparison with a refined barrier. We solve the shallow water equations as our underlying PDEs to simulate water interaction with the barrier, as they are commonly used in tsunami and storm simulations. We implement our work on the PYCLAW framework, which is an objected oriented program that solves conservation laws.

A greenhouse study was conducted involving interactive effects on bean yield of three levels of irrigation water salinity, three frequencies of irrigation water app li cation, two level s of nitrogen, and seven levels of phosphorus fertilization to determine if the effects of adverse saline conditions or water stress could be overcome by fertility and / or saline water management. Dry matter and bean yields were reduced with decreasing irrigation frequency (2 days to B days} and increasing salinity of irrigation water (0.5 mmho/cm to 8.0 mmho/cm). At low salinity levels (0 .5 mmho/cm) dry matter production and the number of pods per pot were increased with the addition of nitrogen in the irrigation water (at the rate of 112 kg N/ha). The application of banded fertilizer phosphorus helped beans overcome the effects of saline conditions and water stress and resulted in increased yield. The application of liquid 10-34-0 fertilizer produced a statistically significant increase in all yield parameters at every level of salinity, and every irrigation frequency studied. Nitrogen fixation was found to decrease as irrigation water salinity increased. The application of 0-50-40 as a fertilizer band treatment increased nitrogen fixation in t he presence of added nitrogen, due probably to the presence of potassium.

Abstract in English and German / The reported PhD research study was conceived from real water problems experienced by a rural community in South Africa (SA). Specifically, water quality in the Nandoni Dam situated in the Vhembe District, Limpopo Province, South Africa was assessed in order to determine its fitness for use, following complaints by community members using this water for drinking and domestic purposes. The dam supplies water to 55 villages with approximately 800 000 residents. At the inception of the study, there was little scientific information relating to the quality of the water in the dam. Water samples from various sites across the Nandoni Dam, a primary source of domestic water supply in the region, were collected through each season of the year over a period of 12 months to ascertain the concentrations of dissolved salts in the dam. Additionally, harmful polycyclic aromatic hydrocarbons (PAHs) and phenols were assessed. The concentrations of the ions contributing to water salinity were generally lower than the brackish water bracket (i.e. 500 – 30 000 mg/L) but too high for potable water. The concentration of the phenols was relatively higher than the threshold limit of drinking water. Therefore, the water sourced from the Nandoni Dam was found not suitable for human consumption and therefore required integrated water resource management, as well as robust and cost-effective water treatment especially since the salinity of the water was high even after treatment by a water treatment plant sourcing water from the dam. In an attempt to develop a suitable energy-efficient technology or system for complete removal of salts (desalination) from the salty water (including brackish water), electrospun polyvinylidene fluoride (PVDF) nanofibre membranes were synthesised and evaluated for removal of salts using the Direct Contact Membrane Distillation (DCMD) process. The nanofibre membranes were synthesised with combined high mechanical stability, porosity, and superhydrophobicity to prevent fouling and wetting while maintaining high salt rejection and water flux. Organically functionalised silica nanoparticles (f-SiO2NPs) were embedded on PVDF nanofibre membranes using an in-situ electrospinning