Renewable feedstocks Thursday 29th October 2009

PLATFORM CHEMICALS

Adapted from Introduction to Chemicals from Biomass, ed. Clark, J.; Deswarte, F. Wiley, 2008

Chemicals from Crude oil

Oil  Brassica  Artemisia Artemisinin Animal feed Biofuels Food  Wheat (straw) Animal feed Lignocellulose Food

Lignin Cellulose Hemi-cellulose Cell membrane Artemisia annua Artemisinin Artemisinin derivatives Flavonoids, Terpenes & other phenolics WaxesSugars

PHENOLICS FROM ARTEMESIA

Flavones Functionalizing Flavones

Monomers for polyester formation

Monomers for polyether formation Monomers for methacrylate formation

PHENOLICS FROM WASTE STRAW

Lignin is a major component of plant cell walls Lignin-degrading microbes Bacterial aromatic degraders

Fluorescent Assay for Lignin Degradation Time dependence (0-2 hr) 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 ExtractMass (g)Percentage of total (wet) Percentage of total (dry) Aqueous %38.6% Organic %3.57% Dry Straw %57.9% Water content-72.7%-

HPLC traces with time Degrader Pseudomonas putida Non-degrader Bacillus subtilis shows no change

GC-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 o C. Mass spectrum of peak at RT 7.02 min, assigned to monosilylated derivative of ketone (1), m/z 268 (M- SiMe 3 )+, 253 (M-SiMe 3 - CH 3 )+.

Aromatic metabolites identified (so far) CompoundLC-MS Retention time (min) LC-MS m/z GC-MS Retention time (min) GC-MS m/z (silylated) Observed with MK M CH 3 P. Putida 6hr, 1d, 3d Rhodococcus RHA1 2hr, 4hr Miscanthus & wheat straw MNa MK M CH 3 P. Putida (straw) 7d Rhodococcus RHA1 Miscanthus 1d, straw 2d MH M-CH 3 P. Putida 6hr Rhodococcus RHA1 2hr, 6hr Miscanthus only MK M- CH 3 P. Putida 6hr Rhodococcus RHA1 4hr, 6hr Miscanthus only MH + Rhodococcus RHA1 6hr Miscanthus only

Ferulic acid. 379 papers in on biological activity alone £1 per 1g Anti-oxidant Active breast cancer, liver cancer Active ingredient in anti-ageing creams / plumping creams Carboxy vanillic acid. 0 papers in 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 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

’00’ Canola High ErucicHigh Oleic Natural profiles of some rapeseed oils now available

Polyurethanes (polymers)

Composite type Fibre volume (%) Tensile strength (MPa) Young’s Modulus (GPa) Composite density (Kg/m 3 ) Impact strength (kJ/m 2 ) HEMP/ EUPH (1.06) (2.17) HEMP / RAPE (2.21) (1.21) JUTE / EUPH (2.60) (2.27) JUTE / RAPE (3.37) (1.95) Vegetable Oils as Polymer Feedstocks (monomers) Rapeseed oil Euphorbia oilJuteHemp

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 TypeProcessingExtracted mass / mg % dry mass extracted UntreatedNone UntreatedWater UntreatedChopped P. ChrysosporiumNone P. ChrysosporiumWater P. ChrysosporiumChopped

Tungstan mediated fatty acid functionalisation: J. Appl. Poly. Science, In Prep

Future work

Expand to renewable ’Waste Products’ further down manufacturing line. e.g. food industry, Confectionary Use outputs to make demonstrator pieces for media and industrial dissemination

Electrospinning Lignin Filler in biocomposite structures May promote resin / matrix adhesion between for natural fibres Future work Use in electrospun nanofibres Solutions not ideal for electrospinning Potential to be co-spun with other polymers (e.g. PVOH) Degradation products may have beneficial anti-oxidant properties which can be incorporated