Beyond Biorecovery:

environmental win-win

by Biorefining of

metallic wastes into

new functional

materials…..B3

Novel Functional Nanomaterials

Biofabricated from Wastes

Lynne Macaskie, Angela Murray

Iryna Mikheenko

Four strands to B3.

Goal is proof of

potential

applications and

SUPPLY CHAINS

Barrie Johnson and Carmen Falagan

Hylke Glass and Beth Colgan

Supply chains set up in B3

SOUTH AFRICA

PGM wastes from mining operations

U of

Cape Town

Industrial project:

primary product

B3 catalyst

upgrade of

Product into

high value

chemical

U U of

Western

Cape

Fuel cell

technology

B3 FC

electrode

catalysts

Electricity

from bio-H2

CANADA

Road

dusts

B3 catalyst

for heavy oil

upgrading

Mine wastes

Contain rare

earths and UBio-

Separation

process

REE

recovery

into

B3

catalysts

U recovery into

nuclear fuel

cycle UK Mine

wastes

contain base

metalsUK industrial

Wastes contain

U and metals

Onward refining

Quantum

dots

Photobiotechnology

Algal products,

foodstuffs,

biohydrogen

Book

on

RRfW

LCA

Delivery

And delivery of outcomes

1

23

Novel catalysts!

Chemical Energy Remediations Fuel

syntheses appli- toxic metals cells

(green cations organics

chemistry) (cracking

catalysts)

Introduction

Aim’s

Is biologically recovered Palladium electrocatallitically active before further

treatment?

What is the effect of reducing agent, Genus and original salt formed from

the hydrometallurgical step? Biohydrometallurgy

Biofabrication of precious metal catalysts by bacteria topic 1

Products, platform

chemicals

Environment

Electricity

Pd(0)

Nano-

Particles:

cell

surface

and

within

cells

Cells only: no

Cl- release

70

75

80

85

90

95

100

105

0 10 20 30 40

Volumn passed (ml)

Cr(

VI)

reduced (

ml)

a) Pure bio-Pd(0)Flow rate 12 mL/h; column vol 10 mL

30

40

50

60

70

80

90

100

110

0 10 20 30 40

Volumn passed (ml)

Cr(

VI)

reduced (

%)

Cr(VI) reduction by bio-PGMs made from industrial waste (Degussa)

b) Bio-PGMsFlow rate 6 mL/h; column vol 10 mL

Cells as biofilm on

reticulated foam;

Pd(0) or PGMs

loaded to 10% of

biomass dry wt.

Foams packed

into columns;

Cr(VI) flowed

upwards through

columns

containing biofilm-

catalyst

PGM

recovery

from

auto

motive

catalyst

leachate

From pure

solution took 15

mins

Cr(VI)

reduction

Pure

Biorecovered

Catalyst

commercial catalyst bio-catalyst on E.coli

Pd/Al2O3 pre-palladised bio-Pd after target metal recovery bio-PdPt

loading (wt%) 2 5 2 5 16 20

selectivity to trans -

pentene (mol%)

37.63 35.1 19.65 19.91 20.65 15.93

cis/trans-pentene ratio 0.71 0.68 2.82 2.58 1.52 3.45

Selectivity of commercial catalyst and bio-catalyst in 2-pentyne hydrogenation

Commercial catalyst Bio-catalysts on E.coli

0.7 2.7 2.5

0

200

400

600

800

1000

1200

2 3 4 5 6

Reduction r

ate

(µ

mol C

r(V

I)/h

/mg)

Use

Cr(VI) reduction rate per strain after each re-use

Model strain Exporting strain Acid resistant strain

Bio-gold: oxidation catalyst from jewellery waste

0

20

40

60

80

100

120

0 10 20 30 40 50 60 70 80 90 100 110 120 130

Time (mins)

% A

u(I

II)

rem

ain

ing

Waste: a sink trap in a jewellery company.

