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Potential of Organosolv Lignin Nanoparticles as a Sustainable Flotation Reagent: Towards a Low-Carbon Footprint Mining Industry
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering.ORCID iD: 0000-0002-1132-8947
2024 (English)Doctoral thesis, comprehensive summary (Other academic)Alternative title
Potential för organosolv lignin nanopartiklar som en hållbar flotations reagens : ett steg mot en gruvindustri med ett lågt koldioxidavtryck (Swedish)
Abstract [en]

The green transition is driving a steep increase in the demand for minerals, which has put the focus on more responsible and sustainable mining practices as there is a growing pressure on mining operations to minimise their environmental footprint, mitigate risks in neighbouring communities, and decrease the consumption of natural resources. In 2022, mineral froth flotation was used to recover 18 million tonnes of copper from copper ore, accounting for 80% of total copper mine output. The mineral froth flotation process can be made more sustainable through the use of bio-based and biodegradable flotation reagents. Currently, xanthates are used as collectors for the recovery of copper-bearing sulfide minerals from sulfide ores. However, xanthates are fossil-based and pose significant risks, particularly to aquatic life and ecosystems. Additionally, a significant part of xanthates is currently obtained from production sites in Asia, which can lead to supply dependency and delays, as evident during the global pandemic.

The aim of this thesis was to develop an efficient, sustainable, and environmentally friendly mineral froth flotation process based on total or partial replacement of xanthates with bio-based, biodegradable, and low-carbon footprint organosolv lignin particles (OLP). The lignin was obtained through organosolv fractionation of residual forest biomass, i.e. spruce and birch. The particles were produced via solvent exchange method from the homogenized lignin solution. As a result, 4 different particle types were produced: birch nanoparticles (BN), birch microparticles (BM), spruce nanoparticles (SN), and spruce microparticles (SM). At first, the characterization and surface chemistry study of the OLP was carried out to deepen the understanding of interaction mechanism between the OLP and mineral surfaces. The lignin was characterized by gel permeation chromatography and nuclear magnetic resonance for its molecular size and content of functional groups. While morphology, surface charge and stability in dispersion of the particles was determined using scanning electron microscopy, ζ-potential, and Turbiscan. All 4 particles were spherical with the diameter around 100 nm for nanoparticles and 1μm for microparticles. The ζ-potential measurement showed the surface variation caused by the difference in size and content of functional groups. Spruce particles, SN and SM, had higher negative charge due to higher content of carboxylic and total phenolic groups. Under alkali conditions, the ζ-potential below -20mV for all particles, with the lowest at −55.1 mV for SM. Finaly, the interaction of OLP with mineral surfaces was examined using quartz crystal microbalance. While the attachment of all OLP was very rigid for both, chalcopyrite and pyrite surfaces, the affinity for attachment was notably greater in the case of pyrite compared to chalcopyrite.

The OLP was tested in proof-of-concept study on three different ore samples, and improvements in the flotation performance was observed, including better selectivity and increased recovery. The further evaluation of the OLP as flotation reagent was conducted with copper ore samples. The flotation trials were carried out with 600 g of ore sample in laboratory flotation cell. Starting with the dosage study, the results were confirmed in rougher-cleaner flotation tests. However, the OLP could not be used as a sole collector, it was shown that significant part of xanthate in the flotation mix could be replaced by OLP resulting in improved copper recovery and selectivity. Additionally, a synergy was observed when the OLP and xanthate mixture was used as combined reagents performed better than each of them separately at the same dosage. The copper recovery was increased from 82.2% to 88.7% in a semi-pilot rougher flotation when 50% of xanthate was replaced by OLP compared to the xanthate alone. Significant depression of iron recovery was observed when the OLP was utilized, even in absence of lime. Thus, the OLP reagents eliminated the need for lime, which is required on an industrial scale. Further positive effect of OLP application was indicated recovery of other valuable elements in the concentrates, such as cobalt and molybdenum, while there was no increase in penalty elements. The amount of OLP needed was up to 10 g/ton of ore, which is very small amount, and it is roughly 10 times less compared to any other modifier used in such a process. Therefore, this thesis demonstrates the potential of OLP as flotation reagent. If implemented, the proposed flotation system would lead to better resource efficiency and lower environmental impact.