technique for superhydrophobicity enhancement. These modified membranes displayed Young’s modulus of ~43 MPa and showed highly porous properties (~80% porosity, 1.24-1.41 μm pore sizes) with superhydrophobic surfaces (contact angle >150°). Membranes embedded with octadecyltrimethoxysilane (OTMS), and chlorodimethyl-octadecyl silane (Cl-DMOS), octadecyltrimethoxysilane (ODTS)-modified SiO2NPs were the most efficient; rejecting >99.9% of NaCl salt, with a water flux of approximately 30.7-34.2 LMH at 60°C, thus indicating their capacity to produce potable water. The superhydrophobic membranes were coated with a thin layer consisting of carboxylated multiwalled carbon nanotubes (f-MWCNTs) and silver nanoparticles (AgNPs) to reduce membrane fouling. The AgNPs and f-MWCNTs were uniformly distributed with size diameters of 28.24±1.15 nm and 6.7±2.1 nm respectively as evidenced by transmission electron microscopy (TEM) micrographs. The antibacterial AgNPs embedded in the PVDF nanofibre membranes inhibited the growth of Gram-positive Geobacillus stearothermophilus and Staphylococcus aureus as well as Gram-negative Pseudomonas aeruginosa and Klebsiella pneumoniae indicating their potential to prevent biofilm formation. Fouling tests were conducted using bovine serum albumin (BSA), sodium alginate, colloidal silica, and thermophilic bacteria effluent as model organic, inorganic, and bio-foulants, respectively, using DCMD. The uncoated membranes were characterised by a flux decays ranging from 30% to 90% and salt rejection decays ranging from 1.4% to 6.1%. Membrane coating reduced the flux and salt rejection decays to 10–24% and 0.07–0.75%, respectively. Although the initial flux decreased from 42 to  16 LMH when using coated membranes, the resistance of these coated membranes to water flux and salt rejection decays indicated that coating could be a suitable one-step solution for fouling mitigation in DCMD. The major challenge would be to design the MD membranes with architectures that allow a high-water flux to be maintained i.e., a highly porous layer. Furthermore, the volatile compounds bearing hydrophobic groups were pretreated to reduce their fouling capacity on PVDF nanofibre membranes. In this study, polyacrylonitrile (PAN) and polyethylene-imine (PEI) functionalised-PAN nanofibre membranes were synthesised and evaluated as a pretreatment for the removal of chlorophenol and nitrophenol from solutions. Under optimised experimental conditions, adsorption capacities ranging from 27.3 – 38.4 mg/g for PAN and PEI-modified nanofibres, respectively, were recorded. The PEI-functionalised nanofibres showed a high potential as a pretreatment step to be integrated to MD process. Ultimately an integrated water desalination system was developed. This involved a pretreatment filter (pore size ~100 μm) containing PEI-functionalised PAN nanofibre materials to reduce particulates and large molecules of dissolved organic/inorganic compounds from the water to be treated. In this research, it was observed that the pre-treatment step was not sufficient in removing all traces of compounds causing fouling of the superhydrophobic PDVF nanofibre membranes. As such, coating of the membranes with a thin hydrophilic layer and coupled with the filtration pretreatment step was found to provide fouling-resistance properties, high salt rejection, and low flux decays on brackish water collected at an estuary in Belgium and the Nandoni Dam in South Africa, demonstrating the potential of the MD separation process towards potable water recovery from brackish water. / Het onderzoek in dit proefschrift was gebaseerd op concrete waterproblemen die een landelijke gemeenschap in Zuid-Afrika (SA) ervaart. In het bijzonder werd de waterkwaliteit in het Nandoni-reservoir in het Vhembe-district in de provincie Limpopo in Zuid-Afrika onderzocht, om te bepalen of dit