Leach: aqua regia; pH adjusted to ~2

Controls

Au recovery from

3 leachates

Leach- Au

ate ppm

I 116

II 115

III 65From

pure

Au(III)

solution

From

Leachate

Au(0) NPs

(confirmed by

XRD and EDX)

Oxidation of glycerol to glycerate

Glycerol: produced

at tonnage waste

from biodiesel

Glycerate: organic

acid feed for bio H2

photoproduction

(8-10 mol/mol

sugar)

Catalyst Conversion at 3 h in air

(1% Au)

Au/graphite 56%

Bio-Au(0)pure 30%

Bio-Au(0)waste 30%

Commercial catalysts have been extensively optimised.

THAI-CAPRI Process and Heavy Oil Upgrading

Greaves, M and Xia T.X. 2001. CAPRI-Downhole Catalytic Process for Upgrading Heavy Oil: Produced Oil Properties

and Composition. Presented at the Petroleum Society, Canadian International Petroleum Conference, Calgary, Alberta,

Canada, June 12 – 14.

Heavy oil Light oil

THAI-CAPRI

Objective is to

convert heavy oil

to light oil in situ

• The main aims of catalytic

upgrading of heavy oil are

-Increase API gravity

-Reduce viscosity

-Remove impurities like asphaltenes, metals, sulphur, nitrogen, etc

-Improve market value

Must be economic! Depends on current price of oil

Catalyst Coke% API gravity# Viscosity

inc (mPas)

Native oil - 13.8 1031None (no catalyst; only thermal) 10.2 20.1 13.8

Cells alone (control) 6.6 19.9 16.0

Comm. Catalyst: Ni-Mo-alumina 5.0 24.9 3.7

Set 1 (D.d. & B.b) D.d Bb D.d B.b D.d B.b

5% Pd/Pt 3.9 3.7 23.4 23.9 5.8 7.0

20% Pd/Pt 4.1 4.2 22.2 23.1 6.2 7.1

***********************************************************************************************************

Set 2: (E.c & Bb) controls 7.8 18.1 15.4

E.c B.b E.c B.b E.c B.b

Sample 1 (5% metals) 6.5 4.4 20.7 21.2 11.7 7.2

Sample 2 (5% metals 6.3 4.4 21.2 21.4 11.5 6.4

Set 3 (real leachate (road dust) Identical results in all criteria

*Thermal upgrading only. **Ni-Mo/alumina. #API gravity: an increased value is success

D.d: D.desulfuricans. B.b: B.benzeovorans. E.c E. coli

Set 1: catalysts made from pure metal solutions.

Set 2: Catalysts made from surrogate leachates. All ‘primed’ with 2% Pd then made up as shown.

Set 1: primed then 0.5% Pd/2.5% Pt Set 2: primed then 1.5% Pd/1.5% Pt

Catalytic upgrading of heavy THAI oil

Anode

Cathode

Electrolyte

Hydrogen fuel (can be

biohydrogen)

2 H2 → 4 H+ + 4 e-

O2 + 4 e- + 4 H+ → 2 H2O

H+

O2 in (usually from

the air)

Powered

device

Pt

catalyst

Pt

catalyst

e-

flow

H2O and

heat out

Biocatalysts as fuel cell electrodes

Deposit cells/metal

NPs on electrode

In carbon carrier

Metallised biofilm

Test power output

Nafion

Fuel cell catalyst Power (mW)

Pt commercial catalyst 170

Bio-Pt D.desulfuricans 170

Bio-Pd D.desulfuricans 100

Bio-Pd E.coli MC4100 29

Bio-Pd E coli HD701* 28

Bio-Pd E. coli IC007** 115

Bio-Pd E. coli IC007 PMs 68

*From MC4100:Upregulated formate hydrogen lyase.

** From HD701: multiply engineered to overproduce clean

H2 from food wastes.

PMs: PGMs made from a processing waste (Degussa).

