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Summer course (IVC)
27 August 2021
Recycling of metals using
microbes and plants
SITI KHODIJAH CHAERUN
Department of Metallurgical Engineering, Faculty of Mining & Petroleum Engineering, Institut Teknologi Bandung
Biosciences and Biotechnology Research Center (BBRC), Institut Teknologi Bandung
Educational and Work Background:
 B.Eng (Ir.) – Environ Engineering, ITB, Indonesia (1988-1993)
 M.Eng (M.T.) – Environ Bioengineering, ITB, Indonesia (1996-1999)
 PhD. – Petroleum and Environ Geomicrobiology,
Biomining/Biometallurgy, Minerals Biotechnology, Bioremediation,
Dept of Earth Sciences, Kanazawa University, Japan (2001-2004)
 Postdoctoral Researcher, ZALF Centre, Berlin, Germany (2006)
 Visiting Scientist, Tokyo University of Agriculture and Technology,
Japan (2007)
 Postdoctoral Associate, Dept. of Microbiology, Atlanta, Georgia, USA
(2008-2009)
 Visiting Research Fellow, Dept. of Energy & Resources Engineering,
Peking University, Beijing, China (2011-2014)
Current Position:
Associate Professor
Department of Metallurgical Engineering, Faculty of Mining
and Petroleum Engineering, Institut Teknologi Bandung (ITB),
Indonesia
Metal Resources
Naturally occurring resources
(Primary sources)
Secondary resources
bisnis.tempo.co
www.google.com
“Urban mine” resources
Tailings
slags
wikipedia
Biomining (biohydrometallurgy)
Spent catalyst: Ledoux&Co
Kennecott: The largest copper mine in the world! Kennecott provides approximately 13 percent of the
country's copper with production of over 300,000
tons of refined copper each year.
Copper bioleaching at the Kennecott Copper
Bingham Mine, in Utah, USA since the 1950s
Biohydrometallurgy technology
Use of microbes (bacteria, archaea, fungi) to recover metals
from low-grade ores, mine wastes and metallic wastes
Biomining: a technology that harnesses the
abilities of certain microbes to accelerate the
dissolution of minerals, thereby facilitating the
recovery of metals of value (Johnson, 2010)
Biomining: the use of microorganisms to recover
precious and base metals from mineral ores and
concentrates (Rawlings & Johnson, 2007)
Biomining is the use of microorganisms to extract
metals from sulfide and/or iron-containing ores
and mineral concentrates (Rawlings et al., 2003)
Biohydrometallurgy
BioMineWiki
Interdisciplinary study field that involves processes that:
•make the use of microbes, usually bacteria, archaea, fungi---- BIO
•mainly take place in aqueous environment-------------- HYDRO
•deal with metal production & treatment of metal-containing
materials and solution --------------------- METALLURGY
-Low cost (less energy intensive)
-Processing of lower-grade ores
-Processing of complex ores (polymetallics)
-Recovery of by-product
-Environmentally friendly
-No emission of any harmful gas or chemical in the environment
-Selective, enhanced bioleaching
(Johnson, 2010; Brierley, 2010; Rawlings, 2004)
Czichos, 1987
(Bio-) Hydrometallurgy
(Aqueous chemistry)
Chemical Leaching
Bioleaching
Bio-reactor
Heaps
Low cost
Low-grade ores
Pyrometallurgy
(thermal treatment)
Smelting process
Melting furnace
High cost
High-grade ores
Microbes playing roles in biohydrometallurgy
No protein coat
No DNA or RNA
• Chemolithotrophs/chemolithoautotrophs/chemoautotrophs
• Chemoorganotrophs/heterotrophs
• Mixotrophs
• Iron-oxidizing
• Sulfur oxidizing
• Acidophilic
• Metals-resistant
• Biosurfactant-producing (e.g., EPS)
• Organic acid-producing
From the viewpoint of microbial metabolism
Fungi/Fungus
Bacteria/Bacterium
Expected microbes for biomining process:
Indigenous Fungi
Indigenous Bacteria (Chemoorganotrophs and Mixotrophs)
Taxonomy level in Microbial systematics
(Classification, identification, nomenclature)
Bergey's International Society for Microbial Systematics
Prokaryotes
Aspergillus sp.
