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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/


• 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


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• Metal removal from aqueous wastestreams is useful

• Recovery of valuable metals would be better still

Public

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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


• Can BES systems be developed for recovery of copper from dilute copper containing

wastestreams?

• Environmental benefit

• Recovery of a valuable product from waste



Chuquicamata open pit copper mine, Chile.


• A proof of concept from the Scotch Malt Whisky industry



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


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


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


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.


bioelectrochemical systems

Spent Lees



• Cu removal down to sub ppm levels in ca. 2 days

Cu0

Cu2+

Cu+



• 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



http://www.lme.com/

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



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)



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





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 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

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