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Bioelectrochemical systems for resource recovery and
integrated waste management
https://www.mcgill.ca/https://cdn.henheaven.co.uk/w1280-h450/locations/newcastlelong.jpg
School of Natural and Environmental Sciences &
School of Engineering
Newcastle University, UK
Ian M. HeadEileen Yu, Keith Scott, Tom Curtis, Ed Milner, Beate Christgen, Martin Spurr, Henriette Christensen, Alison Vipond, Ana Suarez-
Suarez, Rick Kimber, Jon Lloyd, Vicky Coker, Hitesh Boghani, Iano Premier, Alan Guwy, Richard Dinsdale, Kok Siew Ng, Bolaji
Shemfe, Jhuma Sudhukhan
http://www.meteorr.ac.uk/
Bioelectrochemical systems for metal recovery from
wastewater
• Bioelectrochemical systems
Copper
• Cu as a global resource
• Cu toxicity an environmental perspective
• Copper recovery from malt whiskey distillery wastewater
• The malt whisky distilling process and sources of Cu in wastewater
• Recovery of copper from a distillery wastestream with bioelectrochemical systems
• Regulatory implications
Bioelectrochemical systems
• Bioelectrochemical systems (BES) harness the power of microbial catalysts in
electrochemical systems
• Rely on natural processes involved in organic carbon turnover in anoxic environments
• Rather than using chemicals as oxidants or energy sources as in normal metabolism
organisms in BES use electrodes as a sink or source of electrons
• They can also use materials in a range of wastestreams as fuel or ultimate electron sinks
Cu recovery from wastewater using BES
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• Copper is an essential metal for modern society
• 17 million tonnes produced in 2017 and increasing
• Copper 140-300 kg per capita in developed countries
• Desktop computer ca. 1.5 kg of copper
• Average home ca. 100 kg
• Wind turbine ca. 5 tonnes.
• 'peak copper’ may be reached somewhere 2025-2030
• Ca. 95% of all copper has been extracted since 1900.
• Copper globally is among the most traded commodities (cf. oil and gold)
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Chalcocite (Cu2S), Cu ore
By Native_Copper_Macro_Digon3.jpg: “Jonathan Zander (Digon3)"derivative work: Materialscientist (talk) -Native_Copper_Macro_Digon3.jpg, CC BY-SA 3.0, https://commons.wikimedia.org/w/index.php?curid=7223304
http://www.greenspec.co.uk/building-design/copper-production-environmental-impact/
Cu recovery from wastewater using BES
• Global demand for copper projected to increase by 213% to 341% by 2050
• This could result in 2.4% of global energy demand being directed towards Cu recovery
• Copper reserves could be depleted in 20 to 60 years
• New and better ways to recycle and recover Cu are needed
CC BY-SA 2.0 de, https://commons.wikimedia.org
/w/index.php?curid=351497
Chuquicamata open pit copper mine, Chile.
Elshkaki, A., Graedel, T., Ciacci, L. & Reck, B. (2016). Copper demand, supply, and associated energy use to
2050. Global Environmental Change, 39: 305–315. DOI: 10.1016/j.gloenvcha.2016.06.006.
Cu recovery from wastewater
using BES
Environmental perspective
• Cu is a toxic metal
• Even low level contamination can be a
problem and copper is toxic to a wide
range of organisms at micromolar (sub
ppm) levels
PlantsAlgaeProtistsCrustaceansInsectsRotifersFish
Toxic effect at < 10 micromolar Cu2+
Toxic effect at > 10 micromolar Cu2+
Sanchez et al., 2007. Bull Environ Contam Toxicol 78:421–426
10 micomolar Cu2+ = ca. 0.64 ppm
Cu recovery from wastewater using BES
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• Metal removal from aqueous wastestreams is useful
• Recovery of valuable metals would be better still
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Chalcocite (Cu2S), Cu ore
By Native_Copper_Macro_Digon3.jpg: “Jonathan Zander (Digon3)"derivative work: Materialscientist (talk) - Native_Copper_Macro_Digon3.jpg, CC BY-SA 3.0, https://commons.wikimedia.org/w/index.php?curid=7223304
Cu recovery from wastewater using BES
• Can BES systems be developed for recovery of copper from dilute copper containing
wastestreams?
