economic extraction, recovery, and upgrading of rare earth

1
Economic Extraction, Recovery, and Upgrading of Rare Earth Elements From Coal-Based Resources To test solvent extraction a solution of 50 ppm Dy, Nd, Pr, and Sm with 1000 ppm Fe was made to simulate leaching product. 10mL 10% D2EHPA in kerosene was used to load 30mL of solution. It was observed from the loading of organic that it is possible to load 100% of the rare earths by a pH of 1.9. Stripping was done using 30mL Nitric Acid with 10 mL loaded organic. Stripping results gave fairly good recovery by pH 0.2, though stripping at even lower values should yield higher recovery. Michael Free, Prashant Sarswat, Gerald Luttrell, Aaron Noble, Xianwei Hu, Landon Allen, Marina McNeill, Dae Jin Kim, and Isaias Arce Utilize low-cost technologies to enable larger resource utilization Utilize selective separation technologies to upgrade REE concentration in feedstock. Utilize heap leaching technology for large- scale, low cost extraction Utilize biooxidation and pyrite to provide low cost reagents and rapid leaching Utilize solvent extraction and precipitation to concentrate and recover product Perform a technoeconomic analysis to provide investment and commercialization guidance Course refuse samples from four coal plants in WV, PA, and VA. All crushed to -1 inch; REE content varies from 250 to 300 PPM Some coal seams tend to be elevated in pyrite, which can oxidize to produce sulfuric acid. To counteract downstream environmental issues, some modern coal preparation facilities employ a “desulfurization circuit” to isolate pyrite from the clean coal product. Three cases for further investigation: A) High Sulfur Coal With Desulfurization B) High Sulfur Coal Without Desulfurization C) Low Sulfur Coal Pyrite vein in coal sample. Framboidal Pyrite = Highly Reactive FINE WASTE Dense Medium Cyclones CLEAN COAL COARSE WASTE FEED COAL Clean D&R Screen Reject D&R Screen Raw Coal Screen Raw Coal Cyclones Coal Spirals Refuse Screen Sieve Deslime Cyclones Froth Flotation Thickener Desulfurization Spirals PYRITE WASTE Size Control Heap Feed Material 300 – 350 PPM REE 2” x 0.25” Biooxidation Enhancer/ Leaching Accelerator 15 – 20% Sulfur 250 micron x 50 microns Current Coal Preparation Facility Raw Stream Waste Stream Clean Stream REE Feed Stream Rare Earth Heap Leach Case A: High Sulfur Coal with Desulfurization Circuit Screenbowl FINE WASTE Dense Medium Cyclones CLEAN COAL COARSE WASTE FEED COAL Clean D&R Screen Reject D&R Screen Raw Coal Screen Raw Coal Cyclones Coal Spirals Refuse Screen Sieve Screenbowl Thickener Size Control Heap Feed Material 300 – 350 PPM REE 2” x 0.25” Biooxidation Enhancer/ Leaching Accelerator 15 – 20% Sulfur 250 micron x 50 microns Current Coal Preparation Facility Raw Stream Waste Stream Clean Stream REE Feed Stream Rare Earth Heap Leach CASE C: Low Sulfur Coal External Pyrite Source Froth Flotation Deslime Cyclones Coal Comparisons Each of the coal samples is being leached using: 30 wt% Coal waste 10 g/L Ferric Sulfate in DI Water 150 mL Ferric Sulfate solution pH 1.5 pH adjusted hourly for the first 8 hours, then again at 25 hours for acid consumption. 96 hours Acquisition of active bacteria cultures (acidithiobacillus ferrooxidans) to facilitate biooxidation. Growth of bacteria in 9K base medium (using essential salts with potassium, nitrogen, magnesium, phosphorus, and additional ferrous sulfate) along with air-sparging for numerous leaching tests. Monitoring of redox potential to check the bioactivity of the bacteria cultures. Periodic ferrous oxidation testing to quantify the bacterial population using predetermined quantity of ferrous ion addition. The rare earth elements will be recovered by precipitation from the solvent extraction stripping solution. Bath and mixer for use in 500mL leach tests Comparison leaching tests Schematic diagram showing flows and host rock particles (hrp) and valuable mineral particle (vmp) interactions Loading of organic with REEs Separatory funnel with organic and aqueous phases McCabe-Thiele diagram showing the relationship between the metal content in the organic and aqueous phases Bacterial growth vessels Eh vs time (indicative of bacterial activity) Gaudin-Schumann Plot for Coarse Refuse Sample REE Content of Various Preparation Plant Products Acknowledgement: Funding provided by the Department of Energy: Grant # DE- FE0031526 Iron precipitate Stripping solution from solvent extraction

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Economic Extraction, Recovery, and Upgrading of Rare Earth Elements From Coal-Based Resources

• To test solvent extraction a solution of50 ppm Dy, Nd, Pr, and Sm with 1000ppm Fe was made to simulate leachingproduct.