water geschikt is voor gebruik, na klachten van leden van de gemeenschap die dit water gebruiken als drinkwater en voor huishoudelijk gebruik. Het reservoir levert water aan 55 dorpen met ongeveer 800.000 inwoners. Bij het begin van het onderzoek was er weinig wetenschappelijke informatie over de kwaliteit van het water in het reservoir. Watermonsters van verschillende locaties in het reservoir, dat een primaire bron van drinkwater is in de regio, werden gedurende verschillende seizoenen van het jaar verzameld over een periode van 12 maanden, om de concentraties van de meest voorkomende ionen in het reservoir te bepalen. Bovendien werden de concentraties van schadelijke polycyclische aromatische koolwaterstoffen (PAK's) en fenolen gemeten. De concentraties van de ionen die bijdroegen aan het zoutgehalte van het water waren in het algemeen lager dan de drempel om het water als brak water te bestempelen (dat wil zeggen 500 – 30 000 mg/l), maar waren te hoog voor drinkwater. De concentratie van de fenolen was hoger dan de limiet voor drinkwater. Daarom bleek het water afkomstig van het Nandoni reservoir niet geschikt voor menselijke consumptie. Een beter geïntegreerd waterbeheer is dus nodig om deze bron voor drinkwater te beschermen, naast een robuuste en kosteneffectieve waterbehandeling. Deze waterbehandeling moet vooral het zoutgehalte van het water naar beneden halen, maar ook de concentraties van fenolen. In een poging om een geschikte energie-efficiënte technologie of een systeem voor de volledige verwijdering van zouten (~ontzilting) uit brak water te ontwikkelen, werden elektrisch gesponnen polyvinylideenfluoride (PVDF) nanovezelmembranen gesynthetiseerd en beoordeeld op verwijdering van zouten met behulp van Direct Contact Membraandestillatie (DCMD). De nanovezelmembranen hadden een gecombineerde hoge mechanische stabiliteit, porositeit en superhydrofobiciteit, die hielp om vervuiling (fouling) en vloeistofintrede in de poriën (wetting) te voorkomen, terwijl een hoge zoutverwijdering en hoge waterflux doorheen de membranen gehandhaafd bleven. Organische gefunctionaliseerde silica-nanodeeltjes (f-SiO2NP's) werden nadien geïncorporeerd in de PVDF nanovezelmembranen met behulp van een in-situ elektrospinning techniek om zo een nog grotere superhydrofobiciteit te bekomen. Deze gemodificeerde membranen hadden een degelijke treksterkte (Young's modulus van ~ 43 MPa) en waren zeer poreus (~ 80% porositeit, 1.24-1.41 μm poriegrootte). Het oppervlak van de membranen vertoonde inderdaad superhydrofobe eigenschappen (contacthoek met water > 150 °). De membranen ingebed met octadecyltrimethoxysilaan (ODTS) SiO2NP's waren het meest efficiënt: ze toonden een zoutretentie van> 99.9% voor NaCl, bij een waterflux van ongeveer 30.7-34.2 l/(m².h) bij 60 ° C (ten opzichte van 20°C in het permeaat), wat aangeeft dat ze in staat zijn om drinkbaar water te produceren. De superhydrofobe membranen werden nadien ook gecoat met een dunne laag bestaande uit gecarboxyleerde multiwall-carbon nanotubes (f-MWCNT's) en zilver nanodeeltjes (AgNP's), in een poging om membraanvervuiling te verminderen. De AgNP's en f-MWCNT’s hadden uniforme diameters van respectievelijk 28,24 ± 1,15 nm en 6,7 ± 2,1 nm (zoals bleek uit transmissie-elektronenmicroscopie (TEM)). De antibacteriële AgNP's ingebed in de PVDF-nanovezelmembranen remden de groei van Gram-positieve Geobacillus stearothermophilus en Staphylococcus aureus bacteriën, evenals Gram-negatieve Pseudomonas aeruginosa en Klebsiella pneumoniae bacteriën. Dit toont het potentieel van deze membranen om biofilmvorming te voorkomen. Vervuilingsproeven (in DCMD) werden uitgevoerd met behulp van runderserumalbumine (BSA), natriumalginaat, colloïdaal silica, en thermofiele bacteriën - als respectievelijk organische, anorganische en biologische vervuiling. De niet-gemodificeerde membranen werden gekenmerkt door