Catalysts loaded @ ~ 20% biomass dry weight

Biocatalysts as fuel cell electrodes

example power outputs

Cells were

carbonised

(heat) and

mixed with

activated

carbon to

make

electrode

Biocatalysis SummaryMetallic waste

stream (s)Supported Metal

Catalysts

Waste

Biomass Heavy

oil up-

grade Fuel

cells Platform

chemicals

+

Biorefined Catalysts from

Wastes: Summary

Remediation

Also ongoing work ():

(UK supply chain)

Upgrading of pyrolysis oil

from lignocellulosic biomass to

‘drop in’ fuel

Catalytic upconversion of

5-hydromethyl furfural

(platform chemical for ‘drop in

Fuel’ and plastics precursors

Sulphate-Reducing Bacteria and quantum dots… topic 3

• Produce H2S gas in dissimilatory sulphate reaction

• Biogenic H2S used in acid mine drainage bioremediation – precipitates toxic

metal ions as sulphides

• Some metal sulphides display unique optical properties – quantum dots

• Novel method of ZnS quantum dots synthesis using biogenic H2S

• Excess H2S is produced by metal bioremediation process treating real acid mine

drainage at U. Bangor- Bangor have achieved metal separation

• Semi-conductor nanocrystals –display unique fluorescence properties

• Absorb and emit light at different wavelengths

• ZnS previously characterisedabsorb in UV and emit in visible –at 410 nm

• Chlorophyll a has broad absorbance peak at 428 nm

Quantum dots

Photosynthetic Biotechnology

• Developing ‘green’ ways of energy and food production

• Limiting factor to photosynthetic biotech in UK (and Europe) is lack of light!

• Efficient usage of sunlight (or artificial light) necessary…or boosting

• QDs (by slight modulation) - a means to convert light into useful wavelengths for boosting chlorophyll a?

Makes

hydrogen

(with Blue

Sky Bio)

Makes

Oils

(with U.

Exeter:

John Love)

Makes

Food

(edible biomass)

Photoproductivity of all three was doubled by using Q-dots (Invitrogen)

Q-dots cost £100’s for a few mg…. Unscalable!

R. sphaeroides B.braunii Spirulina

waste H2S

SRB

metal

sulfides

Energy + H2S

UV

LIGHT

Zn2+ (+

buffer!)

solution

colloidal ZnS

quantum dots

Boost photosynthetic output?

(currently under test) Also testing Zn2+ recovered

at Bangor

AMD

emission at 428 nm

by modulating

synthesis? ()

sulphate

• Hydrogen

• Biofuel

• Food

Added value from

waste + light

Economic way to boost photoproductivity

Collect for

refining

Bangor

bioremediation

?

Bioleaching of mine tailings

PLS

Continuous flow low pH

sulfate reducing bacteria

reactor

Off-line

precipitation

of copper

CuS

Acid mine

drainage

AMD

Cu-free

liquor

H2S

ZnS

H2SH2S

Other ongoing investigations

• Developing a biotechnology for eliminating the use of cyanide for gold recovery.

• Salt-enhanced bioleaching of chalcopyrite.

Recovering metals from mine wastes

• Red shift in ex (left)/emm (right) peak with decreased citrate concentration ( 0.05 – 0.01M M).

• Loss of optical property with no buffer – pH regulation important consideration.

• Samples synthesised at pH 6 based on previous work.

• Fine tuning by use of other buffers and use of metal doping (feasible)

• Delivery system to avoid metal toxicity – glass inserts were used

0.E+00

5.E+04

1.E+05

2.E+05

2.E+05

200 250 300 350 400

Inte

nsity (

cps)

wavelength (nm)

0.E+00

1.E+05

2.E+05

3.E+05

4.E+05

5.E+05

300 350 400 450 500

wavelength (nm)

0.01M tri-sodium citrate0.025M tri-sodium citrate0.05M tri-sodium citrate0.1M tri-sodium citrateno tri-sodium citrateEmission

Excitation

peak

Emission

peak

0.01 M 323 nm 424 nm

0.025 M 315 nm 417 nm

0.05 M 310 nm 410 nm

0.1 M 316 nm 418 nm

Samples synthesised

using same volume of

culture head gas

ZnS Q-dots from waste H2S in citrate buffer

Excitation

Hooray!