Place, publisher, year, edition, pages
Luleå: Luleå University of Technology, 2024.
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
Keywords [en]
Organosolv lignin particles, Nanoparticles, Flotation reagent, Copper recovery
National Category
Chemical Process Engineering
Research subject
Biochemical Process Engineering
Identifiers
URN: urn:nbn:se:ltu:diva-105140ISBN: 978-91-8048-542-5 (electronic)ISBN: 978-91-8048-543-2 (print)OAI: oai:DiVA.org:ltu-105140DiVA, id: diva2:1852220
Public defence
2024-09-26, C305, Luleå University of Technology, Luleå, 09:00 (English)
Opponent
Supervisors
Available from: 2024-04-17 Created: 2024-04-17 Last updated: 2024-09-05Bibliographically approved
List of papers
1. Organosolv lignin hydrophobic micro- and nanoparticles as a low-carbon footprint biodegradable flotation collector in mineral flotation
Open this publication in new window or tab >>Organosolv lignin hydrophobic micro- and nanoparticles as a low-carbon footprint biodegradable flotation collector in mineral flotation
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2020 (English)In: Bioresource Technology, ISSN 0960-8524, E-ISSN 1873-2976, Vol. 306, article id 123235Article in journal (Refereed) Published
Abstract [en]

Flotation is a key step during mineral separation. Xanthates are the most commonly used collectors for recovering Cu, Ni, and Zn from sulphide ores. However, xanthates are fossil-based and toxic for the environment. The aim of this study was to evaluate the use of lignin nanoparticles and microparticles as sustainable and environmentally friendly collectors. Lignin particles demonstrated good selectivity toward Cu (chalcopyrite), with total recoveries exceeding 80% and grades of up to 8.6% w/w from a Cu-Ni ore in rougher flotation tests. When floating Zn-Pb-Cu ore, lignin nanoparticles could reduce the use of xanthates by 50%. Moreover, they outperformed xanthates alone, achieving total recoveries of up to 91%, 85%, and 98% for Cu, Pb, and Zn, respectively. These results prove the potential of lignin as a flotation collector.

Place, publisher, year, edition, pages
Elsevier, 2020
Keywords
Lignin, Nanoparticles, Flotation, Collector, Organosolv
National Category
Bioprocess Technology
Research subject
Biochemical Process Engineering
Identifiers
urn:nbn:se:ltu:diva-78359 (URN)10.1016/j.biortech.2020.123235 (DOI)000532714500003 ()32229063 (PubMedID)2-s2.0-85082530221 (Scopus ID)
Note

Validerad;2020;Nivå 2;2020-05-04 (alebob)

Available from: 2020-04-06 Created: 2020-04-06 Last updated: 2024-04-17Bibliographically approved
2. Characterization of Organosolv Lignin Particles and Their Affinity to Sulfide Mineral Surfaces
Open this publication in new window or tab >>Characterization of Organosolv Lignin Particles and Their Affinity to Sulfide Mineral Surfaces
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2023 (English)In: ACS Applied Nano Materials, E-ISSN 2574-0970, Vol. 6, no 19, p. 17387-17396Article in journal (Refereed) Published
Abstract [en]

Organosolv lignin nanoparticles have been recently evaluated for their use in mineral froth flotation as a flotation reagent, and as a result, the recovery of the target minerals was improved and the selectivity of the process was increased. However, the mechanism of lignin activity in mineral froth flotation is not known. Therefore, this study is the first step in understanding the interaction of organosolv lignin with the mineral surface. As such, the organosolv lignin was characterized by GPC and 31P NMR, where the structural differences between the birch and spruce lignins were determined. The molecular size and lignol unit composition were evaluated. Subsequently, the morphology and size of the organosolv lignin particles were examined for all 4 produced types: BN, BM, SN, and SM. The ? potential was measured in the pH range of 2-11. All particles had a high negative charge, which indicated good stability of the dispersion in the alkali range. The stability of their colloidal dispersion was observed under increasing concentrations of mono- and divalent cations, and electrostatic repulsion was identified as the main stabilization mechanism. Finally, QCM-D was used to study the interaction of the lignin particles with the mineral surfaces of chalcopyrite, pyrite, and galena, which gave insight into the possible mechanism during the flotation process.

