MgCl2 brines present a number of potential advantages for the processing of saprolite ores for nickel production. Concentrated MgCl2 solutions enhance the activity of acid used, allow atmospheric leaching at elevated temperature and inhibit magnesium dissolution, which reduces acid consumption and increases metal selectivity. However, with a chloride system it is economically requisite to recover hydrochloric acid, conventionally accomplished by pyrohydrolysis. This work was performed in conjunction with a novel flowsheet for the processing on saprolite ores, which recovers HCl by the precipitation and subsequent decomposition of magnesium hydroxychlorides, alleviating some of the issues with pyrohydrolysis. Leaching and iron control experiments have been conducted in concentrated MgCl2 brines, up to 4.5 m, to determine the most amenable process conditions. It was determined that > 95% extraction of metals was possible using both aqueous and gaseous HCl. In addition, the feasibility of iron control by precipitation with MgO addition was proven.

MgCl2 brines present a number of potential advantages for the processing of saprolite ores for nickel production. Concentrated MgCl2 solutions enhance the activity of acid used, allow atmospheric leaching at elevated temperature and inhibit magnesium dissolution, which reduces acid consumption and increases metal selectivity. However, with a chloride system it is economically requisite to recover hydrochloric acid, conventionally accomplished by pyrohydrolysis. This work was performed in conjunction with a novel flowsheet for the processing on saprolite ores, which recovers HCl by the precipitation and subsequent decomposition of magnesium hydroxychlorides, alleviating some of the issues with pyrohydrolysis. Leaching and iron control experiments have been conducted in concentrated MgCl2 brines, up to 4.5 m, to determine the most amenable process conditions. It was determined that > 95% extraction of metals was possible using both aqueous and gaseous HCl. In addition, the feasibility of iron control by precipitation with MgO addition was proven.

Hydrochloric acid leaching of saprolite nickel ores has been proposed as an effective means of recovering nickel and cobalt. However, the leach produces a concentrated brine of magnesium chloride which must be hydrolyzed to recover the HCl lixiviant. The processing of carnallite similarly produces a concentrated MgCl2 brine; converting this brine into HCl and MgO provides an attractive way of adding value while effectively disposing of this waste product. Direct pyrohydrolysis of magnesium chloride brines by the reaction, MgCl2,a + H2Oa  MgOs + 2HClg is energy-intensive as large volumes of water must be evaporated. The energy cost is high, and the HCl stream produced is limited to approximately 20 wt% HCl. This thesis explores alternative methods of obtaining HCl from aqueous magnesium chloride solutions. Two methods are considered: the hydrolysis, under autogenous pressure, of concentrated MgCl2 molten salt hydrates; and the precipitation of magnesium hydroxychloride compounds such as 2MgO·MgCl2·6H2O and 3MgO·MgCl2·11H2O, which are subsequently decomposed at high temperature. Considerable experimental difficulties were encountered in studying pressure hydrolysis of molten salt hydrates, despite extensive equipment modifications. Ultimately, the work moved on to precipitation and decomposition of hydroxychlorides. This was found to bear promise, and conceptual flowsheets based on these reactions are presented. A phase stability diagram giving the areas of predominance of the different hydroxychloride phases is presented, and fundamental thermochemical data are derived. The results of a kinetic study on magnesium hydroxychloride thermal decomposition are also presented. / Thesis (Ph.D, Mining Engineering) -- Queen's University, 2011-03-11 10:14:53.455

The emissions of nitrogen oxides (NOx) are a serious environmental problem due to its relationship with the formation of smog, acid rain and because they are dangerous for human and animal health. These gases are produced in high quantities in diesel engines used for automotive applications, and different strategies are being used to reduce them, among which are the Selective Catalytic Reduction (SCR) systems. For its operation, it is necessary a supply of ammonia as NOx reducing agent, but the inefficiency at low temperatures of the systems used nowadays has led to the conception of the solid ammonia storage units (ASS). Unfortunately, the materials currently used, i.e. metal halides, do not meet the ammonia supply requirements at low temperatures and have problems of swelling and agglomeration. In order to find a material with better properties for its application as an ammonia sorbent material, MgCl2 composites with different carbon materials (graphite, graphene, and SWCNTs) were prepared by direct mixing and wet impregnation methods, and characterized in this work. Despite the decrease of total storage capacity, improvements were found in thermal stability and mass retention, as well as in sorption and desorption kinetics, making these materials a first result towards the improvement of the solid ammonia storage units.