een fluxverval, met een daling van de flux met 30% tot 90%, naast een daling van de zoutretentie met 1.4% tot 6.1%. Bij de gecoate membranen daalde de flux slechts met 10-24% en de zoutverwijdering slechts met 0.07-0.75% respectievelijk. Hoewel de initiële flux ook afnam (van 42 naar ± 16 l/(m².h)) bij het gebruik van gecoate membranen, toonde de hogere weerstand tegen vervuiling van deze gecoate membranen aan dat deze coating een geschikte oplossing zou kunnen zijn tegen vervuiling in DCMD. Bovendien kan de synthese in één stap verlopen. De grootste uitdaging zal echter zijn om MD-membranen te ontwerpen waarbij de coating de oorspronkelijke waterflux/de porositeit van de membranen niet teveel verlaagt. Daarnaast werden gemodificeerde PVDF nanovezels geproduceerd om de verwijdering van vluchtige, hydrofobe stoffen (zoals fenolen) door adsorptie aan deze vezels te verhogen. Er werden polyacrylonitril (PAN) en polyethyleen-imine (PEI) gefunctionaliseerde PAN nanovezels gesynthetiseerd, waarna deze geëvalueerd werden als adsorbens (en dus voorbehandeling voor de membraanstap) voor chloorfenol en nitrofenol. Onder geoptimaliseerde experimentele omstandigheden werden adsorptiecapaciteiten tussen respectievelijk 27.3 en 38.4 mg / g voor PAN- en PEI-gemodificeerde nanovezels gemeten. De PEI-gefunctionaliseerde nanovezels vertoonden een hoog potentieel als een voorbehandelingsstap voor de hierboven beschreven DCMD. Tenslotte werd ook een geïntegreerd waterontziltingssysteem ontwikkeld. Dit systeem bestond uit een voorbehandelingsstap met PEI-gefunctionaliseerde PAN-nanovezels (in de vorm van een membraan met poriegrootte ~100 μm), gevolgd door een gemodificeerde DCMD stap. De voorbehandeling diende om deeltjes en grote opgeloste organische verbindingen uit het te behandelen water te verwijderen voor de DCMD-stap. In dit onderzoek werd waargenomen dat de voorbehandelingsstap niet voldoende was om alle organische contaminanten te verwijderen die vervuiling veroorzaakten op de superhydrofobe PDVF nanovezelmembranen in de DCMD-stap. Toch bleek coating van de DCMD membranen met een dunne hydrofiele laag (gekoppeld aan de voorbehandelingsstap) een voldoende bescherming tegen vervuiling te bieden zodat de zoutretentie en waterflux van deze membranen hoog bleef. De combinatie van voorbehandeling – gemodificeerde DCMD werd succesvol getest op water uit de Schelde en uit het Nandoni reservoir, waarmee het potentieel van de technologie om drinkwater uit brak water te produceren werd aangetoond. / School of Science / Ph.D. (Applied Biological Science : Environmental Technology)

Thesis (MEng)--Stellenbosch University, 2000. / ENGLISH ABSTRACT: Fouling is readily acknowledged as one of the most critical problems limiting the wider application of membranes in liquid separation processes. A better understanding of fouling layer formation and its monitoring is needed in order to improve on existing cleaning techniques. Plant operation can be optimised if fouling can be monitored by noninvasion means either on the plant itself or on an attached monitoring device. The overall scope of this research was to develop a non-destructive, real-time, in situ visualisation technique or device for concentration polarisation and fouling layer monitoring. Ultrasonic-time-domain-reflectometry (UTDR) was employed as a visualisation technique to provide real-time characterisation of the fouling layer. A 24 cm-long rectangular flat sheet aluminium cell was designed and used as separation device for a desalination system. The experimental results obtained using this module confirmed that there are an excellent correspondence between the flux decline behaviour and the UTDR response from the membrane. The ultrasonic technique could effectively detect fouling layer initiation and growth on the membrane in real-time. In addition to the measurement of fouling, the