• Environmental benefit
• Recovery of a valuable product from waste
CC BY-SA 2.0 de, https://commons.wikimedia.org
/w/index.php?curid=351497
Chuquicamata open pit copper mine, Chile.
Cu recovery from wastewater using BES
• A proof of concept from the Scotch Malt Whisky industry
CC BY-SA 2.0 de, https://commons.wikimedia.org
/w/index.php?curid=351497
The malt whisky distilling process and sources
of Cu in wastewater
Annual exports of
£4 bn
10,800 Scottish Jobs
>7,000 in Rural Communities
40,000 in UK
Direct exports to
175 countries
1.5 mn distillery visits
Courtesy of Ronald Daalmans, Chivas Brothers
The Scotch Whisky Industry
The malt whisky distilling process and sources
of Cu in wastewater
www.scotch-whisky.org.uk
September 2016
https://consult.scotland.gov.uk/zero-waste-
delivery/making-things-
last/supporting_documents/ZWS645%20B
eer%20Whisky%20Fish%20Report_0.pdf
The malt whisky distilling process and sources
of Cu in wastewater
“Single Malt Scotch Whisky means a Scotch Whisky produced from only water and malted barley at
a single distillery by batch distillation in pot stills.”
Pot Stills are made from copper and the copper is an essential part of the process as it removes sulfur compounds that affect the aroma and taste
Reaich, D., The influence of copper on malt whisky character. Proceedings of the Fifth Aviemore Conference on Malting, Brewing and Distilling, Institute of Brewing: London, 1998, pp. 141-152
Courtesy of Ronald Daalmans, Chivas Brothers
Courtesy of Ronald Daalmans, Chivas Brothers
Courtesy of Ronald Daalmans, Chivas Brothers
Medium sized distillery - ca. 388,000 L spent lees per week
Cu2+ concentration of 20 mg/l (315 micromolar)
7.76 kg Cu2+ per week
403.5 kg Cu2+ per year
biofilm
organics
anode cathode
Cu2+ + 2e-
Membrane
e-
K+,Na+,H+
Rext
HnPO4z-,OH-
nCO2 + nH+ + ne-
Cu(s)
Recovery of copper from a distillery wastestream with
bioelectrochemical systemsPower source
Cu removal vs recovery
Ni
Cu
• Preliminary experiments in half cell and acetate fed MFC with graphite cathodes (Cathode
potential -0.2V SHE) showed Cu recovery from high concentration synthetic solutions
• In 3 MFC runs percentage Cu removal of;
• 99.5 ± 0.02 %, 90.5 ± 0.78, 46.1 ± 0.77
Anode Cathode
Recirculation Vessel 1.23 L
RE
Pump (43 ml/min)
AEM
Power source
Rext
N2
Bioelectrochemical system Setup
• Carbon veil anode with electrogenic biofilm (1 g/L acetate in
50 mM phosphate buffer)
• Graphite plate cathode
• Spent lees recirculated at cathode
Mode of operation
• MFC mode over a low external resistance (short-circuit).
• MEC mode with a +0.5 V input from a power source.
Recovery of copper from a distillery wastestream with
bioelectrochemical systems
Spent Lees
Recovery of copper from a distillery wastestream with
bioelectrochemical systems
• Cu removal down to sub ppm levels in ca. 2 days
Cu0
Cu2+
Cu+
Recovery of copper from a distillery wastestream with
bioelectrochemical systems
• BES set up with an acetate-fed bioanode and copper removal from spent
lees at the cathodeMFC mode
Rext = 10 / 0.6 ohmsMEC mode
Input voltage of +0.5 V
Change in cathode potential
-434 ± 73 mV -91 ± 59 mV AR SL1
7 days with 0.5 V voltage input
16.1 ± 0.5 mg weight gain
20.1 ± 0.6 mg loss from solution(20±0 to 3±0 ppm)
Current = 0.28 ± 0.10 mA
DH SL1
7 days at 10Ω then 3 days at 0.6 Ω
36.6 ± 0.7 mg weight gain
37.3 ± 1.1 mg loss from solution(41±0 to 11±1 ppm)
Current = 0.31 ± 0.16 mA
MEC mode MFC mode
MEC mode
SEM with EDX
• Cu and Cu/O/C
XRD
• Cu dominant peaks
• Cu2O minor peak
MFC mode
SEM with EDX
• Cu oxide
XRD
• Cu2O (cuprite)
What are the economics of the process?