Bacillus sp.
Eukaryotes
Aspergillus spp.
Bacillus spp.
Sulfide Minerals Oxide Minerals
Hematite: Fe2O3
Rutile: TiO2
Magnetite:Fe3O4
Goethite: αFeO(OH)
Quartz: SiO2
Calcite: CaCO3
Pyrite: FeS2
Galena: PbS
Sphalerite: ZnS
Chalcopyrite: CuFeS2
Tungstenite: (WS2)
Molybdenite: MoS2
Fundamental principles of biohydrometallurgy
Biooxidation Bioleaching
Pentlandite
Arsenopyrite
Johnson, 2010
Au(CN)2
-
Principle of Biooxidation
Contact Bioleaching Non-contact Bioleaching
Johnson, 2010
M0
Attached microbial
cells
Ore/material
M+
Liquid media
M0 M+
cells
pH ↓
M0
M+
M+
Thiosulfate mechanism Polysulfide mechanism
Schippers et al., 1999
Af: Acidithiobacillus ferrooxidans
Lf: Leptospirillum ferrooxidans
At: Acidithiobacillus thiooxidans
A B
Thiosulfate mechanism
Schippers et al., 1999
FeS2 , MoS2 , and WS2
Polysulfide mechanism
Schippers et al., 1999
e.g. ZnS (Sphalerite), CuFeS2 , or PbS (Galena)
Fungi: Genus Aspergillus & Penicillium
Fungi are capable of oxidizing substrate only partially
and then secreting it. This incomplete oxidation
causes the accumulation of organic acids, which are
able to extract metals from solid materials
Proton attack:
NiO + 2H+ ---- Ni2+ + H2O
CaCO3 + 2H+ ---- Ca2+ + H2O + CO2
Reduction: MnO2 + 2e- + 4H+ ---- Mn2+ + 2H2O
Complexation/Chelation:
Ni2+ + C6H5O7 ---- Ni(C6H5O7) + 3H+
Bioleaching of nickel laterite ores (saprolite and limonite)
High selective leaching:
The leaching using metabolic organic acids of Aspergillus
niger is selective to magnesium
Biooxidation of carbonaceous refractory gold ores
Control: without bacterial inoculation
AC: chemolithotropic bacterium
SKC1: iron-oxidizing mixotrophic bacterium
SKC2:sulfur-oxidizing mixtrophic bacterium
Bioleaching of copper sulfide ores
T1: bioleaching experiment without addition of
pyrite and sulfur adjusted to pH 3;
T2: bioleaching experiment with addition of 1%
w/v pyrite and 0.25% w/v sulfur adjusted to pH 3;
T3: bioleaching experiment with addition of 1%
w/v pyrite and 0.25% w/v sulfur without pH
adjustment;
T4: bioleaching experiment with addition of 5%
w/v pyrite and 2.5% w/v sulfur
adjusted to pH 3;
T5: bioleaching experiment with addition of 5%
w/v pyrite and 2.5% w/v sulfur
without pH adjustment;
T6: abiotic control without the bacterium which
was identical to
bioleaching experiment (T1)
29.25 g/l NaCl
T: 28 oC
a particle size = 75 μm
5% pulp density
Bioleaching of organic sulfur from coal
Treatment A: a combination of biooxidation
for 15 days and bioflotation;
Treatment B: a combination of biooxidation
for 40 days and bioflotation;
Treatment C: bioflotation;
Treatment D: column flotation
Recycling of metals from E-wastes
Primary source
Natural ores
Base metals:
Cu, Fe, Al
Platinum group
metals: Pd, Pt
Precious group
metals: Au, Ag
Other elements:
Plastic, ceramic
“Urban mine” resources
Secondary source
Au Ag
Cu Fe
Al Pd Pt
Year 2016
Proposed reactions of copper bioleaching from PCBs
(Ilyas et al., 2013; Zhu et al., 2011; Xiang et al., 2010)
Indirect mechanism
4Fe2+ + O2  4Fe3+ + H2O
2Fe3+ + Cu0  2Fe2+ +Cu2+
Direct mechanism, in the absence of Fe, elemental sulfur as the energy source. Cu is
solubilized by protons, although in such case, molecular O2 is involved
S0 + H2O  H+ + SO4
2-
2Cu0 + 4H+ + O2  2Cu2+ + 2H2O
Acidithiobacillus sp. Ferrimicrobium
acidiphilum
Ferroplasma
acidimicrobium
Leptospirillum sp.
