Gypsum (calcium sulphate dihydrate) is of great industrial importance with over 95,000 ktonnes being used in the world per annum. The greatest use of gypsum is in the production of plaster (calcium sulphate hemihydrate) for use as an interior finisher. Plaster is produced by the calcination (thermal decomposition) of gypsum. The most popular design is a continuous calciner where gypsum is fed continuously and is directly heated by hot air. There are a number of different phenomena occurring within a calciner, including heat transfer, mass transfer, particle and gas mixing, elutriation and the dehydration reaction itself. All these processes interact with each other. Although a lot of research has been carried out in these areas already, the literature has been found to contain significant discrepancies. This study contains experimental work which has been carried out in order to better understand the physical processes occurring within a gypsum calciner. The rate of dehydration of gypsum (35-67μm in diameter) has been studied in a fluidised bed reactor. Experiments were carried out at bed temperatures of 100 to 170°C. The fluidising gas was air with water vapour pressures of 0.001 to 0.30 atm. The dehydrations were under differential conditions. The results show that the dehydration under these conditions can be successfully modelled using the two dimensional Avrami-Er'ovev expression. A study of the fluidisation and elutriation properties of gypsum in batch vessels (cylindrical and conical) has been carried out. The mechanics of elutriation has been investigated and modelled for various freeboards, superficial gas velocities and air humidities. Tracer tests have also been carried out on a laboratory scale continuous conical kettle. Sodium carbonate was used as the inert tracer material. Runs were carried out at different air and gas flowrates and different bed temperatures. Residence time distributions were elucidated. Finally, the above experimental data and component models have been investigated for their applicability to producing a model of the laboratory scale gypsum calciner.

published_or_final_version / abstract / toc / Dentistry / Master / Master of Philosophy

No description available.

Deposition of calcium carbonate (CaCO3) and calcium sulfate (CaSO4) causes serious processing problems and limits the productivity of seawater reverse osmosis (RO) desalination. The interactions between CaSO4 and CaCO3 in the dynamic seawater RO systems have been neglected previously because conventional studies mainly focused on individual compounds or mixed compounds in batch systems. The present work evaluates composite fouling behavior of CaSO4 and CaCO3 in a dynamic RO unit. The fouling experiments were performed at constant pressure and velocity by a partial recycling mode which permeate was withdrawn from the system during the recirculation of retentate to simulate the increasing of water recovery level. The fouling phenomena were monitored by the decline of flux. Scanning electron microscopy (SEM) with a combination of elemental dispersive x-ray microanalysis (EDS), and x-ray powder diffraction (XRD) was used to identify the morphological features, chemical compositions and crystalline phases of foulants. The interactions of CaSO4 and CaCO3 were investigated by the comparison between individual CaSO4 or CaCO3 fouling and composite fouling, and by varying SO42-/HCO3- molar ratio of the feed. A recently developed approach, Scaling Potential Index (SPI) incorporated with measured concentration polarization modulus (CP), for assessing the fouling tendency of inorganic salts on the membrane surface was validated in the dynamic tests. In addition, the effectiveness of two generic scale inhibitors, polyacrylic acid (molecular weight =2100, PA) and sodium hexametaphosphate (SHMP) were evaluated. Some of the highlights of the obtained results are as follows: ??????The precipitation kinetics, morphology and adhesive strength of composite scales were different from pure precipitates ??????CaSO4 precipitated as gypsum while CaCO3 precipitated as two crystalline phases: calcite and aragonite ??????The crystalline phases as well as precipitation kinetics were affected by SO42-/HCO3- ratio ??????Scaling Potential Index was able to predict the fouling tendency of CaSO4 and CaCO3 accurately ??????The dosage of PA and SHMP was effective to mitigate fouling Results of this work are significant, not only because they have made contribution to the fundamental understanding of composite inorganic fouling in RO membrane systems which was ignored previously, but also because they may play a key role in the development of scale control.