Place, publisher, year, edition, pages
Amer Chemical Soc, 2023
Keywords
organosolv lignin, nanoparticles, microparticles, surface chemistry, mineral surfaces, QCM-D
National Category
Bioprocess Technology
Research subject
Biochemical Process Engineering
Identifiers
urn:nbn:se:ltu:diva-101664 (URN)10.1021/acsanm.3c02069 (DOI)001068455100001 ()2-s2.0-85175015641 (Scopus ID)
Projects
LIGNOFLOT
Funder
Vinnova, 2017-05456
Note

Validerad;2023;Nivå 2;2023-10-16 (joosat);

CC BY 4.0 License

Available from: 2023-10-16 Created: 2023-10-16 Last updated: 2024-08-15Bibliographically approved
3. Boosting Copper Sulfide Ore Flotation Efficiency through a Substantial Replacement of Xanthate Collectors with Organosolv Lignin Particles
Open this publication in new window or tab >>Boosting Copper Sulfide Ore Flotation Efficiency through a Substantial Replacement of Xanthate Collectors with Organosolv Lignin Particles
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

The green transition requires a lot of metals or minerals that must be mined and processed. One of the most widely used processes to recover sulfidic minerals is froth flotation. Flotation reagents are necessary for the selective recovery of target minerals. The main purpose of the study was to demonstrate a novel sustainable flotation process for selective extraction of chalcopyrite from sulfide ores, based on partial replacement of fossil-based xanthate flotation collectors with bio-based, biodegradable, and non-toxic organosolv lignin particles. The addition of organosolv lignin particles provided increased recovery of copper by almost 20 % with high selectivity in the rougher flotation. The amount of required xanthate was significantly lowered by 75% in the newly proposed process. In addition, the economical and environmental impact of the whole process could be improved by removal of lime, as pH adjustment through lime addition was not necessary to achieve good selectivity.

Keywords
Organosolv Lignin, Nanoparticles, Froth Flotation, Sulfides, Chalcopyrite
National Category
Chemical Process Engineering
Research subject
Biochemical Process Engineering
Identifiers
urn:nbn:se:ltu:diva-105135 (URN)
Available from: 2024-04-17 Created: 2024-04-17 Last updated: 2024-04-17
4. Organosolv Lignin Particles as a Partial Replacement of Xanthate Collector in a Copper Sulfide Ore Flotation: Scale-up Study
Open this publication in new window or tab >>Organosolv Lignin Particles as a Partial Replacement of Xanthate Collector in a Copper Sulfide Ore Flotation: Scale-up Study
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

The transition to a sustainable, green economy indeed requires more access to strategic/critical metals for renewable energy technologies while simultaneously reducing reliance on fossil fuels and their byproducts. In mineral processing, various research for an environment-friendly flotation reagents have been ongoing for many years. In this paper, the potential of organosolv lignin particles (OLP) as a biobased reagent that can improve the grade and recovery of Cu was demonstrated using real sulfide ore. The main advantage of this process is that it requires low dosage of OLP in the tested condition and set-up. The initial laboratory batch flotation tests showed that potassium amyl xanthate (PAX) can be partially replaced with OLP by 50% and in the absence of depressant, lime. These results were further verified in semi-pilot flotation tests that showed an increase in recovery by 8% in the rougher stage and comparable grade in the final cleaner stage when using the OLP-PAX mixture with respect to PAX at full dosage. In general, this paper presents the progress towards validating the viability of OLP as a biobased flotation reagent suitable for industrial-scale applications.

Keywords
Organosolv Lignin, Nanoparticles, Froth Flotation, Sulfides, Chalcopyrite
National Category
Chemical Process Engineering
Research subject
Biochemical Process Engineering
Identifiers
urn:nbn:se:ltu:diva-105137 (URN)
Available from: 2024-04-17 Created: 2024-04-17 Last updated: 2024-04-17

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