Main reason for the current losses in electrolytic magnesium production is the reaction between electrode products. Present study was devoted to effective separation of chlorine gas from the electrolysis environment by a new cell design and thus reducing the extent of back reaction between magnesium and chlorine to decrease energy consumption values. The new cell design was tested by changing temperature, cathode surface, current density, anode cathode distance and electrolyte composition. Both the voltages and the current efficiencies were considered to be influenced by the amount and hydrodynamics of chlorine bubbles in inter-electrode region. Cell voltages were also found to be affected from the nucleation of magnesium droplets and changes in electrolyte composition that took place during the electrolysis. A hydrodynamic model was used to calculate net cell voltage by including the resistance of chlorine bubbles on anode surface to theoretical decomposition voltage during electrolysis. Good correlations were obtained between experimental and calculated voltages. The same model was used to calculate current efficiencies by considering chlorine diffusion from bubble surfaces. A general agreement was obtained between calculated and experimental current efficiencies. Desired magnesium deposition morphology and detachment characteristics from cathode were obtained when MgCl2-NaCl-KCl-CaCl2 electrolytes were employed. Current efficiencies higher than 90% could be achieved using the above electrolyte. The cell consumes around 8 kWh&amp / #903 / kg-1 Mg at 0.43 A&amp / #903 / cm-2 as a result of high chlorine removal efficiency and capability of working at low inter-electrode distances. Furthermore, the cell was capable of producing magnesium with less than the lowest energy consumption industrially obtained, at about double the commonly practiced industrial current density levels.

Prestressed concrete piles are commonly used to support over-water highway bridges in marine environments. The reinforcing steel within will ultimately be degraded via corrosion damage due to the penetration of chloride ions from sea water. The service life of these structures is, in part, dictated by the time required to diffuse chloride ions through the concrete cover and subsequently corrode the steel. Therefore, by slowing the rate of diffusion or increasing the chloride threshold of the steel (or both) an increased service life can be expected. This thesis focuses on the latter whereby stainless steel reinforcing alternatives were investigated to elevate the chloride threshold before corrosion begins. The designation "stainless" steel implies corrosion resistance. However, corrosion resistance in itself is not a sufficient condition to make it a suitable alternative for prestressed concrete applications. In this study, the corrosion susceptibility of stainless steel alloys was scrutinized with the understanding that high strength stainless steels are vulnerable to stress corrosion cracking (SCC). This investigation screened three candidate alloys that span the norms of stainless steel compositions: a common austenitic stainless steel with high nickel content (316L), a less common austenitic stainless steel with low nickel but high manganese (XM 29), and a duplex stainless steel with high chromium and an additional constituent, molybdenum (2205). Each alloy was subjected to two stress conditions imposed by varied mechanical fixtures then subjected to various forms of high chloride concentrations. The pH of these conditions was also varied and in one case simulated the high pH common to concrete pore water solutions. Elevated temperatures were used to accelerate the effects of these exposures. Results of Phase 1 showed that for exposure at 135oC (275oF) cracking of alloys 316 L and 2205 occurred after 1 hour while XM29 experience cracking after 24 hours. At 90oC (194oF) alloy 316L cracked after 4 hours; XM29 did not crack after 96 hours while 2205 did crack after 96 hours. The results were interpreted with an Arrhenius relationship between time to cracking and test temperature to extrapolate toward the anticipated service regime. Results of Phase 2 showed that SCC was less likely to initiate in high pH conditions than in low pH conditions at typical marine environment temperatures and chloride concentration. In these limited tests the SCC performance of XM29 was better relative to that of the other two alloys.

The report formulates the experiments conducted to remove phosphorus from the return sludge wastewater subjected to side-stream hydrolysis. The experiments are conducted using the wastewater from the outlet of side-stream hydrolysis and is tested in a laboratory at the Duvbackens wastewater treatment plant in Gävle. Chemical precipitation is used in the experiments and displays remarkable results using magnesium chloride and calcium chloride as the precipitants. A successful removal rate of 79-99% is achieved through this method. The phosphate phosphorus content is chosen to be the criterion for estimating the phosphorus removal rate. Possible parametric variations are also reviewed in the report. The decline in ammonium nitrogen is also studied alongside. Struvite and calcium phosphate are the possible precipitates and are recovered with the prospect of recycling. Both the precipitates are known as slow fertilizers and are used in the agricultural industry. If recovered by proper means, these precipitates can reduce the pressure on phosphate industry and on naturally occurring phosphate rocks. Calcium phosphate is selected among the precipitation methods for its rapid reaction and its minimum response to parametric variations. It also expresses a faster settling property with a clear solution after precipitation. The removal and recovery of phosphorus from the side-stream hydrolysis is evaluated with a notion to operate in a pilot scale.