Deposition of calcium carbonate (CaCO3) and calcium sulfate (CaSO4) causes serious processing problems and limits the productivity of seawater reverse osmosis (RO) desalination. The interactions between CaSO4 and CaCO3 in the dynamic seawater RO systems have been neglected previously because conventional studies mainly focused on individual compounds or mixed compounds in batch systems. The present work evaluates composite fouling behavior of CaSO4 and CaCO3 in a dynamic RO unit. The fouling experiments were performed at constant pressure and velocity by a partial recycling mode which permeate was withdrawn from the system during the recirculation of retentate to simulate the increasing of water recovery level. The fouling phenomena were monitored by the decline of flux. Scanning electron microscopy (SEM) with a combination of elemental dispersive x-ray microanalysis (EDS), and x-ray powder diffraction (XRD) was used to identify the morphological features, chemical compositions and crystalline phases of foulants. The interactions of CaSO4 and CaCO3 were investigated by the comparison between individual CaSO4 or CaCO3 fouling and composite fouling, and by varying SO42-/HCO3- molar ratio of the feed. A recently developed approach, Scaling Potential Index (SPI) incorporated with measured concentration polarization modulus (CP), for assessing the fouling tendency of inorganic salts on the membrane surface was validated in the dynamic tests. In addition, the effectiveness of two generic scale inhibitors, polyacrylic acid (molecular weight =2100, PA) and sodium hexametaphosphate (SHMP) were evaluated. Some of the highlights of the obtained results are as follows: ??????The precipitation kinetics, morphology and adhesive strength of composite scales were different from pure precipitates ??????CaSO4 precipitated as gypsum while CaCO3 precipitated as two crystalline phases: calcite and aragonite ??????The crystalline phases as well as precipitation kinetics were affected by SO42-/HCO3- ratio ??????Scaling Potential Index was able to predict the fouling tendency of CaSO4 and CaCO3 accurately ??????The dosage of PA and SHMP was effective to mitigate fouling Results of this work are significant, not only because they have made contribution to the fundamental understanding of composite inorganic fouling in RO membrane systems which was ignored previously, but also because they may play a key role in the development of scale control.

La presente tesis doctoral (i.e., “New developments in calcium phosphate bone cements: approaching spinal applications”) aporta nuevos conocimientos en el campo de los cementos óseos de fosfato de calcio (CPBCs) en relación a su aplicación clínica en el campo de la cirugía vertebral mínimamente invasiva. La hipótesis central de esta investigación fue formulada en los siguientes términos: “Los cementos apatíticos pueden ser (si se optimizan) una alternativa mejor (debido a sus propiedades de fraguado, endurecimiento y bioactividad) a los actuales cementos poliméricos utilizados en vertebroplastia y cifoplastia”. En este sentido, la presente tesis doctoral ha investigado nuevas soluciones para obtener cementos apatíticos con: (a) mejores propiedades mecánicas (Cap. 2); (b) capacidad para desarrollar macroporosidad abierta e interconectada (Cap. 3); (c) mejor estabilidad y reactividad química (Cap. 4 & 5); (d) óptimas propiedades de biocompatibilidad y osteogénicas (Cap. 6, 7 & 8); y (e) mejores propiedades de inyectabilidad (Cap. 7). Además, en esta tesis se ha investigado la aplicación de los ultrasonidos a la monitorización del fraguado inicial de cementos de base cerámica con el objetivo de relacionar la evolución de las propiedades acústicas con las características de inyectabilidad de estos cementos (Cap. 9 &10). El Capítulo 2 muestra que las propiedades mecánicas, de trabajabilidad y de fluidez de los cementos apatiticos pueden mejorarse con la adición de superplastificantes en la fase líquida de los cementos. Los resultados muestran que estos aditivos pueden mejorar la inyectabilidad inicial de los cementos sin afectar a su resistencia mecánica final. El Capítulo 3 muestra que la adición de cristales de sulfato de calcio dihidratado (CSD) a la fase en polvo de un cemento de base alfa-fosfato tricálcico (α-TCP) puede modular la formación de macroporosidad durante su fraguado. Las propiedades resultantes del fraguado de