Novel Functional Nanomaterials Biofabricated from Wastes … · 04-12-2016 · Novel Functional...
Transcript of Novel Functional Nanomaterials Biofabricated from Wastes … · 04-12-2016 · Novel Functional...
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