ultrasonic technique was also successfully employed for monitoring membrane cleaning. Since no real-time permeation data is available during cleaning operations in industrial applications, a UTDR monitoring device may prove to be a very valuable technique in optimising cleaning strategies. The technique was further tested on an 8-inch diameter spiral wrap industrial module and good results were obtained. Stagnant zones, as well as flux flow behaviour inside the module could be determined. However, more research IS needed to fully understand the complex phenomena inside a spiral wrap module. Overall, the UTDR technique and its use in monitoring devices have a major impact in the membrane industry due to its extremely powerful capabilities. / AFRIKAANSE OPSOMMING: Membraan-bevuiling of -verstopping is die grootste struikelblok wat die algemene aanwending van membrane vir verskillende watersuiweringsprosesse negatief beinvloed. 'n Beter begrip van membraan-bevuiling, asook beter metingsmetodes daarvan is nodig om op bestaande skoonmaaktegnieke te verbeter. Die hoofdoel van hierdie studie was die ontwikkeling van 'n nie-destruktiewe-in-lyn visuele tegniek vir die meting van konsentrasie polarisasie en membraan-bevuiling. Deur gebruik te maak van ultrasoniese klank golwe, is 'n tegniek ontwikkel wat 'n direkte visuele aanduiding kon gee van die toestand van membraan-bevuiling binnein die module. 'n Reghoekige aluminium-module, 24 cm lank, is ontwerp en gebou waarbinne die membraan geplaas is vir die skeidingsproses. Resultate dui daarop dat daar 'n uitstekende verband bestaan tussen die afname in permeaatvloei en die ultrasoniese eggo vanaf die membraan. Die ultrasoniese tegniek kon die vorming van en toename in membraan-bevuiling doeltreffend karakteriseer. In teenstelling hiermee, is die tegniek ook suksesvol aangewend om die skoonmaak-proses van membrane te ondersoek. Met min of geen data beskikbaar vir die skoonmaak-proses van membrane in die industriële sektor, het die tegniek enorme potensiaal in die optimisering van bestaande skoonmaak-tegnieke. Die tegniek is verder aangewend op 'n industriële 8-duim deursnee spiraal-module en goeie resultate is verkry. Stagnante sones asook vloed-vloei-patrone binne-in die module kon suksesvol bepaal word. Baie navorsing is egter nog nodig om die ingewikkelde data wat gegenereer word tydens die ondersoek van 'n spiraal-module ten volle te verstaan. Die enorme potensiaal en moontlikhede van die ultrasoniese tegniek kan die begin wees van 'n revolusie in die membraan-industrie.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007. / Electrodialysis is a method of water desalination which involves the separation of TDS through an ion-exchange membrane under a potential gradient. In this study it was attempted to reverse engineer the composite carbon ion-exchange membrane used in a prototype plant and electrochemically evaluate a prototype desalination cell. The influence of applied potential on the capacitance of the various electrode surfaces and possible electrode reactions was investigated. A model was also suggested to describe the conductivity through the membrane. The composition of composite carbon membranes were determined by compositional analysis using various analytical tools. Elemental analysis, done with PIXE and EDS, showed that the membranes contained chloride, fluoride, oxygen, carbon, and possibly hydrogen. With LC-MS and IR it was established that the membranes consisted of two polymers with no carbonyl or aromatic functional groups. After further thermal analysis the following possible compounds remained: hexafluoropropylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene (PCTFE), polyoxyethylene oxide (PEO) and polyethylene glycol (PEG). This assessment is in good agreement with the contents of US patent 4,153, 661, which describes the composite membrane.