estos nuevos cementos bifásicos son debidas a la disolución del α-TCP y a la precipitación de una matriz de cristales entrecruzados de hidroxiapatita deficiente en calcio (CDHA) que contiene porosidad homogéneamente distribuida gracias a la disolución pasiva de la fase de CSD. Estos cementos bifásicos mostraron resistencias mecánicas adecuadas para la aplicación en hueso trabecular. El Capítulo 4 trata sobre la problemática del proceso de fabricación de la fase reactiva principal de los cementos apatíticos, i.e. del α-TCP (α- Ca3(PO4)2). Los resultados muestran que si la relación calcio-fosforo (Ca/P) de la mezcla reactiva inicial se desvía de la relación estequiométrica Ca/P=1.50 entonces los cementos resultantes poseen malas propiedades de fraguado y de endurecimiento. Estas desviaciones ocurren fácilmente durante el proceso de sinterización del α-TCP cuando los reactivos de mezcla utilizados varían su pureza de un lote a otro. En estos casos el α- TCP obtenido produce cementos no-reactivos, i.e. que no fraguan ni endurecen. El Capítulo 5 plantea nuevas soluciones para controlar y mejorar la reactividad química del α-TCP. En este sentido, se han estudiado nuevas soluciones sólidas sinterizadas del tipo (3.CaO-1.P2O5)1-x(FeO)x con el objetivo de reemplazar al reactivo α-TCP en las actuales formulaciones de CPBCs. Los resultados muestran que la modificación del α-TCP con hierro permite recuperar la reactividad química de cementos no-reactivos de base α-TCP con una mejora adicional de las propiedades de fraguado y reológicas de los cementos resultantes. El Capítulo 6 centra su atención sobre la citocompatibilidad de las nuevas formulaciones de cementos (investigadas en los Caps. 3-5). Los resultados mostraron que los nuevos cementos de fosfato de calcio modificados con hierro (IM-CPCs) poseen características apropiadas de citocompatibilidad ya que la adhesión y la viabilidad celular no fueron afectadas con el tiempo de cultivo por la concentración de hierro. El Capítulo 7 hace referencia a nuevas aproximaciones para mejorar la inyectabilidad de los cementos óseos de base α-TCP. Los resultados demostraron que la adición de nanopartículas de óxido de hierro en la fase en polvo de un cemento de base α-TCP mejora la inyectabilidad inicial y también la resistencia máxima a compresión del cemento sin afectar a sus reacciones físico-químicas de fraguado ni a su citocompatibilidad. El Capítulo 8 se centra sobre el carácter de citocompatibilidad, biocompatibilidad y osteogénico de los nuevos cementos bifásicos porosos/modificados con hierro (estudiados en los Caps. 3-7). Los resultados demostraron que los cementos bifásicos formulados a base de CSD y α-TCP modificado con hierro poseen la habilidad de favorecer la colonización celular in vitro y proporcionan aposición ósea firme in vivo. Se concluye que estas nuevas formulaciones tienen características de cito- y biocompatibilidad de interés como biomaterial para la sustitución/reconstrucción del tejido óseo esponjoso en aplicaciones de cirugía vertebral tales como la vertebroplastia o la cifoplastia. En el Capítulo 9 y en el Capítulo 10 se aproximan los ultrasonidos como una técnica fiable para caracterizar las propiedades iniciales de fraguado de materiales de tipo cemento. Esta técnica no-destructiva permite monitorizar el fraguado del cemento en su totalidad. Los resultados obtenidos relacionan las propiedades acústicas y de material con factores experimentales del proceso de fabricación y con características reológicas. Se concluye que la monitorización ultrasónica del fraguado de cementos óseos puede contribuir a establecer protocolos prácticos adecuados para su inyección mediante técnicas de cirugía mínimamente invasivas en cirugía vertebral. Finalmente, el Capítulo 11 presenta un resumen de los resultados más relevantes de esta investigación. / This thesis is aimed at contributing to close the gap between the research conducted on the field of calcium phosphate bone cements (CPBCs) and their specific spinal clinical use. The main working hypothesis was formulated as follows: “Apatitic cements could be (after further optimization) an alternative or better option (due to its natural setting, hardening and bioactive properties) to the present use of polymeric cements in vertebroplasty and kyphoplasty”. In this regard, this thesis has approached new solutions to obtain apatitic bone cements (ABCs) with: (a) improved mechanical properties (Chapter 2); (b) the ability to develop open-interconnected macroporosity (Chapter 3); (c) improved chemical reactivity and stability (Chapter 4 & 5); (d) suitable biocompatible and osteogenic properties (Chapter 6, 7 & 8); and (e) improved injectability properties (Chapter 7). Moreover, this thesis has also approached ultrasound in order to monitor the early setting stages of ceramic based bone cements to link acoustic and material properties with some intrinsic cement-injectability features (Chapter 9 & 10). Chapter 2 showed that workability, flowing and mechanical properties of ABCs can be improved by adding superplasticizers to the liquid cement phase. The results indicated that superplasticizers can be used to improve the injectability and the strength of apatitic bone cements. Chapter 3 showed that calcium sulfate dihydrate (CSD) crystals can be added into the cement powder phase to modulate the macroporosity of the cement during its setting. This was proved with an alpha-tricalcium phosphate (α-TCP) bone cement. The setting properties of the new biphasic cements resulted from the progressive dissolution-precipitation of α-TCP into calcium-deficient hydroxyapatite (CDHA) crystals and the passive dissolution of the CSD phase, which render porosity homogeneously distributed into an entangled matrix of CDHA crystals. The biphasic cements showed suitable strength for trabecular bone applications. Chapter 4 focused the manufacturing process of α-TCP (α-Ca3(PO4)2), the main cement reactant of most commercial ABCs. It has been shown that if calcium-to-phosphorous (Ca/P) ratio deviated from Ca/P=1.50, the resulting cements had worse setting and hardening properties. These deviations can result from sintering if reactives are not pure from batch to batch; in this case the α-TCP shows no-cement reactivity at all. Chapter 5 approached new solutions to control and improve the chemical reactivity of the α-TCP phase. In this sense, new solid solutions like (3.CaO-1.P2O5)1-x(FeO)x were investigated to replace the α-TCP of the present CPBCs. The results showed that iron modification of α-TCP recovered the chemical reactivity of unreactive α-TCP cements with even better setting and rheological end-cement properties. Chapter 6 focused the attention into the cytocompatibility of the new cement formulations (investigated previously; chapters 3-5). It is showed that the new iron-modified calcium phosphate cements (IM-CPCs) have cytocompatible features (i.e. cells’ adhesion and viability were not affected with culturing time by the iron concentration dose). Chapter 7 concerned a new approach to improve the injectability of α-TCP based bone cements. It has been shown that the addition of iron oxide nanoparticles into the powder phase of α-TCP based cement improved both, the initial injectability and maximum compressive strength of the cement without affecting their physico-chemical setting reactions and their cytocompatibility. Chapter 8 pointed to the cytocompatibility, the biocompatibility and the osteogenic character of new biphasic porous/iron-modified cements (investigated previously; chapters 3-7). The results showed that biphasic cements made of CSD and iron-modified α-TCP had the ability to support cellular colonization in vitro and lead firm bone binding in vivo. It is concluded that these new formulations has cyto- and biocompatible features of interest as further cancellous bone replacement biomaterial for spinal surgery applications such as vertebroplasty or kyphoplasty. Chapter 9 & 10 approached ultrasound as more reliable characterisation technique of the early setting properties of bone cement-like materials than the Gillmore needles standard. This non-destructive technique allowed monitoring the whole setting period of experimental calcium sulphate and calcium phosphate bone cements. The results linked acoustic and material properties with the experimental factors studied and with cement flowing features. It is expected that, after further optimization, ultrasound monitoring should help, in combination with recent approaches that measure certain injectability characteristic for calcium-based bone cements (CBC’s), to set up good practice protocols for CBC’s injection during minimally invasive surgery. Finally, Chapter 11 presents a summary of the major findings of this thesis.

No description available.