Waste H2S obtained from metal

remediation process for AMD at U.Bangor

Rare Earths and Uranium: topics 2 &4

REE/U mine

tailing wastes

Rare earth ore mining

REE: group of elements (similar chemistries)

used in:

Magnetic applications; switching, electronics, guided missile systems, smart cars, computers etc etc…. 21st C!

Optical applications: phosphors, fluorescence etc; LEDs

Catalysis e.g. making rubber (polymerisation reactions)

More than 95% of global supply is controlled by China.

Commercial refining is > 100 steps. What can Biotech offer?

REE recovery from wastes

Removing uranium & REEs from wastes using

enzymatically-driven phosphate mineralization

Phosphatase activity makes

biomineral deposit

Glycerol-2-phosphate

Periplasmic

phosphatase

Phosphatase

within the EPS

Metal

phosphate

precipitate

HPO42-

HUO2PO4.nH2O

UO22+

1 – 2 mm

Bacterium

Rare earth

phosphates are

also formed;

here NdPO4

Immobilized

biofilm in column

accumulates

more than 10 x

biomass weight

as metal

Uranium phosphate

solid was made by

columns treating real

AMD water ~ pH 3-4

(ENUSA mine, Spain)

Selectivity for La3+ against UO22+

La3+ removal

UO22+ removal

FA1/2= 1.2

ml/min for

U

FA1/2 =

5.2

ml/min

for La

Ln flow rate ml/min

%

Input

metal

remo

ved

In the circled

region ~ 90%

of the La3+ is

recovered with

<10% UO22+

recovery

Exact correct

flow rate

depends on the

exact

solution

composition

An extra trick

is needed to

completely

separate

REE(III) from

U(VI)!

Vol of flow passed (L)

2mM Bu3P supports removal of

additional 40% of 2 mM Cd2+

0.5 mM

G2P

Removal of

Cd2+ from

flow (%)

100

1 mM G2P

2 mM

TBP/

1mM

G2P

Boost due to

TBP

TBP alone

is

ineffective

TBP + 0.5

mM G2P is

ineffective

Serratia sp.

1. TBP can only be used in co-metabolism

(need a primary substrate).

2. Futile cycle- liberated Pi transferred back

onto butanol by

transphosphorylation

(shown by 31P NMR)

Key issues:

Tributyl phosphate supports removal of Cd2+ and UO22+

by immobilised cells (polyacrylamide gel)

50

Use of tributyl

phosphate to

selectively hold

back UO22+

Some progress towards REE

separation one from another

(collaboration with U. Plymouth

Separation concept

REE (III)

removed

REEPO4

U(VI)

removed

HUO2PO4

Th(IV)

removed

Th

(NH4PO4)2

Refinery

Nuclear

fuel cycle

U & Th

rejectedTh

rejected

Flow in:

G2P + TBP

High flow rate

Flow in:

G2P + TBP

Slow flow

rate

Flow in:

G2P +

NH4+ ion

Slow flow

rate

Excess

Pi

Mine

Tail-

ings:

REE)

+

U(VI)

+

Th(IV)

Conclusions so far

Bacteria can make precious metal catalysts for a suite of potential

green applications. Active catalysts from several types of PGM wastes

Waste H2S from metal remediation process is used to make quantum dots

that emit at photosynthetically active wavelengths; x2 boost was shown

with commercial QDs

Thanks for

listening…Questions?

Serratia sp. recovers U from AMD waste to high load of UP

Serratia sp. also recovers REEs as phosphate ~ 14 nm crystallites

(= catalysts???)

Towards selective REE recovery from mine wastes:

Use of tributyl phosphate to enhance metal selectivity:

separate product streams for

(i) value REE products

(ii) nuclear fuel precursors nuclear fuel cycle

Case histories of

waste to product

Life Cycle

Analysis

Supply

chains