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Theses Doctoral

Chemical Fate Studies of Mining Reagents: Understanding the Decomposition Behavior under Various Conditions

Shen, Yang

The decomposition behavior of several mining reagents (i.e., xanthate, dithiocarbamate, dithiophosphate and dithiophosphinate) used widely in mineral processing operations was studied. Decomposition has been reported to generate toxic compounds such as CS₂ (carbon disulfide) and COS (carbonyl sulfide), causing severe concerns to SHE (safety, health and environment). With the global trend of becoming sustainable/green and the increasingly strict regulations, the mining industry is facing an unprecedented pressure to handle the problematic reagents that can lead to the adverse impacts. Unfortunately, the interests of the prior research are biased on the performance of the reagents to optimize the efficiency and lower the cost, while the examination of the decomposition behavior is almost neglected. Under the circumstance of poor endeavor found in the prior investigations, the knowledge gap awaits to be filled in a systematic and integrated manner to recommend countermeasures for those problematic reagents.
It can be seen from those fragmented studies collected from literature that only a limited understanding of thermal or aqueous decomposition behavior is achieved. It is far from sufficient for industrial guidance of mitigation. One key reason is the lack of robust methods to investigate decomposition under various conditions that are interesting to the mining companies (e.g., the flotation conditions). Consequently, the method development has always been considered of the utmost importance upon the start of this work to align with our overall goal of understanding the decomposition behavior under the various conditions.
Three methods under a consistent strategy were designed to examine the decomposition under three conditions from Simple (in aqueous solutions alone), to Complex (in ore pulp under flotation conditions), to Specific (in solution containing metal ions). These three conditions were chosen based on the general interests from several prominent mining companies (Vale, Barrick, Freeport McMoRan and Newmont) to understand the decomposition mechanism and kinetics. The Simple is to serve as control for all other conditions. Besides, most of the prior studies in the literature are only conducted for the Simple condition. Therefore, the Simple is to resolve all discrepancies and conflicts, and provide a relatively comprehensive summary of the decomposition under the control condition. The Complex puts decomposition in a new environment that has never been explored before: the ore pulp under the simulated batch flotation conditions. Conclusions drawn from this part provide the most practical guidance for industrial mitigation. The Specific goes after the Complex to thoroughly understand the effect of a specific factor on decomposition. The decomposition responding to the variation of a certain factor is followed within a closed system with the compositional changes measured in all phases. The integrated analysis enables the correlation of the decomposition behavior to its original causes, which are the interactions of the reagent with other components in the system.
Through the systematic investigation of decomposition of various reagents under various conditions, it is concluded that decomposition depends heavily on those parallel or sequential interactions that occur along with the decomposition reaction. For example, the decomposition reaction of xanthate throughout our entire study is regarded as ROCS₂⁻→CS₂. When xanthate forms xanthic acid, monothiocarbanate or dixanthogen with the change of pH, its breakup into CS₂ is altered. When xanthate interacts with Cu²⁺ forming Cu₂X₂, decomposition is depressed, but with Fe³⁺ forming FeX₃ decomposition is promoted. The CS₂ generated from decomposition could interact with OH- to form CS₃²⁻ or dissolve in solution or adsorb on minerals, leading to the decrease of CS₂ detected. The bonding properties between the –CS₂ moiety and other atoms or radicals in the molecule affect the stability of the reagents and the subsequent decomposition. The necessity to include a list of the side-interactions as complete as possible is key to understand and predict the decomposition behavior.
With experimental efforts taken to develop methodologies to measure the decomposition under various conditions, the attempt to model the decomposition behavior is also initiated in this work. Based on the conclusions from experimental results, major components determining the output of the final decomposition products are identified. Unsurprisingly, the decomposition reaction together with its parallel and sequential interactions is critical. Simulation using Matlab to assess the decomposition of a simplified system containing SIBX and Cu²⁺ ions has achieved preliminary success by matching well with the experimental measurements. This establishes the groundwork for furthering the simulation of more complex systems and model development.
Reagents decompose differently, although they might be applied to function similarly during an operation. As flotation collectors used for sulfide ore beneficiation, dithiocarbamate and xanthate possess some similarities in the decomposition in terms of generating CS₂. Their decomposition also decreases with the chain length. On the other hand, the decomposition of dithiophosphate and dithiophosphinate are different as the breakup of the molecule is mainly at their alkyl chain to generate moieties such as olefins.
Compared to the studies carried out to understand the performance of the reagents when being used, research on decomposition requires more attention. Therefore, derivative work can be conducted based on results achieved in this work. For example, it is useful to further examine how reagents decompose after adsorbing on the mineral surfaces. It complements the knowledge to thoroughly understand decomposition at different spots within a complex system.
The chemical fate studies of mining reagents with respect to the understanding the decomposition open up the window of developing methodologies to examine adverse behaviors. The experimental setups are applicable to simulate various conditions under which the reagent is being used and generating the adverse impacts. The strategy of analyzing decomposition within a complex system as shown in this study also provides insight into systematically investigating the other types of adverse behaviors.


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More About This Work

Academic Units
Earth and Environmental Engineering
Thesis Advisors
Somasundaran, Ponisseril
Ph.D., Columbia University
Published Here
March 24, 2016
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