Thesis (MScEng)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: South Africa is a relatively dry country with an annual average rainfall of 464mm compared to a world average of 860mm (WSA, 2009). Water shortages and droughts are fairly common to the western and high lying of regions South Africa. Due to its population growth and the rapid development, like the rest of the world, there has been an increased demand for water. Due to increasing costs of procuring water and its decreasing availability, the option of using seawater as a source for freshwater or directly in industrial processes has become competitive, especially in the arid parts of the world. The design of seawater intakes forms an integral part of providing a secure source of seawater. The objective of this thesis is to aid in the development of guidelines for the design of small scale seawater abstraction systems on rocky coastlines using the Horizontal Well Method. Recommendations for guidelines will be given. / AFRIKAANSE OPSOMMING: Geen opsomming

The principal objective of water resources planning is generally recognized to be the satisfaction of the continually growing desires and requirements of a population for usable water. In long term planning of such resources, fulfillment of these needs at a minimum cost can be defined as the objective. The time-capacity relationship that describes the decision process for the arrival at an optimum and feasible construction schedule hold the answer to the decision question: how much to build and when. The application of the time-capacity approach is used in the problem of staging of investment in desalination capacity and associated storage facilities. The forward dynamic programming technique is utilized in the solution process. A preliminary analysis is performed, with artificial data, in the initial development of a decision rule governing , an idealistic model of an arid region. The area of study is assumed to depend solely on desalination of sea water for its supply of potable water, with no appreciable groundwater source available in the region. Desire for water is assumed to follow a linearly rising trend for a finite period into the future taken as the duration of the project. A more realistic set of data is later considered in the development of an optimal incrementation rule for the augmentation of desalination production. The State of Kuwait is considered as the area of study, and pertinent data were collected from that region. Rate of demand growth for water use is described here to follow an exponential trend resembling that of the projected population growth at an assumed rate of growth. Capital costs only are considered in the minimizing functional equation of the decision rule, and an appropriate discount rate is assumed in the obtainment of the present value of incurred costs. A spatial construction schedule is described by the solution algorithm which specifies the sizes of the required increments to production and their optimal time of erection. An economic analysis of the state of the art in storage facilities resulted in the elimination of storage capacity as a state variable in the dynamic program. The operational problems of desalination units in production are dealt with, all within the total supply system requirements of meeting the desired demand for fresh water. The capacities of the incrementation schedule of desalination plants are modified to accommodate the expected shortages due to the annual scheduled maintenance, forced outages and peaking of the water use curve due to seasonal variations. Technical data of actual plants in operation in Kuwait are analyzed to obtain the restrictions on the operational requirements of the production plants. The plants considered are of the multi-stage flash type (MSF) currently in use in Kuwait. Simulation of the production operation of the required units at every stage of incrementation is performed. The final costs of the modified supply system components are obtained in accordance with the assumed probability of meeting demand within the total number of simulations. The general solution algorithm is viewed in two interrelated parts. The first part produces the schedule of incrementation and construction of the necessary desalination units. The second part modifies these capacities to account for the operational and seasonal requirements of the project. The ultimate result is a schedule of modified capacities of production and a maintenance program for every unit in operation, with the effects of forced outages and peaking of the demand curve applied on each plant.