• 10mL 10% D2EHPA in kerosene wasused to load 30mL of solution.

• It was observed from the loading oforganic that it is possible to load 100%of the rare earths by a pH of 1.9.

• Stripping was done using 30mL NitricAcid with 10 mL loaded organic.

• Stripping results gave fairly goodrecovery by pH 0.2, though stripping ateven lower values should yield higherrecovery.

Michael Free, Prashant Sarswat, Gerald Luttrell, Aaron Noble, Xianwei Hu, Landon Allen, Marina McNeill, Dae Jin Kim, and Isaias Arce

• Utilize low-cost technologies to enable larger resource utilization

• Utilize selective separation technologies to upgrade REE concentration in feedstock.

• Utilize heap leaching technology for large-scale, low cost extraction

• Utilize biooxidation and pyrite to provide low cost reagents and rapid leaching

• Utilize solvent extraction and precipitation to concentrate and recover product

• Perform a technoeconomicanalysis to provide investment and commercialization guidance

• Course refuse samples from four coal plants in WV, PA, and VA.

• All crushed to -1 inch; REE content varies from 250 to 300 PPM

Some coal seams tend to be elevated in pyrite, which can oxidize toproduce sulfuric acid.To counteract downstream environmental issues, some modern coalpreparation facilities employ a “desulfurization circuit” to isolate pyritefrom the clean coal product.Three cases for further investigation:

A) High Sulfur Coal With DesulfurizationB) High Sulfur Coal Without DesulfurizationC) Low Sulfur Coal

Pyrite vein in coal

sample.

Framboidal Pyrite = Highly Reactive

FINEWASTE

Dense MediumCyclones

CLEANCOAL

COARSEWASTE

FEEDCOAL Clean

D&R Screen

RejectD&R

Screen

Raw CoalScreen

RawCoal

Cyclones

CoalSpirals

RefuseScreen

Sieve

DeslimeCyclones

FrothFlotation

Thickener

Desulfurization Spirals PYRITE

WASTE

Size Control

Heap Feed Material300 – 350 PPM REE

2” x 0.25”

Biooxidation Enhancer/Leaching Accelerator

15 – 20% Sulfur250 micron x 50 microns

Current Coal Preparation Facility

Raw StreamWaste StreamClean Stream REE Feed Stream

Rare Earth Heap Leach

Case A: High Sulfur Coal with Desulfurization Circuit

Screenbowl

FINEWASTE

Dense MediumCyclones

CLEANCOAL

COARSEWASTE

FEEDCOAL Clean

D&R Screen

RejectD&R

Screen

Raw CoalScreen

RawCoal

Cyclones

CoalSpirals

RefuseScreen

Sieve

Screenbowl

Thickener

Size Control

Heap Feed Material300 – 350 PPM REE

2” x 0.25”

Biooxidation Enhancer/Leaching Accelerator

15 – 20% Sulfur250 micron x 50 microns

Current Coal Preparation Facility

Raw StreamWaste StreamClean Stream REE Feed Stream

Rare Earth Heap Leach

CASE C: Low Sulfur Coal

External Pyrite Source

FrothFlotation

DeslimeCyclones

Coal Comparisons• Each of the coal samples is

being leached using:• 30 wt% Coal waste• 10 g/L Ferric Sulfate in DI Water• 150 mL Ferric Sulfate solution• pH 1.5• pH adjusted hourly for the first

8 hours, then again at 25 hoursfor acid consumption.

• 96 hours

• Acquisition of active bacteria cultures(acidithiobacillus ferrooxidans) to facilitatebiooxidation. Growth of bacteria in 9K basemedium (using essential salts withpotassium, nitrogen, magnesium,phosphorus, and additional ferrous sulfate)along with air-sparging for numerousleaching tests.

• Monitoring of redox potential to check thebioactivity of the bacteria cultures.

• Periodic ferrous oxidation testing to quantifythe bacterial population usingpredetermined quantity of ferrous ionaddition.

• The rare earth elements will be recovered by precipitation from the solvent extraction stripping solution.

Bath and mixer for use in 500mL leach tests

Comparison leaching tests

Schematic diagram showing flows and host rock particles (hrp) and valuable

mineral particle (vmp) interactions

Loading of organic with REEs Separatory funnel with organic and aqueous phases

McCabe-Thiele diagram

showing the relationship between the

metal content in the organic and aqueous

phases

Bacterial growth vessels

Eh vs time (indicative of bacterial activity)

Gaudin-Schumann Plot for Coarse Refuse Sample

REE Content of Various Preparation Plant Products

• Acknowledgement:• Funding provided by the Department of Energy: Grant # DE-

FE0031526

Iron precipitate

Stripping solution from solvent extraction