Renewable feedstocks
Thursday 29th October 2009
Structural
cellulosehemicelluloselignin
stems, leaves
Fibresstems, leaves
Waxes and Gumsstems, leaves,
seeds f ruit
Secondary metabolites
phenolicsalkaloidsterpenes
stems, leaves, roots,seeds, f ruit
Dyes, Essential Oilsstems, leaves, roots,
seeds, f ruitStorage metabolites
oilscarbohydratesproteins
tubers, roots,nutsseeds, f ruit
Sugars
O
H
HO
H
HO
H
OHOHH H
OH
C2
Acetic acidEthanol
Oxalic acid
C3
1,2-Propanediol1,3-Propanediol
AcetoneLactic acid
Propionic acid
C4
1,4-butanediol3-hydroxybutryolactone
AcetoinAspartic acid
ButanolFumeric acid
Malic acidSuccinic acid
C5
Itaconic acidLevulinic acidXylonic acid
C6
Citric acidGluconic acid
Sorbitol
PLATFORM CHEMICALS
Polymerisation
Esterification
Dehydration
Hydrogenation
Reduction
Oxidation
Lactic acid
Polylactic
Lactate
Acrylic Acid
1,2-Propanediol
Propionic acid
Oxalic acid
Polymers
Solvents
Fine Chemicals
Adapted from Introduction to Chemicals from Biomass, ed. Clark, J.; Deswarte, F. Wiley, 2008
Chemicals from Crude oil
Oil
Brassica
Artemisia
O
O
HCH3
H
O
O
H3C O
HCH3
Artemisinin
Animal feed
Biofuels
Food
Wheat (straw)Animal feed
Lignocellulose
Food
Lignin
Cellulose
Hemi-cellulose
Cell membrane
PHENOLICS FROM ARTEMESIA
FlavonesOHO
OH O
OHO
OH O
OH
OH
OH
OHO
OH O
OH
OH
O
OOO
OH
OH
OHOHOH
OH
O
O
HO
OH
O
O
RO
OH
derivitizePolyethers, polyesters,poly(methacrylate) with
antioxidant/UV absorbing properties
Functionalizing Flavones
O
OOH
OO
OH
O
O
O
OOH
OO
OH
O
O
O
OOH
OOO
O OH
O
OOH
OEtO
O
O
O
OOH
O
O
MeO
O
O
OOH
OHO
OH
Monomers for polyester formation
Monomers for polyether formation
O
OOH
OBr
O
OOH
OBr
O
OOH
OBr
Monomers for methacrylate formation
O
OOH
O
O
O
OOH
OO
O
PHENOLICS FROM WASTE STRAW
OH OMe
OMe
O
RO
OHO
OH
OMe
OMe
HO
OH
OMe
HO O
OH
R
MeO
OH
OMeO
O
OMe
OHOH
OMe
O
HOOMe
OMe
HO
MeO CO2H
OH
HO2COH
OMe
HO
OH
OH
OMe
OH
OMe
CHO
HO
MeOOH
OMe
R
OH
O
OMe
OHMeO
OH
O
OMe
OMe
HO
MeO CO2H
HO2C
O
CO2HHO
HO OMe
O
O
OMe
OH
HO
lyase
CO2H
HO
MeO CO2H
OH
OMe
CO2H
OH
OH
CO2H
peroxidase
-aryl ether phenylcoumarane biphenyldiarylpropanepinoresinol
1) demethylase2) extradioldioxygenase
aldehyde dehydrogenase
CO2H
OHCO2Hdemethylase
decarboxylase
C-C hydrolase
lignostilbenedioxygenase
HCHO
OHCOH
CO2H
HO2C CO2H
CO2H
OHO CO2H
CO2H
OO
extradioldioxygenase
aldehydedehydrogenase
CO2H
CO2H O
HO
CO2H
O2 x
hydratase
aldolase
decarboxylase
CO2
Lignin is a major component of plant cell walls
Lignin-degradingmicrobes
Bacterialaromaticdegraders
Fluorescent Assay for Lignin Degradation
OH
OMe
HO
LIGNIN
attach fluorophore
O
OMe
HO
LIGNIN
OFl
lignindegrader
Fluorescence change
Could be performed in 96-wellmicrotitre plate reader
Fluoresence Vs Time For P. Putida Supernatant
16000
16500
17000
17500
18000
18500
0 20 40 60 80 100 120
Time (min)
Fluo
rsen
ce
30 ul
Time dependence (0-2 hr)Change in fluoresecence in the first 10 min
-2000
-1500
-1000
-500
0
500
1000
Flu
ore
scen
ce
Streptomyces Viridosporus
B. Subtillis
P.Putida
Rhodococcus RHA1
Rhodococcus sp
Nocardia autotrophica
Leuconostoc Mesentoides
Non-degraders
Assay can distinguish degraders from non-degraders:
Tim Bugg, Paper Submitted to Molecular Biosystems
Large Scale Extraction
• 1.5 kg (wet) of P.chrysosporium-degraded straw was extracted using 20 L reactor
• 12 L of water and 8 L of THF used to extract straw• THF was used due to combination of interesting
peaks from LTQ analysis and mass recovered in previous trials
17
Extract Mass (g) Percentage of total (wet)
Percentage of total (dry)
Aqueous 156.88 10.6% 38.6%
Organic 14.5 0.98% 3.57%
Dry Straw 235.3 15.9% 57.9%
Water content - 72.7% -
HPLC traces with time
Degrader Pseudomonas putida
Non-degrader Bacillus subtilisshows no change
GC-MS data for small scale lignocellulose degradation trialsGC-MS data for small scale lignocellulose degradation trials GC-MS total ion chromatogram with EI ionisation for Rhodococcus RHA1 incubated with wheat straw lignocellulose for 7 days at 30 oC.