Thesis (MEng) -- Stellenbosch University, 2014. / ENGLISH ABSTRACT: When desalinating brackish water by reverse osmosis (RO) or other techniques, high overall water recoveries are essential to minimize brine production and the associated disposal costs thereof. As the overall water recovery increases, concentrations of sparingly soluble salts (e.g. barium sulphate, calcium sulphate) reach levels above saturation, especially near the membrane surface, drastically increasing the scaling propensity. Antiscalants are typically dosed into the feed water to prevent such scaling during RO desalination. However, the carry-over of antiscalant into the concentrate stream can complicate subsequent salt precipitation processes that may be used to increase overall water recovery. These precipitation techniques are sometimes used to reduce the levels of super-saturation in the RO concentrate prior to a subsequent RO desalination step. The purpose of this study was to assess the feasibility of reducing calcium sulphate scaling on RO membranes, by using periodic permeate flushing when feeding a lab-scale RO unit with a supersaturated calcium sulphate solution in the absence of anti-scalant. The overall water recovery was increased by recycling the concentrate, after an intermediate de-supersaturation step. This simulated a multiple-stage RO system, typical of processes used in high-recovery acid mine drainage (AMD) treatment plants. De-supersaturation of the concentrate intermediate was achieved with direct seeded gypsum precipitation, in the absence of any antiscalant. On the membrane surface inside the membrane unit, calcium sulphate concentrations greatly exceeded saturation levels – a combined consequence of the normal concentration process and the well-known surface-based concentration polarisation phenomenon. Therefore, periodic forward-flushing of the supersaturated solution from the membrane unit was performed with permeate. In theory, the periodic flushing removes the highly concentrated layer at the membrane surface during every flush, before scaling can occur. Various flushing regimes were evaluated to assess the effectiveness of the process. A lab-scale desalination unit with a 0.106 m2 flat sheet polyamide RO membrane was designed and constructed. The unit could operate at a feed rate of 12-14 L/h and at permeate fluxes of 12-24 LMH. Super-saturated feed solutions were prepared by mixing sodium sulphate and calcium chloride dihydrate salts with demineralised water, with an initial salinity of ± 5300 mg/L TDS, corresponding to a gypsum saturation index (SIg) of 1.2 for most experiments. The total production time, net permeate production and flux decline were used to compare the flushing efficiency in different experimental runs. Initial tests showed that scaling could be prevented (when operating the unit in full recycle mode, i.e. where both concentrate and permeate were recycled to feed), at flushing frequencies between 12 and 2.4 h-1, when the membrane feed and concentrate were slightly under-saturated (SIg = 0.9) and slightly super-saturated (SIg = 1.1) respectively. However, when switching the same system to non-flushing mode after 24 hours of operation, membrane scaling occurred within 2-3 hours, as indicated by a strong decline in flux. However, when operating the system in concentrate recycle mode (i.e. permeate is withdrawn) with super-saturated feed solutions (e.g. SIg = 1.2), and thus a notably more super-saturated solution in the membrane concentrate, scaling could not be prevented (albeit delayed for some time) with intermittent permeate flushing. A fractional 25-1 factorial design was used to determine which factors had the most significant effect on total production time and permeate production rate, testing five