Microorganisms involved: Fe/S-Oxidizing bacteria and archaea
Microorganisms involved: cyanogenic bacteria and archaea
Au dissolution by (bio)cyanidation consists of an anodic and a cathodic reaction
4Au + 8CN-  4Au(CN)2
- + 4e- (anodic)
O2 + 2H2O + 4e-  4OH- (cathodic)
The overall reaction is known as Elsner’s equation (Hedley and Tabachnick, 1953)
4Au + 8CN- + O2 + 2H2O  4Au(CN)2
- + 4OH-
Pseudomonas plecoglossicida
Principles of Phytomining
1997
The Streptanthus polygaloides plant is a hyperaccumulator of
nickel, with hyperaccumulation defined as the presence of at
least 1,000 µg nickel per gram of dry mass. This species
averages 2,430 to 18,600 µg/g. This trait helps protect the plant
against many types of pathogens.
Sheoran, 2009
- Extraction of metals
from soil into the plant
roots by active transport
or sorption
Phytoextraction
- From the roots transfer/
translocation into the
shoot parts
Willscher, 2018
SEM-EDX image of the plant Miscanthus sinensis shows the adsorption ability of elements Si,
P, S, Cl, K, Ca, Fe, Cu, Zn, Pb (Tazaki & Chaerun, 2008).
Phytoaccumulation
Brooks et al., 1997
Requirements for the application
Bioavailability of the metals/ metalloids (mobility)
Occurrence of the metals in the rhizosphere
Tolerance of the plants to high metal concentrations
Satisfying growth of the plants
Phytomining
Substrates for application
- Low grade ores
- Overburden material
- Mill tailings
- Remainders of dump leaching
- Mineralized soil
- in all substrates uneconomical for conventional mining/ processing
- A large part of the processed mineral material contains low metal concentrations
- After the closedown of mining operations for the removal of lower amounts of the
mined metals and first revegetation/ stabilization Photo of Crop of Ni metals: SKC Lab
Willscher, 2018
Advantages of phytomining
- Less intrusive, low energy demand
- Soil recovering effect (improvement of soil ecology)
- Groundwater protection for the case of not too extensive application of
chemicals
- No erosion effects like other mining activities
- For sustainable closure of mining sites
- Reduction of acid mine drainage formation
Challenges
- Solubility and availability as one of the key factors
Appliction of lixiviates (mostly complex forming agents)
- Phytoextraction only in the root zone of the plants
Engineering for mass transport
Willscher, 2018
Sheoran et al., 2013
A Proposed phytomining concept: SKC
Mine
Crushing plant
Phytomining
(Concentrator)
Improved phyto-extraction parameters
Tailings, low-grade ores, the closedown of mining operations
-2 mm
Plant Harvesting
Crop of metals (Biomass)
Biomass burning
Leaching/Bioleaching
ashes
Biomass drying
under sunlight/oven
Biomass Grinding Bioenergy = Biogas
www.portonews.com
Summary
- Utilization of low grade ores, tailings and remainders
- Removal of valuable or toxic metals
- Better soil functions/ revitalization
- Improved soil fertility
- Coupled process with renewable energy production
- Lowering of the process costs
Advantages of the method
- Environmentally benign
- Non-invasive for the soil
- Low energy demand
Sumeks.co
shopee.co.id
Vetiveria zizanioides (Rumput vetiver = ilalang akar wangi)

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Workshop.pdf

  • 1. Summer course (IVC) 27 August 2021 Recycling of metals using microbes and plants SITI KHODIJAH CHAERUN Department of Metallurgical Engineering, Faculty of Mining & Petroleum Engineering, Institut Teknologi Bandung Biosciences and Biotechnology Research Center (BBRC), Institut Teknologi Bandung
