Clean synthesis and Platform molecules · Replacement for non-polar solvents Inherently...
Transcript of Clean synthesis and Platform molecules · Replacement for non-polar solvents Inherently...
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Platform molecules and materials from biomass
residues using green chemistry
Dr Duncan Macquarrie
Green Chemistry Centre of Excellence
University of York
Khon Kaen, September 2017
Where are we?
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York
Green Chemistry Centre of Excellence
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• £5M purpose-built Centre
with Industrial
Engagement Facility
• Currently at: ~100 Staff
and Students
Activities
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The Centre’s Activities can be grouped into 4 areas:
• Research
• Industry collaboration
• Education, including
development of teaching
and promotional materials
• Networking with all
chemical stakeholders
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2. Maximise
incorporation
of materials
7. Use renewables
3. Lower
toxicity4. Design
safer chemicals
12. Accident prevention
11. Monitor and analyse
1. Waste prevention
better than clean-up
5. Don’t use auxiliaries
9. Use
catalysis
8. No
unnecessary
derivatisation
6. Minimise energy
10. Design for
degradation
12 Principles of Green Chemistry
Overview of presentation
• Platform molecules
– Re-inventing petrochemical based products
• Bio-based materials
– Utilising natural porosity and functionality
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Oil Refining…
Crude Oil
Fuel
Chemicals
Energy
OIL
RE
FIN
ER
Y Plastics
Agro-chemicals
Pharmaceuticals
Nutraceuticals
Solvents
Clothing
Many more……
Asphalt
Current: Fossil-derived Base Chemicals
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Cru
de o
il, n
atu
ral
ga
s,
co
al
CH4
Naphtha Ethene
Propene
Butenes
Benzene
Toluene
Xylenes
SYN
GASMethanol
FeedstockBase
Chemicals
Example Bulk
Chemicals
Example
Products
ethene oxide
formaldehydemethyl methacrylate
acetic acid
terephthalic acid
styrene
phenol
cyclohexane
aniline
toluene diisocyanate
styrene-butadiene rubber
polybutadiene rubber
polyethene
polyethene oxide
anti-freeze
ethylbenzene
1,2-dichloroethane
propene oxide
vinyl chloride polyvinyl chloride
polypropenepropan-2-ol
nylon
dyes
polyurethanes
polyetheneterephthalate
adhesives
(iso)phthalic acid
polyesters
propandiols
solvents
bisphenol A
polycarbonates
latex
paintsresins
Biorefining…
Fuel
Chemicals
Energy
BIO
RE
FIN
ER
Y Plastics
Agro-chemicals
Pharmaceuticals
Nutraceuticals
Solvents
Clothing
Many more……
Platform
molecules
Materials
Sustainable
catalysts?
Waste Biomass
Platform Molecules replace Base Chemicals
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BIO
MA
SS
Carbohy
drates
ethanollactic acid
itaconic acid
HMF/CMF
sorbitol
methanol
FeedstockPlatform
Molecules
Key
Derivatives
Bio-based
Products
ethene
formaldehydemethyl methacrylateacetic acid
isosorbide
fumarate
cinnamic acid
levulinates
synthetic rubber
polyethene
polyalkenes
PEG/PEO
NMP
ethene oxide
acrylic acidpropene/butene
polypropene
vanillic acid
nylon
dyes
polyurethanes
adhesives
glycidol
polyesters
solvents
polyethers
polycarbonates
latex
paints
resins
Lignin
Protein
Extracts
Syngas
furfural
unsat. polyesters
vanillinguaiacoleugenol
GluAspProLys
acrylamide
α-pinene
D-limonene(fatty acids)
mannitolPHAs
(glycerol)
antioxidants
surfactants
lubricantsagrichemicals
flavour & fragrance
catalysts
Phe
pharmaceuticalsvarious phenolics
FDCA2,5-dimethylfuran
ZnO-eugenol water soluble polymers
chelators
1,5-pentanediaminemaleate
2-MTHF
terpene oxides
hydroxyacidsepichlorohydrin
Clean Synthesis and Platform Molecules
• Chemicals sustainably
derived from biomass
(bio-PMs)
• Assessment of bio-
based content (14C and
beyond)
• Utilisation of chemicals
derived from waste
• Sustainable catalysts
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• Alternative reaction
activation (MW, US)
• Alternative solvents
(scCO2, bio-derived, no
solvent)
• Catalysis, ideally
heterogeneous
• Addition reactions rather
than condensation or
elimination
• Flow chemistry
Clean
Synthesis
Sustainable
Chemicals
Bio-Platform Molecules (bio-PMs)
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2004 - Report by US-DOE to focus research on promising bio-PMs:
We have interest in some other promising bio-PMs:
5-chloromethyl furfural (CMF)
• Bi-phasic reaction
• A range of carbohydrates investigated
• Alternative solvents screened:
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Green Chem., 15 (2013), 72-75
Tom Farmer
CMF as a bio-PM
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Green Chem., 15 (2013), 72-75
CMF Lignin – A Free Catalyst
• The waste produced from converting ligno-cellulose
to CMF can be recovered and used as a porous
heterogeneous catalyst
• Texture of surface can be tuned via thermal
treatment (as for Starbons®)
CMF
Water
Immiscible
Solvent
Aq. HCl
“CMF lignin”
CatalystΔ
H2O EtOHLignocellulose
H2SO4
LA EL
ChemSusChem, 8, 2015, 24, 4172–4179
Tabitha Petchey
Platform molecules from protein waste
• Proteins exist in several food-related waste streams
• Breakdown to amino acids
• Decarboxylate:
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Microwave-assisted / isophorone catalysed
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15mins 200W MW
propanol solvent
65% yield
Isophorone recovered
Yann Li
Sustainable Solvent Selection Service
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Andy Hunt, James Sherwood
Solvent property mapping
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Aprotic solvents
Amines
Dipolar aprotics
ChlorinatedHydrocarbon
Nitro
Ethers Ester Ketones
Nitriles
Cyrene - a bio-based dipolar aprotic
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Levoglucosenone CyreneBiomassStep 1 Step 2
Green Chem., DOI: 10.1039/C7GC00112F
ChemSusChem, 9(24), 3503-3512.