Zirconium tetrachloride (ZrF4) is extensively used in the manufacturing of zirconium metal. The concept of producing zirconium tetrafluoride from dissociated zircon and ammonium bifluoride is well established at the South African Nuclear Energy Corporation (Necsa) State Owned Company (SOC) Limited. Zirconium and hafnium are always found in the same minerals. In nuclear application zirconium is used for structural construction and as a cladding material for fuel, because of the low thermal neutron absorption, while hafnium is used as control rod in nuclear reactor, because of the high thermal neutron absorption. The methods of separating hafnium from zirconium prefer the use of ZrCl4 than ZrF4. This is because of the high solubility in both aqueous solutions and organic solvents and low sublimation temperature of ZrCl4, while ZrF4 is almost insoluble in organic solvent and has a high sublimation temperature. Thermodynamic evaluations showed that chlorinating ZrF4 with either CaCl2, KCl, LiCl or NaCl respectively was not favourable, while chlorinating ZrF4 with either BeCl2 or MgCl2 was favourable. But due to cost consideration chlorinating ZrF4 with BeCl2 was not investigated. A thermogravimetric apparatus was used to investigate the isothermal and the non-isothermal kinetics of chlorinating analytical grade ZrF4 with MgCl2. The thermogravimetric apparatus revealed that chlorination of ZrF4 commence at temperature above 350°C. Isothermal kinetics of chlorinating analytical grade ZrF4 with MgCl2 was investigated at temperatures of 400, 450, 480, 500°C. The reaction progressed towards completion prematurely before the isothermal temperatures were reached, due to a low heating rate of 20 °C/minutes was used to heat up the reaction mixture to the desired isothermal temperatures. As a result, the isothermal kinetics could not be determined. Heating rates of 5, 10, 15 and 20 °C/minutes were used to investigate the non-isothermal kinetics. The apparent activation energy of chlorinating ZrF4 with MgCl2 varied significantly when the non-isothermal kinetics was investigated. The variation was due to changes in the reaction mechanism. As a result, rate law of chlorinating ZrF4 with MgCl2 could not be determined due to variation of the apparent activation energy. Crude ZrF4 prepared at Necsa SOC ltd. was chlorinated with MgCl2, a mixture of MgCl2 and KCl, a mixture of MgCl2 and LiCl, and a mixture of MgCl2 and NaCl respectively. Chlorination of the crude ZrF4 was conducted at temperatures of 400, 450 and 500°C respectively. The aim of chlorinating the crude ZrF4 was to investigating the effect of the chlorinating on the purity of the produced ZrCl4. A batch reactor was used in this study. The reactor was divided into two sections, namely the reaction zone and the condensation zone. The diameter of the condensation zone was larger than that of the reaction zone. Reactants were placed into the reaction zone and the products were collected at the reaction zone and the condensation zone. Samples were collected from these products and analysed using for X-Ray Diffraction analysis (XRD) and Inductive Coupled Plasma Optical Emissions Spectroscopy (ICP-OES). XRD was used to identify the compounds that were present in the products and ICP-OES was used to determine the concentration of the elements that were present in the products. The analysis of the results obtained showed that the highest recovery of zirconium in the products collected from the condensation zone, the sublimed products, was achieved by chlorinating ZrF4 with MgCl2 at 500°C. About 80% was recovered. About 96% of the concentration of the impurities in the sublimed products was reduced when ZrF4 was chlorinated with a mixture of MgCl2 and LiCl at 450°C. About 36% of hafnium in the sublimed products was reduced when ZrF4 was chlorinated with a mixture of MgCl2 and NaCl at 400°C. / Chemical Engineering / M.Tech. (Chemical Engineering)