factors: 1) flushing frequency, 2) flushing volume, 3) permeate soak time, 4) permeate flux and 5) instantaneous recovery. The ANOVA analysis showed that total production times were, not surprisingly, primarily affected by the permeate flux, where operation at 24 LMH resulted in a lower net permeate production between 3.0 - 4.2 L, compared to 7.6 - 9.7 L at 12 LMH. Higher permeate fluxes clearly resulted in higher levels of concentration polarisation at the membrane surface, thus increasing the propensity for membrane scaling. Flushing frequency and instantaneous recovery also affected the net permeate production, where 6 h-1 and 10 % were the optimal values respectively within the range of test conditions. The lowest permeate production rate resulted in the highest net permeate volume production (i.e. also longest total production time), confirmed by a least squares regression. In summary: This study showed that periodic permeate flushing could delay the membrane scaling process. However, it failed to prevent membrane scaling completely when operating the system with supersaturated calcium sulphate solutions in the absence of antiscalants. The flushing technique effectively delayed the onset of precipitation, but scaling eventually occurred if the lab-scale RO system was operated in concentrate recycle mode with oversaturated feed solutions (SIg = 1.2). Additional experiments at different cross-flow velocities during permeate flushing, while using an optimised RO test cell flow channel design, are recommended for future studies. / AFRIKAANSE OPSOMMING: Gedurende die ontsouting van brakwater deur tegnieke soos tru-osmose (TO), is ʼn maksimum herwinning van water noodsaaklik om die produksie, en die gepaardgaande kostes van verwydering, van die sout/brak neweproduk te minimeer. Soos die herwinning van water verhoog, so ook verhoog die konsentrasie van moeilik-oplosbare soute (soos bariumsulfaat, kalsiumsulfaat) in die sout konsentraat stroom, totdat die soute uiteindelik superversadiging bereik. Hierdie superversadiging gebeur veral naby die membraanoppervlak, waar dit lei tot ʼn verhoogde kans van presipitasie en skaalvorming. Om dit te voorkom word die voerwater na ʼn TO stelsel tipies gedoseer met antiskaalmiddels. Hierdie antiskaalmiddels verlaat die stelsel saam met die konsentraat, waar hulle gevolglike die presipitasie van soute bemoeilik. Presipitasie van soute uit die konsentraat kan tipies gebruik word om die vlak van superversadiging in die konsentraat te verlaag, waarna verdere TO behandeling gebruik word om selfs ʼn hoër algehele waterherwinning te bewerkstellig. Die doel van hierdie studie was om die vatbaarheid van die vermindering van kalsiumsulfaat (gips) skaalvorming in die afwesigheid van antiskaalmiddels op TO membrane te toets. Dit is bewerkstellig deur ʼn laboratoriumskaal TO eenheid te voer met ʼn superversadigde kalsiumsulfaat oplossing en die membraan periodies met skoon produkwater (permeaat) te was. Die algehele waterherwinning is verhoog deur met ʼn tussenstap die versadigingsvlak van gips in die konsentraat te verlaag, waarna dit hersirkuleer is na die voertenk. Sodoende is ʼn multi-stadium TO stelsel nageboots, soos dit tipies in hoë herwinningsaanlegte, soos met die herwinning van suur mynwater (E: acid mine drainage, AMD), gebruik word. ʼn Verlaging in superversadiging van die konsentraat in die tussenstap is behaal deur die konsentraat direk aan gipskristalle bloot te stel om presipitasie te bewerkstellig in die afwesigheid van enige antiskaalmiddels. Gedurende eksperimente het die soutkonsentrasie op die membraanoppervlak in die TO eenheid superversadigingsvlakke vêr oorskry, as gevolg van die natuurlike konsentrasie proses en die bekende konsentrasie polarisasie oppervlaksverskynsel. Om