Selective Mercury Sequestration from a Silver/Mercury Cyanide Solution

Silver and mercury are both dissolved in cyanide leaching and the mercury co-precipitates with silver during metal recovery. Mercury must then be removed from the silver/mercury amalgam by vaporizing the mercury in a retort, leading to environmental and health hazards. The need for retorting silver can be greatly reduced if mercury is selectively removed from leaching solutions. Theoretical calculations were carried out based on the thermodynamics of the Ag/Hg/CN- system in order to determine possible approaches to either preventing mercury dissolution, or selectively precipitating it without silver loss. Preliminary experiments were then carried out based on these calculations to determine if the reaction would be spontaneous with reasonably fast kinetics. In an attempt to stop mercury from dissolving and leaching the heap leach, the first set of experiments were to determine if selenium and mercury would form a mercury selenide under leaching conditions, lowering the amount of mercury in solution while forming a stable compound. From the results of the synthetic ore experiments with selenium, it was determined that another effect was already suppressing mercury dissolution and the effect of the selenium could not be well analyzed on the small amount of change. The effect dominating the reactions led to the second set of experiments in using silver sulfide as a selective precipitant of mercury. The next experiments were to determine if adding solutions containing mercury cyanide to un-leached silver sulfide would facilitate a precipitation reaction, putting silver in solution and precipitating mercury as mercury sulfide. Counter current flow experiments using the high selenium ore showed a 99.8% removal of mercury from solution. As compared to leaching with only cyanide, about 60% of the silver was removed per pass for the high selenium ore, and around 90% for the high mercury ore. Since silver sulfide is rather expensive to use solely as a mercury precipitant, another compound was sought which could selectively precipitate mercury and leave silver in solution. In looking for a more inexpensive selective precipitant, zinc sulfide was tested. The third set of experiments did show that zinc sulfide (as sphalerite) could be used to selectively precipitate mercury while leaving silver cyanide in solution. Parameters such as particle size, reduction potential, and amount of oxidation of the sphalerite were tested. Batch experiments worked well, showing 99.8% mercury removal with only ≈1% silver loss (starting with 930 ppb mercury, 300 ppb silver) at one hour. A continual flow process would work better for industrial applications, which was demonstrated with the filter funnel set up. Funnels with filter paper and sphalerite tested showed good mercury removal (from 31 ppb mercury and 333 ppb silver with a 87% mercury removal and 7% silver loss through one funnel). A counter current flow set up showed 100% mercury removal and under 0.1% silver loss starting with 704 ppb silver and 922 ppb mercury. The resulting sphalerite coated with mercury sulfide was also shown to be stable (not releasing mercury) under leaching tests. Use of sphalerite could be easily implemented through such means as sphalerite impregnated filter paper placed in currently existing processes. In summary, this work focuses on preventing mercury from following silver through the leaching circuit. Currently the only possible means of removing mercury is by retort, creating possible health hazards in the distillation process and in transportation and storage of the final mercury waste product. Preventing mercury from following silver in the earlier stages of the leaching process will greatly reduce the risk of mercury spills, human exposure to mercury, and possible environmental disasters. This will save mining companies millions of dollars from mercury handling and storage, projects to clean up spilled mercury, and will result in better health for those living near and working in the mines.

Boron nitride nanotubes : synthesis, characterization, functionalization, and potential applications

Boron nitride nanotubes (BNNTs) are structurally similar to carbon nanotubes (CNTs), but exhibit completely different physical and chemical properties. Thus, BNNTs with various interesting properties may be complementary to CNTs and provide an alternative perspective to be useful in different applications. However, synthesis of high quality of BNNTs is still challenging. Hence, the major goals of this research work focus on the fundamental study of synthesis, characterizations, functionalization, and explorations of potential applications. In this work, we have established a new growth vapor trapping (GVT) approach to produce high quality and quantity BNNTs on a Si substrate, by using a conventional tube furnace. This chemical vapor deposition (CVD) approach was conducted at a growth temperature of 1200 °C. As compared to other known approaches, our GVT technique is much simpler in experimental setup and requires relatively lower growth temperatures. The as-grown BNNTs are fully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), Energy Filtered Mapping, Raman spectroscopy, Fourier Transform Infra Red spectroscopy (FTIR), UV-Visible (UV-vis) absorption spectroscopy, etc. Following this success, the growth of BNNTs is now as convenient as growing CNTs and ZnO nanowires. Some important parameters have been identified to produce high-quality BNNTs on Si substrates. Furthermore, we have identified a series of effective catalysts for patterned growth of BNNTs at desirable or pre-defined locations. This catalytic CVD technique is achieved based on our finding that MgO, Ni or Fe are the good catalysts for the growth of BNNTs. The success of patterned growth not only explains the role of catalysts in the formation of BNNTs, this technique will also become technologically important for future device fabrication of BNNTs. Following our success in controlled growth of BNNTs on substrates, we have discovered the superhydrophobic behavior of these partially vertically aligned BNNTs. Since BNNTs are chemically inert, resistive to oxidation up to ~1000°C, and transparent to UV-visible light, our discovery suggests that BNNTs could be useful as self-cleaning, insulating and protective coatings under rigorous chemical and thermal conditions. We have also established various approaches to functionalize BNNTs with polymeric molecules and carbon coatings. First, we showed that BNNTs can be functionalized by mPEG-DSPE (Polyethylene glycol-1,2-distearoyl-sn-glycero-3-phosphoethanolamine), a bio-compatible polymer that helps disperse and dissolve BNNTs in water solution. Furthermore, well-dispersed BNNTs in water can be cut from its original length of >10µm to(>20hrs). This success is an essential step to implement BNNTs in biomedical applications. On the other hand, we have also succeeded to functionalize BNNTs with various conjugated polymers. This success enables the dispersion of BNNTs in organic solvents instead of water. Our approaches are useful for applications of BNNTs in high-strength composites. In addition, we have also functionalized BNNTs with carbon decoration. This was performed by introducing methane (CH4) gas into the growth process of BNNT. Graphitic carbon coatings can be deposited on the side wall of BNNTs with thicknesses ranging from 2 to 5 nm. This success can modulate the conductivity of pure BNNTs from insulating to weakly electrically conductive. Finally, efforts were devoted to explore the application of the wide bandgap BNNTs in solar-blind deep UV (DUV) photo-detectors. We found that photoelectric current generated by the DUV light was dominated in the microelectrodes of our devices. The contribution of photocurrent from BNNTs is not significant if there is any. Implication from these preliminary experiments and potential future work are discussed.