  • 2. Educational and Work Background:  B.Eng (Ir.) – Environ Engineering, ITB, Indonesia (1988-1993)  M.Eng (M.T.) – Environ Bioengineering, ITB, Indonesia (1996-1999)  PhD. – Petroleum and Environ Geomicrobiology, Biomining/Biometallurgy, Minerals Biotechnology, Bioremediation, Dept of Earth Sciences, Kanazawa University, Japan (2001-2004)  Postdoctoral Researcher, ZALF Centre, Berlin, Germany (2006)  Visiting Scientist, Tokyo University of Agriculture and Technology, Japan (2007)  Postdoctoral Associate, Dept. of Microbiology, Atlanta, Georgia, USA (2008-2009)  Visiting Research Fellow, Dept. of Energy & Resources Engineering, Peking University, Beijing, China (2011-2014) Current Position: Associate Professor Department of Metallurgical Engineering, Faculty of Mining and Petroleum Engineering, Institut Teknologi Bandung (ITB), Indonesia
  • 3. Metal Resources Naturally occurring resources (Primary sources) Secondary resources bisnis.tempo.co www.google.com “Urban mine” resources Tailings slags wikipedia Biomining (biohydrometallurgy) Spent catalyst: Ledoux&Co
  • 4. Kennecott: The largest copper mine in the world! Kennecott provides approximately 13 percent of the country's copper with production of over 300,000 tons of refined copper each year. Copper bioleaching at the Kennecott Copper Bingham Mine, in Utah, USA since the 1950s Biohydrometallurgy technology
  • 5. Use of microbes (bacteria, archaea, fungi) to recover metals from low-grade ores, mine wastes and metallic wastes Biomining: a technology that harnesses the abilities of certain microbes to accelerate the dissolution of minerals, thereby facilitating the recovery of metals of value (Johnson, 2010) Biomining: the use of microorganisms to recover precious and base metals from mineral ores and concentrates (Rawlings & Johnson, 2007) Biomining is the use of microorganisms to extract metals from sulfide and/or iron-containing ores and mineral concentrates (Rawlings et al., 2003) Biohydrometallurgy BioMineWiki Interdisciplinary study field that involves processes that: •make the use of microbes, usually bacteria, archaea, fungi---- BIO •mainly take place in aqueous environment-------------- HYDRO •deal with metal production & treatment of metal-containing materials and solution --------------------- METALLURGY
  • 6. -Low cost (less energy intensive) -Processing of lower-grade ores -Processing of complex ores (polymetallics) -Recovery of by-product -Environmentally friendly -No emission of any harmful gas or chemical in the environment -Selective, enhanced bioleaching (Johnson, 2010; Brierley, 2010; Rawlings, 2004) Czichos, 1987
  • 7. (Bio-) Hydrometallurgy (Aqueous chemistry) Chemical Leaching Bioleaching Bio-reactor Heaps Low cost Low-grade ores Pyrometallurgy (thermal treatment) Smelting process Melting furnace High cost High-grade ores
  • 8. Microbes playing roles in biohydrometallurgy No protein coat No DNA or RNA
  • 9. • Chemolithotrophs/chemolithoautotrophs/chemoautotrophs • Chemoorganotrophs/heterotrophs • Mixotrophs • Iron-oxidizing • Sulfur oxidizing • Acidophilic • Metals-resistant • Biosurfactant-producing (e.g., EPS) • Organic acid-producing From the viewpoint of microbial metabolism Fungi/Fungus Bacteria/Bacterium Expected microbes for biomining process:
  • 10. Indigenous Fungi Indigenous Bacteria (Chemoorganotrophs and Mixotrophs)
  • 11. Taxonomy level in Microbial systematics (Classification, identification, nomenclature) Bergey's International Society for Microbial Systematics Prokaryotes Aspergillus sp. Bacillus sp. Eukaryotes Aspergillus spp. Bacillus spp.