hierdie superversadiging teen te werk is periodiese saamstroom spoeling van die membraan met skoon produkwater uitgevoer. In teorie het die periodiese spoeling die hoogs gekonsentreerde oplossing van die membraan oppervlak verwyder voor skaalvorming kan plaasvind. Verskillende spoelpatrone is ondersoek om die doeltreffendheid van die spoeling te bepaal. Om die eksperimente uit te voer is ʼn laboratoriumskaal ontsoutingsaanleg met ʼn maklik verwyderbare 0.106 m2 plat-vel poli-amied TO membraan ontwerp en gebou. Die aanleg kan vloeistof voertempo’s tussen 12-24 L/h hanteer en skoon produkwater teen 12-24 LHM lewer. Die superversadigde voer oplossings, soos gebruik in die meerderheid van die eksperimentes is voorberei deur natriumsulfaat en kalsiumchloried-dihidraat soute te meng in gedemineraliseerde water, tot ʼn soutgehalte van ± 5300 mg/L TDS bereik is. Hierdie soutgehalte stem ooreen met ʼn gips versadigingsindeks (E: gypsum saturation index, SIg) van 1.2. Die skoon produkwater totale produksietyd en netto produksie, asook die membraan vloed afname, is gebruik as veranderlikes om die spoel doeltreffendheid tussen eksperimentele lopies te vergelyk. Aanvanklike toetse het getoon dat skalering voorkom is by effens onderversadigde (SIg = 0.9) en effens superversadigde (SIg = 1.1) voer oplossings met die onderskeie spoel frekwensies van 12 en 2.4 h-1, (terwyl die aanleg in algehele hersirkulasie bedryf is, m.a.w. wanneer beide die konsentraat en produkwater gedurig na die voertenk hersirkuleer word). ʼn Effens-superversadigde eksperiment is ook sonder spoeling uitgevoer vir 24 uur. In hierdie geval het skaalvorming binne twee tot drie uur gebeur, soos bevestig deur ʼn skerp afname in die membraan vloed. Skaalvorming kon nie verhoed word terwyl die aanleg bedryf word met superversadigde (SIg = 1.2) voeroplossings en slegs konsentraat hersirkulasie nie (m.a.w. skoon produkwater word opgevang), alhoewel skaalvorming vertraag kon word. Hierdie operasie het tot beduidend meer gekonsentreerde oplossings in die membraan gelei. Om te bepaal watter faktore die grootste invloed op totale produksietyd en netto produksie van skoon produkwater het, is ʼn fraksionele faktoriaalontwerp van 25-1 uitgelê wat vyf faktore toets, naamlik: 1) spoel frekwensie, 2) spoel volume, 3) skoon produkwater weektyd, 4) membraanvloed en 5) oombliklike herwinning. ʼn AVOVA analise het getoon dat totale produksietyd hoofsaaklik deur membraanvloed beïnvloed is, soos verwag kan word. Dit word gestaaf deurdat die aanleg, bedryf teen 24 LMH, slegs 3 - 4.2 L netto produkwater gelewer het, teenoor 7.6 - 9.7 L by 12 LMH. Hoër membraan vloedtempo’s het tot hoër vlakke van konsentrasie polarisasie op die membraanoppervlak gelei, wat ʼn groter neiging tot skaalvorming tot gevolg gehad het. Spoelfrekwensie en oombliklike herwinning het ʼn invloed op die netto produksie van skoon produkwater gehad, met 6 h-1 en 10 % as die onderskeie optimale waardes. ʼn Kleinstekwadraat regressie het aangedui dat die laagste produksietempo van skoon produkwater die hoogste netto produksie van skoon produkwater gelewer het, (asook die langste produksietyd). In opsomming: Hierdie studie het getoon dat gereelde spoeling met skoon produkwater die membraan skaalproses kan vertraag. Gedurende bedryf met superversadigde kalsiumsulfaat oplossings sonder enige antiskaalmiddels is daar gevind dat skaalvorming nie geheel en al vermy kon word nie. Die spoeltegniek, soos gebruik in hierdie studie, het die aanvang van skaalvorming in die laboratorium skaal TO eenheid vertraag, maar bedryf met konsentraat hersirkulasie en superversadigde oplossings (SIg = 1.2) het steeds skaal gevorm. Bykomende eksperimente teen verskeie kruisvloei snelhede gedurende die spoel stap word aanbeveel vir toekomstige studies.