Salts in solution should be removed by desalination techniques to prevent equipment fouling and corrosion. Common desalination technologies are energy intensive such as Multi Stage Flash (MSF) distillation which requires 14.5 J/m3 (Ribeiro. J, 1996) of energy. Desalination technologies produce purified water and a concentrated salt solution, where the salt concentration is dependent on the desalination technology used. This work investigates gas hydrate technology as a possible desalination technology. Hydrates are composed of guest molecules and host molecules. Guest molecules may be in the form of a liquid or gas. During hydrate formation, host molecules, water, form a cage enclosing the guest molecule. Common hydrate formers or guest molecules such as; methane, ethane, propane and carbon dioxide are currently being investigated in literature, for use in gas hydrate desalination technology. Common hydrate formers form hydrates at low temperatures; below 288 K and high pressures; above 2 MPa. To increase the temperature and reduce the pressure at which gas hydrates form, commercially available hydrofluorocarbon hydrate formers such as R14, R32, R116, R134a, R152a, R218, R404a, R407c, R410a and R507 are preliminarily investigated in this work. The criteria for choosing the most suitable fluorine-based formers require the former to be: environmentally acceptable where it is approved by the Montreal Protocol; non-toxic where it has a low acute toxicity; non-flammable; chemically stable; a structure II hydrate to simplify the washing process; available in commercial quantities; low cost in comparison to other hydrate formers; compatible with standard materials and contain a high critical point for a large heat of vaporisation (McCormack and Andersen, 1995). Taking all these criteria into account, R134a was chosen for further investigation as a possible hydrate former. In this work, hydrate-liquid-vapour phase equilibrium measurements are conducted using the isochoric method with a static high pressure stainless steel equilibrium cell. The Combined Standard Uncertainty for the 0-1 MPa pressure transducer, 0-10 MPa pressure transducer and the Pt100 temperature probes are ±0.64 MPa, ±5.00 MPa and ±0.09 K respectively. Vapour pressure measurements for Hydrofluoropropyleneoxide, CO2, R22 and R134a were measured to verify the pressure and temperature calibrations. Hydrate test systems for R22 (1) + water (2) and R134a (1) + water (2) were measured to verify calibrations, equipment and procedures. New systems measured included R134a (1) + water (2) + {5wt%, 10wt% or 15wt%} NaCl (3). For the system R134 (1) + water (2) at 281 K the dissociation pressure is 0.269 MPa. However, addition of NaCl to the system resulted in a shift of the HVL equilibrium phase boundary to lower temperatures or higher pressures. The average shift in temperature between the system R134a (1) + water (2) containing no salt and the systems containing {5, 10 and 15} wt% NaCl are -1.9K, -4.8K and -8.1K respectively. In this work, the measured systems were modelled using two methods of approach. The first method is where hydrofluorocarbon hydrate former solubility is included, (Parrish et al., 1972) and the second is where hydrofluorocarbon hydrate former solubility is ignored, (Eslamimanesh et al., 2011). From these models, it is found that hydrofluorocarbon solubility could not be neglected. In this work, the hydrate phase was modelled using modifications of the van der Waals and Platteeuw model, (Parrish et al., 1972). The liquid and vapour phases are modelled using the Peng- Robinson equation of state with classical mixing rules (Peng, 1976). The electrolyte component is modelled using the Aasberg-Peterson model (Aasberg-Petersen et al., 1991) modified by Tohidi (Tohidi et al., 1995). The percent absolute average deviation (%AAD) for the systems, which includes solubility, is 0.41 for R22 (1) + water (2) and 0.33 for R134a (1) + water (2). For the system R134a (1) + water (2) + {5 wt%, 10 wt% or 15 wt%} NaCl (3) the % AAD is 5.14. Using the hydrate former, R134a, is insufficient to ensure gas hydrate technology is competitive with other desalination technologies. Hydrate dissociation temperature should be increased and pressure decreased further to ambient conditions. As evident in literature, promoters, such as cyclopentane, are recommended to be added to the system to shift the HLV equilibrium phase boundary as close to ambient conditions as possible. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2011.

Barometric distillation is an alternative method of producing fresh water by desalination. This proposed process evaporates saline water at low pressure and consequently low temperature; low pressure conditions are achieved by use of barometric columns and condensation is by direct contact with a supply of fresh water that will be augmented by the distillate. Low-temperature sources of heat, such as the cooling water rejected by electrical power generating facilities, can supply this system with the latent heat of evaporation. Experiments are presented that show successful distillation with a temperature difference between evaporator and condenser smaller than 10ê C. Accumulation of dissolved gases coming out of solution, a classic problem in lowpressure distillation, is indirectly measured using a gas-tension sensor. The results of these experiments are used in an analysis of the specific energy required by a production process capable of producing 15 liters per hour. With a 20ê C difference, and neglecting latent heat, this analysis yields a specific energy of 1.85 kilowatt-hour per cubic meter, consumed by water pumping and by removal of non-condensable gases. / by Eiki Martinson. / Thesis (M.S.C.S.)--Florida Atlantic University, 2010 / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2010. Mode of access: World Wide Web.