Woody Biomass As a Sustainable Feedstock for Bio-Based Chemicals

Woody Biomass as a sustainable feedstock for Bio-based chemicals

Professor James Clark Green Chemistry Centre of Excellence (UK)

We live in a chemically-dependent society

97% of all goods are manufactured using at least one chemical reaction But its not sustainable…..in products, process or resources…. Our consumption patterns are changing

Global reliance on metals is growing: being CARBON neutral = being METALS dependent We are using non-renewable, diminishing resources. Making more waste than product, and using dangerous substances

140 REACh! 120 Number of 100 Environmental Laws 80 60 40 20 0 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 2010 Oil Refining…

Fuel

Plastics

Asphalt Agro-chemicals

Pharmaceuticals

Base Cleaning agents Chemicals Crude Oil OIL REFINERY REFINERY OIL Solvents

Dyes and clothing Energy Many more……

>90% of organic chemicals are derived from non-renewable fossil resources 10% of petroleum is used to make chemicals= 50% of the value

We are heavily reliant on non-renewables.....but our crude oil reserves are finite and increasingly difficult to access

BUT time is running out for petrochemical feedstocks!(and for other traditional resources)

Biomass is the only practical and sustainable source of carbon for chemicals The bio-economy is a global priority

But we need to learn from early mistakes… 125 M hectare = 0.8% world land area

75 billion € 97 billion € 180 billion € 60€/ T of biomass 80€/ T of biomass 140€/ T of biomass

1200 Mt CO2 savings 1200 Mt CO2 savings 1500 Mt CO2 savings

Biorefining will improve the process economics (Energy -> Fuels -> Chemicals)

& Johan Sanders - Wageningen University, The Netherlands Biorefinery, the bridge between Agriculture and Chemistry 2G bioethanol Fuels Bio-diesel others Plastics Materials Agro-chemicals

Pharmaceuticals

Chemicals Nutraceuticals BIOREFINERY BIOREFINERY Solvents Platform Molecules Clothing Waste/low value Energy Biomass Biomass (co)firing AD Evaluation of industrial side streams

Criteria for category Criterion 1 Criterion 2 selection: Industrial side stream (ISS) Carbohydrate Geographical capacities distribution Carbohydrate capacities: Fruit and vegetables juice Low Low 1. Low: < 1 million t production side streams Cheese production side stream 2. Medium: 1 to 2 million t High Medium (whey) 3. High: > 2 million t Winery side streams Low Low

Brewer’s spent grains Medium Low Geographical distribution of Rapeseed meal High Medium sugars derived from ISS with Sunflower meal Medium Medium annual availability higher Biowaste fraction of Municipal than 100,000 t sugars: High High Solid Waste 1. Low: availability in less Spent coffee Grounds Low Low than 4 countries. Crude Glycerol Medium Low 2. Medium: availability in 4 -

Sugar Beet Pulp High Medium 7 countries. 3. High: availability in more Pulp and paper thick liquor High High than 7 countries. Wastes from industrial bread High Not available making Geographical distribution of total thick liquor derived annually from the pulp and paper industry

Thanks to Apostolis Koutinas, AUA Bio-based Platform Molecules

3 or less Small Contain functionality for Bio-derived steps* molecule derivatisations

Product 1

Product 2 reaction Biomass Processing Platform Feedstock Technology Molecule reaction Product 3

*Steps could include fractionation Product4 and purification as well

T J Farmer and M Mascal, Chapter 4: Platform Molecules, in Introduction to Chemicals from Biomass 2nd Ed., 2014, 89-155 UK Top 20 Bio-based chemicals

9. Fatty alcohols (many structures)

15. poly(hydroxy- alkanoates) (many structures)

19. CH3OH

The downstream chemistry from a bio-refinery will be very different to that used today…

Oxidation versus Reduction T.J.Farmer, M.Mascal, Chapter 4: Platform Molecules, in Introduction to Chemicals from Biomass 2nd Ed., Wiley, 2014

oxalic acid

succinic Platform acid Molecules glucose aspartic acid methanol

itaconic acid ethanol levoglucosenone and HMF

5-chloromethyl furfural eugenol lysine lauric acid

Fossil Base Chemicals toluene xylenes ethene, limonene propene butane Oxidation versus Reduction T.J.Farmer, M.Mascal, Chapter 4: Platform Molecules, in Introduction to Chemicals from Biomass 2nd Ed., Wiley, 2014

maleic acid

TA PET

paracetamol surfactant herbicide pTSA Nylon-6,6 polycarbonate dye poly(ethene) liquid crystal Oxidation versus Reduction T.J.Farmer, M.Mascal, Chapter 4: Platform Molecules, in Introduction to Chemicals from Biomass 2nd Ed., Wiley, 2014