A fundamental theoretical and experimental study on calcium sulphate scale formation in hydrometallurgical solutions containing various minerals was conducted. A new database for the Mixed Solvent Electrolyte (MSE) model of the OLI Systems® software was developed through fitting of existing literature data such as mean activity, heat capacity and solubility data in simple binary and ternary systems. Moreover, a number of experiments were conducted to investigate the chemistry of calcium sulphate hydrates in laterite pressure acid leach (PAL) solutions, containing Al2(SO4)3, MgSO4, NiSO4, H2SO4, and NaCl at 25–250ºC. The database developed, utilized by the MSE model, was shown to accurately predict the solubilities of all calcium sulphate hydrates (and hence, predict scaling potential) in various multicomponent hydrometallurgical solutions including neutralized zinc sulphate leach solutions, nickel sulphate–chloride solutions of the Voisey’s Bay plant, and laterite PAL solutions over a wide temperature range (25–250°C). The stability regions of CaSO4 hydrates (gypsum, hemihydrate and anhydrite) depend on solution conditions, i.e., temperature, pH and concentration of ions present. The transformation between CaSO4 hydrates is one of the common causes of scale formation. A systematic study was carried out to investigate the effect of various parameters including temperature, acidity, seeding, and presence of sulphate/chloride salts on the transformation kinetics. Based on the results obtained, a mechanism for the gypsum–anhydrite transformation below 100°C was proposed. A number of solutions for mitigating calcium sulphate scaling problems throughout the processing circuits were recommended: (1) operating autoclaves under slightly more acidic conditions (~0.3–0.5 M acid); (2) mixing recycled process solutions with seawater; and (3) mixing the recycling stream with carbonate compounds to reject calcium as calcium carbonate. Furthermore, aging process solutions, saturated with gypsum, with anhydrite seeds at moderate temperatures (~80°C) would decrease the calcium content, provided that the solution is slightly acidic.

De nombreuses transformations de solides en solution, polymorphiques ou non, en industrie minérale ou pharmaceutique, se déroulent par la dissolution d'un premier solide en vue de la cristallisation du second. Au lieu de la voie traditionnelle de séchage, la transformation du gypse (sulfate de calcium dihydrate) en alpha-bassanite (sulfate de calcium hémihydrate) peut s’effectuer en solution aqueuse : en augmentant suffisamment la température, le gypse devient plus soluble dans l'eau que l’hémihydrate, qui a alors la possibilité de cristalliser. Un appareillage et un mode opératoire originaux ont été conçus pour investiguer la sensibilité de la cinétique de la transformation et des caractéristiques des cristaux d’hémihydrate obtenus à ces conditions opératoires. En effet, cette voie de dissolution-recristallisation permet le contrôle du facteur d'aspect des cristaux d’hémihydrate, voire celui de leur taille moyenne et de leur dispersion de taille, par le choix de ses conditions physico-chimiques : température, pH, utilisation d’additifs, et ensemencement de la solution avec des particules d’hémihydrate appropriées. Les techniques d'analyse images sont développées afin d'identifier le rapport d'aspect des particules. Un modèle cinétique prenant en compte la dissolution du gypse, la nucléation et la croissance du sulfate de calcium hémihydrate, les équilibres en phase aqueuse et de solubilité, a été élaboré, et ses équations résolues avec le logiciel MATLAB. Couplée à une méthode numérique d'optimisation, cette résolution sous MATLAB permet d'examiner la validité des hypothèses sur les processus retenus et d'identifier leurs paramètres cinétiques. / In mineral or pharmaceutical industry, many transformations of solids in solution (polymorphic or not), take place by the dissolution of the first solid and the crystallization of the second solid. Instead of the traditional drying process, the conversion of gypsum (calcium sulfate dihydrate) to alpha-bassanite (calcium sulphate hemihydrate) can be carried out in aqueous solution by increasing the temperature sufficiently. At this moment, the gypsum becomes more soluble in water than the hemihydrate, which then has the possibility to crystallize. An apparatus and an original procedure have been designed to investigate the sensitivity of the kinetics of transformation and the characteristics of the hemihydrate crystals obtained under its operating conditions. In fact, this dissolution-recrystallization route allows to control the aspect ratio of the hemihydrate crystals, and even their average size and size dispersion, by the choice of its physicochemical conditions such as temperature, pH, use of additives, and seeding the solution with the appropriate hemihydrate particles. Image analysis techniques are developed to identify the aspect ratio of the particles.A kinetic model taking into account the dissolution of gypsum, the nucleation and the growth of calcium sulphate hemihydrate and their equilibrium in aqueous phase and solubility had been developed and the equations of this model are solved with the help of MATLAB software. Coupled with a numerical optimization method, this resolution under MATLAB makes it possible to examine the validity of the assumptions on the selected processes and to identify their kinetic parameters.