Date Available

4-28-2017

Year of Publication

2017

Document Type

Doctoral Dissertation

Degree Name

Doctor of Philosophy (PhD)

College

Engineering

Department/School/Program

Mining Engineering

Advisor

Dr. Rick Honaker

Abstract

Rare earth mineral recovery from alternative resources such as coal and coal byproducts is increasingly important to provide an opportunity for economic recovery from U.S. sources. Currently, China produces the majority of the 149,000 tons of rare earth elements used annually worldwide of which the U.S. imports 11% or around 16,000 tons. There are no significant mining operations producing rare earth elements in the U.S. However, there are many U.S. sources containing rare earth minerals such as monazite including heavy mineral sand and phosphate operations. Monazite mineral particles of a few microns have also been detected in Fire Clay seam coal. Preliminary attempts to concentrate the rare earth mineral using flotation test results indicated that monazite was floated together with carbonate minerals. The flotation chemistry of a monazite-carbonate mineral system has received limited attention by researchers. As such, a systematic study of monazite flotation chemistry was conducted and the results reported in this dissertation.

The surface charging mechanisms of monazite in aqueous systems were studied using electrokinetic tests, solution equilibrium calculation, crystal structure analysis, and electrostatic model prediction. The surface charge of monazite was found to be developed by protonation/deprotonation reactions. In other words, the hydrogen and hydroxyl ions were potential determining ions instead of the lattice ions of monazite. Electrokinetic tests of natural monazite mineral showed that the isoelectric point (IEP) occurred at pH 6.0. Solution equilibrium calculation and electrostatic model predictions of cerium monazite (CePO4) yielded an IEP of pH 7.2. The discrepancy between the two IEP values may be due to the different REE composition and/or the amount of carbon dioxide dissolved in solution.

A common collector used to produce a hydrophobic monazite surface is octanohydroxamic acid. Adsorption studies found multilayer formation of octanohydroxamic acid on monazite surfaces at pH values of 3.0, 6.0, and 9.0. A kinetic study showed that the maximum adsorption density and rate for below monolayer coverage occurred at a solution pH value of 9.0, which was attributed to the chemical reaction between octanohydroxamate species and surface active sites (e.g., REE(OH)2+). For beyond multilayer adsorption, maximum adsorption occurred at pH 11.0 due to the abundance of hydroxyl ions in solution. The contributing effect of hydroxyl ions was proven by titration tests and FTIR analyses.

When calcium ions existed in solution, specific adsorption of Ca(OH)+ on monazite surfaces occurred in both neutral and basic environments as indicated by the electrokinetic results. At low concentrations, Ca(OH)+ competed with octanohydroxamic acid for P-OH sites. However, higher dosages of Ca(OH)+ served as active sites for octanohydroxamic acid. The monazite floatability was negatively affected by the hydration of the adsorbed calcium species. The calcium ion dissolved from calcite mineral surfaces, which exist in the coal sources, provided an explanation for the depression of monazite in the combined systems.

Single mineral flotation of monazite and calcite showed that sodium silicate and sodium hexametaphosphate efficiently depressed calcite while providing minimal effects on monazite recovery. However, in the monazite-calcite combined system, both monazite and calcite were depressed using the two regulators. Electrokinetic data and solution equilibrium calculations indicated that hydrolyzed species of calcium such as Ca(OH)+ interacted with silicates and formed a compact hydrophilic layer on monazite surfaces by hydrogen bonding and surface reaction. The compact layer decreased collector adsorption due to steric hindrance. Using 6×10-5 M EDTA together with 2.5×10-4 M octanohydroxamic acid and 0.05 g/L sodium silicate, monazite recovery of more than 90% was achieved while only recovering 20% of calcite. Based on the fundamental study, rare earth concentrates with 4700 ppm of REEs were produced from the Fire Clay fine coal refuse using column flotation.

Digital Object Identifier (DOI)

https://doi.org/10.13023/ETD.2017.167

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