• For a medium sized distillery ca. 388 tonnes of spent lees produced per week
• 388,000 L per week
• Assuming a Cu2+ concentration of 20 mg/l this
• 7.76 kg Cu2+ per week
• 403.5 kg Cu2+ per year
• Revenue (£/year)
• Market value of copper = £4628 per tonne (www.lme.com 12/01/2019).
• Revenue from the spent lees from a medium-sized distillery assuming 100% Cu recovery
• £1867 per year for 1 distillery
• 120 malt whisky distilleries in Scotland = ca. £225,000 per year
• Power input only 30 to 40 Watts for 0.5V power input – low energy lightbulb
Recovery of copper from a distillery wastestream with
bioelectrochemical systems
BES for waste management, resource recovery and the circular
economy
M+ + e-M (metal)
2H+ + 2e- → H2
CO2 +2H+ +2e-HCOOH
NH4+NH3 + H+
Mg2+ + NH4+ +PO4
3- + 6H2OMgNH4PO4.6H2O
MFC/MEC
Sludge
e-
CH3OH, HCOOH
CO2
Waste water
Treated water
CxHyOz + (2x-z)H2O →(y+4x-2z)H+ + xCO2 + (y+4x-2z) e-
Renewable energy
Energy storage
Chemical feedstock
Renewable energy
Resource recovery
e-
Future work and perspective
Integrated system for distillery waste management and minimization
• CO2 conversion by bioelectrochemical reduction
• Chivas Brothers malt distilleries produce 50,000 tonnes/annum of fermentation CO2
• £900,000 in carbon credits (at £18 per tonne).
• All CO2 converted to formic acid worth £24 million (52,286 tonnes/annum at $600 per
tonne)
BES for waste management, resource recovery and the circular
economy
M+ + e-M (metal)
2H+ + 2e- → H2
CO2 +2H+ +2e-HCOOH
NH4+NH3 + H+
Mg2+ + NH4+ +PO4
3- + 6H2OMgNH4PO4.6H2O
MFC/MEC
Sludge
e-
CH3OH, HCOOH
CO2
Waste water
Treated water
CxHyOz + (2x-z)H2O →(y+4x-2z)H+ + xCO2 + (y+4x-2z) e-
Renewable energy
Energy storage
Chemical feedstock
Renewable energy
Resource recovery
e-
Metal recovery from wastewater and regulations for
agricultural use of sludge
Metal recovery from wastewater and regulations for
agricultural use of sludge
Metal recovery from wastewater and regulations for
agricultural use of sludge
Levels of potentially toxic elements (PTEs)
• One of the most important factors dictating levels of sludge application to land
• chromium (mg/kg dry solids)
• zinc (mg/kg dry solids)
• copper (mg/kg dry solids)
• nickel (mg/kg dry solids)
• cadmium (mg/kg dry solids)
• lead (mg/kg dry solids)
• mercury (mg/kg dry solids)
Metal recovery from wastewater and regulations for
agricultural use of sludge
Sewage sludge in agriculture: code of practice for England, Wales and Northern Ireland
Published 23 May 2018
Contin et al., 2012. Science of The Total Environment. 441, 10-18
Metal recovery from wastewater and regulations for
agricultural use of sludge
Metal recovery from wastewater and regulations for
agricultural use of sludge
Levels of potentially toxic elements (PTEs)
• Removal of Cu (and other metals) from wastewater can reduce the PTE burden in sludge
• Can increase the effective land bank for sludge disposal?
https://www.agriland.co.uk
Recovery of copper from a distillery wastestream with
bioelectrochemical systems
• Recovery of copper from distillery wastewater using BES is technically feasible
• Low concentration Cu can be removed from spent lees with recovery of valuable products
• Cu2O in MFC mode
• Cu0 in MEC mode
• Wider benefits when incorporated as part of an integrated waste management system
• Potential benefits in extending sludge disposal routes
• Cu recovery from distillery wastewater could make positive impacts both economically and
environmentally