Mass spectrum of peak at RT 7.02 min, assigned to monosilylated derivative of ketone (1), m/z 268 (M-SiMe3)+, 253 (M-SiMe3-CH3)+.
O OH
O
OH
1
Aromatic metabolites identified (so far)
Compound LC-MS
Retention time (min)
LC-MS
m/z
GC-MS
Retention time (min)
GC-MS
m/z
(silylated)
Observed with..
1 4.29 235 MK+ 7.02 268 M+
253 -CH3
P. Putida 6hr, 1d, 3d
Rhodococcus RHA1 2hr, 4hr
Miscanthus & wheat straw
2 4.56 209 MNa+
225 MK+
7.71 243 M+
228 -CH3
P. Putida (straw) 7d
Rhodococcus RHA1
Miscanthus 1d, straw 2d
3 5.25 195 MH+ 5.27 251
M-CH3
P. Putida 6hr
Rhodococcus RHA1 2hr, 6hr
Miscanthus only
4 5.76 251 MK+ 6.03 341 M-CH3
P. Putida 6hr
Rhodococcus RHA1 4hr, 6hr
Miscanthus only
5 9.09 169 MH+ Rhodococcus RHA1 6hr
Miscanthus only
O OH
OCH3
OH
COOH
COOHHO O
CO2H
OCH3
OH
COOH
COOH
OH
H3CO
COOH
OH
OCH3
OH
OMe
CO2H
Ferulic acid.379 papers in 2008-9 on biological activity alone£1 per 1gAnti-oxidantActive breast cancer, liver cancerActive ingredient in anti-ageing creams / plumping creams
CO2H
OH
OMeHO2C
Carboxy vanillic acid.0 papers in 2008-9
Potential use as fine chemical building block.Vanillic acid precursor.Diacid for use in polyesters and polyamides
Other potential major degradation products-yet to be fully identified from wheat straw
O
OMe
OH
OHO OH
MeO
OH
OH
O
HO
OMe
OH
HO
OMe
OH
O
Derivative of Gallic acid.Anti-fungal, anti-viral, anti-oxidant. Gallic acid is used in dyes
and inks.
No current market.Potential in poly-ethers, -ester or -urethanes
Vanillic acid precursor?Diacid for use in polyesters and polyamides
OIL FROM BRASSICA
RAPESEED
O
O
epoxidationRAPESEED
H2O2, W, H3PO4Room temperature
HO
HO
OH
OH
ring opening
acid, H2ORAPESEED
Saturated
Oleic
Linoleic
Linolenic
Erucic
’00’ Canola High Erucic High Oleic
Natural profiles of some rapeseed oils now available
Saturated
Oleic
Linoleic
Linolenic Saturated
Oleic
Linoleic
Linolenic
hydroxylatedmonomers
OH
OH
Isocyanatemonomers
NCO
NCO
catalyst
hydroxylatedmonomers
O
OO
HN
Isocyanatemonomers
Polyurethanes (polymers)
Compositetype
Fibre volume
(%)
Tensile strength(MPa)
Young’s Modulus
(GPa)
Composite density(Kg/m3)
Impact strength(kJ/m2)
HEMP/ EUPH 21.05 22.91 (1.06)
2.31 649.55 18.81(2.17)
HEMP / RAPE 19.92 38.84 (2.21)
3.40 697.09 9.25(1.21)
JUTE / EUPH 23.77 55.52(2.60)
4.26 658.59 10.60(2.27)
JUTE / RAPE 23.74 46.38(3.37)
3.89 704.93 13.70(1.95)
Vegetable Oils as Polymer Feedstocks (monomers)
Rapeseed oilEuphorbia oil JuteHemp
WAX FROM WASTE STRAW
Wax Extraction - Results
It would appear that a higher content is made available by degradation, but it is unknown to the origin of the material.
Straw Type Processing Extracted mass / mg
% dry mass extracted
Untreated None 80 1.84
Untreated Water 24 0.55
Untreated Chopped 100 1.77
P. Chrysosporium None 310 7.40
P. Chrysosporium Water 40 0.96
P. Chrysosporium Chopped 230 5.35
Fatty acidsNa2WO4.2H2O
H2O2, aliquat, 100 °C, 5hr
HO2C CO2H
Azelaic acid
Rosacea treatmentAcne treatment
Hair growth stimulantNylon-6,9
+ Estolides
LubricantsRust inhibitor
n=4
n=5
n=3
n=2
O C
O
HOOH
HO
NaOOC
n-1
Tungstan mediated fatty acid functionalisation: J. Appl. Poly. Science, In Prep
Future work
Mixtures
(Flavones)Materials
IncreasingComplexity
DecreasingComplexityDiscrete
Smaller building blocks
OHO
OH O
OH
OH
OH
OHO
OH O
OHO
OH O
OH
OH
O
OOO
OH
OH
OHOHOH
OH
ChemicalDegradation
BiologicalDegradation
HO
OH
OH
OH
OH
Future work
Expand to renewable ’Waste Products’ further down manufacturing line.
e.g. food industry, Confectionary
Biodiesel Wealth out of Waste(EP/E002773/01)
(Akzo Nobel)
Use outputs to make demonstrator pieces for media and industrial dissemination
Electrospinning Lignin
Filler in biocomposite structuresMay promote resin / matrix adhesion between for natural fibres
Future work
Use in electrospun nanofibresSolutions not ideal for electrospinningPotential to be co-spun with other polymers (e.g. PVOH)Degradation products may have beneficial anti-oxidant properties which can be incorporated