2,2,5,5-Tetramethyltetrahydrofuran (TMTHF)
✓ Replacement for non-polar solvents
✓ Inherently non-peroxide forming
✓ Clean synthetic route
✓ Potentially bio-based
✓ Comparable solvent performance to toluene
A. J. Hunt et al., Green Chemistry, 2017, accepted.
• The lack of any α-protons to
the ether means that
TMTHF is non-peroxide
forming and is therefore
suitable for use a solvent in
radical polymerisations (see
right)
• The lone pair of e-s on the O
are sterically protected by
the four methyl groups so
TMTHF behaves less like
and ether and more like
toluene
Andy Hunt,
Fergal Byrne
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Silica based chemistries
• A “simple” catalyst for a “simple” reaction
– Amide formation from acid and amine is one of the most
problematic and highest priority reactions identified by ACS
Green Chemistry Institute Pharmaceutical Round Table
– Good yields with 10wt% chromatographic silica
– Product crystallises directly.
– Catalyst completely reusable
– Catalyst not a dehydrating agent
R OH
O
R'NH
2
R NH
O
R H2O+ +
Chem. Comm., (2009), 2562-2564
700 °C
K60 silica
James Comerford, Lyndsey Ledingham, Tabitha Petchey
SBA’s – Mesoporous Silicas
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Arkivoc, vii (2012), 282-293
• Activated structured silica (SBAs) superior to
standard K60 – further advancing our own
technology
– 5%wt activated SBA gives comparable yields to 20%wt
activated K60
SBA’s in Flow
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Arkivoc, vii (2012), 282-293
continous flow,
toluene solvent
• Excellent applicability for catalyst in flow reaction
• Flow facilitates scale-up
• Cymene (from orange peel) also very good solvent
Structured Silica from Ash – Bio-MCMs
• Burning of biomass in power stations leaves bio-ash
• Bio-ash used to form bio-derived structured silica
• Improving the sustainability of heterogeneous catalysts
• Utilisation of waste for catalyst formation
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Green Chem., 15 (2013), 1203-1210
Emma Cooper
Jennie Dodson
Starbons – tunable mesoporous materials
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• Now being produced in multi-kg/day scale
• Registered company currently being bought
from the University
• 3 Patents and over 20 research articles
• Current customers Merck and Trio Healthcare
• Scale-up development through Porous4App
H2020 commercialisation grant
Enhanced CO2 capture by waste-derived mesoporous carbons. Angewandte Chemie, 55, 9173
Treatment of laundrette wastewater using Starbon and Fenton’s reagent. J Env Sci and Health, 51(11), 974
Revisiting the structure of mesoporous α-D-polysaccharide gels. ChemSusChem. 9(3), 280-288.
Cinthia Mena Duran, Mario De bruyn,
Xiao Wu, Vitaliy Budarin Andy Hunt, and many more
Starbon process
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Starting materials can include starch present in waste food, e.g. - Potato peelings- Waste maize (corn) starch- Waste grain or wheat starch- Pectin from orange peel- Alginate from seaweed
Processing
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RoboQbo processor
Ca. 15kg / hour
This project has received funding from the European
Union’s Horizon 2020 research and innovation program
under grant agreement No 686163
Processing
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Freeze dryer – ca. 1.5kg/day
Textural properties
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Succinic acid
Sucrose
1.1 nm
Sucrose
Methylene Blue
1.5 nm
Metal Complex
Catalyst. 2 nm
Activated carbon (Norit)
Average diameter 0.45 nm
Mesopore volume 0.25 ml/g
BET Surface area 800 m2/g
Mesopore surface
area
60 m2/g
Starbon-300
Average diameter 5.0 nm
Mesopore volume 0.65 ml/g
BET Surface area 310 m2/g
Mesopore surface
area
190 m2/g
Succinic acid
0.5 nm
0.45 nm 5.0 nm
Applications
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• Recovery of precious metals from waste streams through reductive adsorption (Starbon® R Series)
• Purification, in particular removal of harmful organics and heavy metals to purify water and clean up waste streams (Starbon® P Series)
• Separation of complex mixtures for production and analysis with Starbon® as the stationary phase in chromatographic systems (Starbon® S Series)
• Catalysis of bio-refinery downstream processes including esterification reactions in aqueous systems (Starbon® C Series)
• Catalysis using adsorbed metal complexes and nanoparticles
• As a hybrid with mixed metal oxides for energy storage
Next generation Starbons ?