Zirconium tetrachloride (ZrF4) is extensively used in the manufacturing of zirconium metal. The concept of producing zirconium tetrafluoride from dissociated zircon and ammonium bifluoride is well established at the South African Nuclear Energy Corporation (Necsa) State Owned Company (SOC) Limited. Zirconium and hafnium are always found in the same minerals. In nuclear application zirconium is used for structural construction and as a cladding material for fuel, because of the low thermal neutron absorption, while hafnium is used as control rod in nuclear reactor, because of the high thermal neutron absorption. The methods of separating hafnium from zirconium prefer the use of ZrCl4 than ZrF4. This is because of the high solubility in both aqueous solutions and organic solvents and low sublimation temperature of ZrCl4, while ZrF4 is almost insoluble in organic solvent and has a high sublimation temperature. Thermodynamic evaluations showed that chlorinating ZrF4 with either CaCl2, KCl, LiCl or NaCl respectively was not favourable, while chlorinating ZrF4 with either BeCl2 or MgCl2 was favourable. But due to cost consideration chlorinating ZrF4 with BeCl2 was not investigated. A thermogravimetric apparatus was used to investigate the isothermal and the non-isothermal kinetics of chlorinating analytical grade ZrF4 with MgCl2. The thermogravimetric apparatus revealed that chlorination of ZrF4 commence at temperature above 350°C. Isothermal kinetics of chlorinating analytical grade ZrF4 with MgCl2 was investigated at temperatures of 400, 450, 480, 500°C. The reaction progressed towards completion prematurely before the isothermal temperatures were reached, due to a low heating rate of 20 °C/minutes was used to heat up the reaction mixture to the desired isothermal temperatures. As a result, the isothermal kinetics could not be determined. Heating rates of 5, 10, 15 and 20 °C/minutes were used to investigate the non-isothermal kinetics. The apparent activation energy of chlorinating ZrF4 with MgCl2 varied significantly when the non-isothermal kinetics was investigated. The variation was due to changes in the reaction mechanism. As a result, rate law of chlorinating ZrF4 with MgCl2 could not be determined due to variation of the apparent activation energy. Crude ZrF4 prepared at Necsa SOC ltd. was chlorinated with MgCl2, a mixture of MgCl2 and KCl, a mixture of MgCl2 and LiCl, and a mixture of MgCl2 and NaCl respectively. Chlorination of the crude ZrF4 was conducted at temperatures of 400, 450 and 500°C respectively. The aim of chlorinating the crude ZrF4 was to investigating the effect of the chlorinating on the purity of the produced ZrCl4. A batch reactor was used in this study. The reactor was divided into two sections, namely the reaction zone and the condensation zone. The diameter of the condensation zone was larger than that of the reaction zone. Reactants were placed into the reaction zone and the products were collected at the reaction zone and the condensation zone. Samples were collected from these products and analysed using for X-Ray Diffraction analysis (XRD) and Inductive Coupled Plasma Optical Emissions Spectroscopy (ICP-OES). XRD was used to identify the compounds that were present in the products and ICP-OES was used to determine the concentration of the elements that were present in the products. The analysis of the results obtained showed that the highest recovery of zirconium in the products collected from the condensation zone, the sublimed products, was achieved by chlorinating ZrF4 with MgCl2 at 500°C. About 80% was recovered. About 96% of the concentration of the impurities in the sublimed products was reduced when ZrF4 was chlorinated with a mixture of MgCl2 and LiCl at 450°C. About 36% of hafnium in the sublimed products was reduced when ZrF4 was chlorinated with a mixture of MgCl2 and NaCl at 400°C. / Chemical Engineering / M.Tech. (Chemical Engineering)

Previous studies reported on the broad-spectrum antiviral function of heparin. Here we investigated the antiviral function of magnesium-modified heparin and found that modified heparin displayed a significantly enhanced antiviral function against human adenovirus (HAdV) in immortalized and primary cells. Nuclear magnetic resonance analyses revealed a conformational change of heparin when complexed with magnesium. To broadly explore this discovery, we tested the antiviral function of modified heparin against herpes simplex virus type 1 (HSV-1) and found that the replication of HSV-1 was even further decreased compared to aciclovir. Moreover, we investigated the antiviral effect against the new severe acute respiratory syndrome coronavirus type 2 (SARS-CoV-2) and measured a 55-fold decreased viral load in the supernatant of infected cells associated with a 38-fold decrease in virus growth. The advantage of our modified heparin is an increased antiviral effect compared to regular heparin.