  • 12. Sulfide Minerals Oxide Minerals Hematite: Fe2O3 Rutile: TiO2 Magnetite:Fe3O4 Goethite: αFeO(OH) Quartz: SiO2 Calcite: CaCO3 Pyrite: FeS2 Galena: PbS Sphalerite: ZnS Chalcopyrite: CuFeS2 Tungstenite: (WS2) Molybdenite: MoS2 Fundamental principles of biohydrometallurgy
  • 15. Contact Bioleaching Non-contact Bioleaching Johnson, 2010 M0 Attached microbial cells Ore/material M+ Liquid media M0 M+ cells pH ↓ M0 M+ M+
  • 16. Thiosulfate mechanism Polysulfide mechanism Schippers et al., 1999 Af: Acidithiobacillus ferrooxidans Lf: Leptospirillum ferrooxidans At: Acidithiobacillus thiooxidans A B
  • 17. Thiosulfate mechanism Schippers et al., 1999 FeS2 , MoS2 , and WS2
  • 18. Polysulfide mechanism Schippers et al., 1999 e.g. ZnS (Sphalerite), CuFeS2 , or PbS (Galena)
  • 19. Fungi: Genus Aspergillus & Penicillium Fungi are capable of oxidizing substrate only partially and then secreting it. This incomplete oxidation causes the accumulation of organic acids, which are able to extract metals from solid materials Proton attack: NiO + 2H+ ---- Ni2+ + H2O CaCO3 + 2H+ ---- Ca2+ + H2O + CO2 Reduction: MnO2 + 2e- + 4H+ ---- Mn2+ + 2H2O Complexation/Chelation: Ni2+ + C6H5O7 ---- Ni(C6H5O7) + 3H+
  • 20. Bioleaching of nickel laterite ores (saprolite and limonite) High selective leaching: The leaching using metabolic organic acids of Aspergillus niger is selective to magnesium
  • 21. Biooxidation of carbonaceous refractory gold ores Control: without bacterial inoculation AC: chemolithotropic bacterium SKC1: iron-oxidizing mixotrophic bacterium SKC2:sulfur-oxidizing mixtrophic bacterium
  • 22. Bioleaching of copper sulfide ores T1: bioleaching experiment without addition of pyrite and sulfur adjusted to pH 3; T2: bioleaching experiment with addition of 1% w/v pyrite and 0.25% w/v sulfur adjusted to pH 3; T3: bioleaching experiment with addition of 1% w/v pyrite and 0.25% w/v sulfur without pH adjustment; T4: bioleaching experiment with addition of 5% w/v pyrite and 2.5% w/v sulfur adjusted to pH 3; T5: bioleaching experiment with addition of 5% w/v pyrite and 2.5% w/v sulfur without pH adjustment; T6: abiotic control without the bacterium which was identical to bioleaching experiment (T1) 29.25 g/l NaCl T: 28 oC a particle size = 75 μm 5% pulp density
  • 23. Bioleaching of organic sulfur from coal Treatment A: a combination of biooxidation for 15 days and bioflotation; Treatment B: a combination of biooxidation for 40 days and bioflotation; Treatment C: bioflotation; Treatment D: column flotation
  • 24. Recycling of metals from E-wastes Primary source Natural ores Base metals: Cu, Fe, Al Platinum group metals: Pd, Pt Precious group metals: Au, Ag Other elements: Plastic, ceramic “Urban mine” resources Secondary source
  • 25. Au Ag Cu Fe Al Pd Pt Year 2016
  • 26. Proposed reactions of copper bioleaching from PCBs (Ilyas et al., 2013; Zhu et al., 2011; Xiang et al., 2010) Indirect mechanism 4Fe2+ + O2  4Fe3+ + H2O 2Fe3+ + Cu0  2Fe2+ +Cu2+ Direct mechanism, in the absence of Fe, elemental sulfur as the energy source. Cu is solubilized by protons, although in such case, molecular O2 is involved S0 + H2O  H+ + SO4 2- 2Cu0 + 4H+ + O2  2Cu2+ + 2H2O Acidithiobacillus sp. Ferrimicrobium acidiphilum Ferroplasma acidimicrobium Leptospirillum sp. Microorganisms involved: Fe/S-Oxidizing bacteria and archaea