• Aims:
• Simpler process
• Better particle size/shape control
• Better mechanical strength
➢ Carbon Silica Composites
➢ Silica provides control of physical properties and mechanical
strength
➢ Carbon layer provides the chemical functionality
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Tengyao Jiang
Konstantina Sotiriou
Collaboration with
Khon Kaen University
Material preparation
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Characterisation
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0.0 0.2 0.4 0.6 0.8 1.0
silica
300
500
800
Vo
lum
e A
dso
rbe
d (
cm3/g
ST
P)
Relative Pressure (P/Po)
Fig. 6 N2 adsorption / desorption
isotherm plots of silica KS60 and CSCs.
Material BET surface area
(m2 g-1)
Pore volume
(cm3 g-1)
Pore diameter
(nm)
Carbon layer thickness
(nm)
Silica K60 467 0.80 6.7 -
CSC 300 321 0.32 4.4 1.15
CSC 500 380 0.39 4.5 1.10
CSC 800 1056 1.22 4.8 0.95
Table 1. Textural properties of silica K60 and CSCs.
Type IV Isotherms.
Nitrogen adsorption/ desorption porosimetry
Metal adsorbency
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Selectivity related to reduction of metals
Capacity of adsorbents
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0
10
20
30
40
50
60
70
80
90
100
% R
em
ova
l
Initial Concentration / mg L-1
CSC300
CSC 500
CSC 800
500 300 150 100 50
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Lignin – a potential source or aromatics
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Biomass processing damages lignin – can we
isolate lignin in a more accessible state?
Long Zhou
Vitaliy Budarin
Jiajun Fan
MW hydrothermal deconstruction
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Solid-state NMR 13C CP-MAS
Pyrolysis GCMS
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Summary
• Holistic approach to biomass utilisation
– Polysaccharides to platform molecules
– Polysaccharides to functional materials
– Lignin as catalyst and as raw material for aromatics
– Inorganics (silica) also utilised as matrices for catalysts and
adsorbents
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Thanks to :
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EPSRC, EU FP7 & H2020, Royal Society, GSK,
Pfizer, Conacyt
Towards a seaweed biorefinery
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Hamnavoe, Shetland,
October 2011Ascophyllum Nodosum
Yuan Yuan
Biorefinery schematic
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Ascophyllum Nodosum
Solid residue
Solid residue
Solid residue
Solid residue (biochar)
Pre extraction: water
then aq. ethanolPre-extraction fractions
Fucoidan extraction
Fucoidan (precipitated)
+
Supernatant
Alginate extractionAlginate precipitated
+
Supernatant
High T hydrolysis Sugars bioethanol
Microwave Chemistry
Fucoidans as antioxidants
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0.00%
5.00%
10.00%
15.00%
20.00%
25.00%
5 min 15 min 30 min 3*3 h
DP
PH
ra
dic
al
sca
ven
gin
g
effe
ct
(%)
Extraction time
150 °C
120 °C
90 °C
Conventional
Ferricyanide (III) to ferricyanide (II)
DPPH scavenging
Yuan and Macquarrie, Carb. Polym. 2015 129 101-107
Fermentation of sugars
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0.00
2.00
4.00
6.00
8.00
10.00
12.00
0 12 24 36 48 60 72 84
Su
ga
r co
nce
ntr
ati
on
(g
/L)
Time (h)
Gal
Glu
Man
-5.00%
5.00%
15.00%
25.00%
35.00%
45.00%
55.00%
65.00%
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
0 20 40 60 80
Eth
an
ol
percen
t th
eo
reti
ca
l y
ield
(%
)
Con
cen
trati
on
(g
/L)
Time (h)
Ethanol
concentration
Ethanol yield
Biochar as a solid fuel
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% C % H % N HHVa (MJ/kg) EDb Mass yield EYc %
Raw seaweed 36.26 4.86 0.84 13.73 / / /
Biorefinery 51.05 5.29 1.87 21.23 1.55 21.44 33.23
Fucoidan extraction
only
39.91 5.50 1.68 15.42 1.12 50.04 56.04
Alginate extraction only 41.47 5.55 1.34 16.65 1.21 39.82 48.18
Hydrolysis only 54.05 5.7 1.6 22.93 1.67 33.23 55.49
HHV almost as high as direct hydrolysis residues,
but also gain alginates and fucoidans
Yuan and Macquarrie ACS Sust. Chem. Eng., (2015) 3 1359-1365