  • 27. Microorganisms involved: cyanogenic bacteria and archaea Au dissolution by (bio)cyanidation consists of an anodic and a cathodic reaction 4Au + 8CN-  4Au(CN)2 - + 4e- (anodic) O2 + 2H2O + 4e-  4OH- (cathodic) The overall reaction is known as Elsner’s equation (Hedley and Tabachnick, 1953) 4Au + 8CN- + O2 + 2H2O  4Au(CN)2 - + 4OH- Pseudomonas plecoglossicida
  • 28. Principles of Phytomining 1997 The Streptanthus polygaloides plant is a hyperaccumulator of nickel, with hyperaccumulation defined as the presence of at least 1,000 µg nickel per gram of dry mass. This species averages 2,430 to 18,600 µg/g. This trait helps protect the plant against many types of pathogens.
  • 29. Sheoran, 2009 - Extraction of metals from soil into the plant roots by active transport or sorption Phytoextraction - From the roots transfer/ translocation into the shoot parts Willscher, 2018
  • 30. SEM-EDX image of the plant Miscanthus sinensis shows the adsorption ability of elements Si, P, S, Cl, K, Ca, Fe, Cu, Zn, Pb (Tazaki & Chaerun, 2008). Phytoaccumulation
  • 32. Requirements for the application Bioavailability of the metals/ metalloids (mobility) Occurrence of the metals in the rhizosphere Tolerance of the plants to high metal concentrations Satisfying growth of the plants
  • 33. Phytomining Substrates for application - Low grade ores - Overburden material - Mill tailings - Remainders of dump leaching - Mineralized soil - in all substrates uneconomical for conventional mining/ processing - A large part of the processed mineral material contains low metal concentrations - After the closedown of mining operations for the removal of lower amounts of the mined metals and first revegetation/ stabilization Photo of Crop of Ni metals: SKC Lab Willscher, 2018
  • 34. Advantages of phytomining - Less intrusive, low energy demand - Soil recovering effect (improvement of soil ecology) - Groundwater protection for the case of not too extensive application of chemicals - No erosion effects like other mining activities - For sustainable closure of mining sites - Reduction of acid mine drainage formation Challenges - Solubility and availability as one of the key factors Appliction of lixiviates (mostly complex forming agents) - Phytoextraction only in the root zone of the plants Engineering for mass transport Willscher, 2018
  • 36. A Proposed phytomining concept: SKC Mine Crushing plant Phytomining (Concentrator) Improved phyto-extraction parameters Tailings, low-grade ores, the closedown of mining operations -2 mm Plant Harvesting Crop of metals (Biomass) Biomass burning Leaching/Bioleaching ashes Biomass drying under sunlight/oven Biomass Grinding Bioenergy = Biogas www.portonews.com
  • 37. Summary - Utilization of low grade ores, tailings and remainders - Removal of valuable or toxic metals - Better soil functions/ revitalization - Improved soil fertility - Coupled process with renewable energy production - Lowering of the process costs Advantages of the method - Environmentally benign - Non-invasive for the soil - Low energy demand Sumeks.co shopee.co.id Vetiveria zizanioides (Rumput vetiver = ilalang akar wangi)