Platform Molecules

REDUCTION

Key Petrochemical Products

OXIDATION Fossil Base Chemicals Levoglucosenone – Precursor to Bio-based Polar Aprotic Solvents • Cyrene (dihydrolevoglucosenone) is a new polar aprotic solvent – high O-content is beneficial • It is derived from cellulose, via the hydrogenation of cellulose- derived levoglucosenone, LGO (via pyrolysis) • Unlike many polar aprotics (DMSO, DMF, NMP, DMAc, sulfolane) it does not contain N or S – Less environmental damage following incineration • Comparable physical (b.p. 203 °C) and solvation properties (π*) to polar aprotics (many of which are under increasing danger of being restricted by legislation, NMP is now restricted)

J. H. Clark et al., Chem.Comm., 2014, 50, 9650 Opportunity: New alternative solvents A bio-based alternative for dipolar aprotic solvents

Cyrene

NMP

HSPiP, 5th edition, version 5.0.03, 2015. CHEM21 SOLVENT GUIDE

But existing solvents are not enough… we need new, preferably bio-based solvents Early Cyrene applications from York

J. Sherwood et al Chem. Commun., A. A. C. Pacheco et al., ChemSusChem, 2014, 50, 9650-9652 2016, 9, 3503 –3512 Solvent selection protocol: Graphite exfoliation and dispersion

H. J. Salavagione et al., Green Chem., 2017, 19, 2550-2560. Renewable solvents with high performance in applications and improved toxicity profiles Now a commercial reality

A Capital JV between Circa and Norske-Skog exploiting a technology JV between Circa and the GCCE

New solvents AND new business for struggling sectors and regions www.york.ac.uk/res/s4 Computational Modelling

Solubility: Electrostatic interactions:

Courtesy of HSPiP and COSMOlogic We can also make polymers (plastics) from bio-based Platform molecules

27 PET (petrochemical)

DET PET

para-xylene PET (bio-based via FDEE)

fructose FDCA

HMF

FDEE

TA DET PET How can we get the chemical value from Biomass?

Using Microwaves to Selectively Target Different Structural Components of Biomass

30 Microwave pyrolysis. Different activity of structural components

Microwave results in pyrolysis at lower temperature for all biomass and biomass components studied " reduced energy See the poster ! Making LGE from Saccharides in Softwood Hydrolysis Lignin: A Sequential Process?

Crude waste Softwood Hydrolysis Lignin (CSHL) contains residual saccharides:

Using an optimized MW process we converted ~40% (9%wt wrt CSHL mass) of this residual saccharide to LGE (isolated in condensate):

MW, 180 °C, 5 mins Note: + LGO is = residual saccharide chiral

5 g CSHL 4.1 g “Cleaner” Lignin Levoglucosenenone SA = 5 m2 g-1 SA = 20 m2 g-1 9%wt wrt starting CSHL, 90% selectivity M. De bruyn et al., Energy Environ. Sci., 2016, 9, 2571-2574 GCCE KEY ENABLING PRODUCTS APPLICATIONS TECHNOLOGIES

#-sitostereol or 1-Heptatriacotanol Treat Heart n-Hexadecanoic acid TreatDisease High ColonCholesterol Cancer Oleic Acid Galltreatment stones Methyl tetracosanoate Cold & flu Docosane Psoriasis Acetovanillone Arthritis Bronchitis Methyl d-lyxofuranoside sc CO only Dietary Supp 2 Methyl tridecanoate Soaps Methyl levulate Cosmetics Inositol Pharmaceutical Methyl linoleate s sc CO2 + Emulsifying 10% Ethanol Xanthosine Solubilisingagent Methyl glycolate Reduceagent Blood Levoglucosan CommercialPressure Levoglucosenone FragrancesChemicals Bio-oil perfumes o-Guaicol 2-methoxy-5-vinylphenol Fatty acid/ester Microwave HMF Nano composites Bio-char Bio fuels Waxes & resins

Nano-cellulose Hydrothermal pyrolysis Fermentable Sugars Metals from wastes using trees and plants!.. Phytocat (www.phytocat.org)

Capture metals in plants via phytoextraction and utilise this trapped metal in situ for catalysis, focusing on the platinum group metals.

Funded by G8 Research Councils Initiative on Multilateral Research Funding: Materials Efficiency in collaboration with Yale University, UBC and Massey university (NZ). Remediating marginal land and providing new businesses in rural areas

The latest results from the Phytocat team….

Green Chemistry, 2018, in press Green Chemistry@York

The world’s leading Centre for Green and Sustainable research, training and commercialisation York, the University of York and the Green Chemistry Centre of Excellence The worlds first hydrothermal microwave pilot plant for processing bio-slurries…. : Global Green Chemistry Centres Over 32 Centres worldwide

Connecting established and fledgling Green Chemistry Centres 2015: UMass, Boston, USA Emphasis on: Networking, Education, Outreach, Industrial collaboration, Funding opportunities, Policy advancement

2014 UCT, Cape Town, RSA 2018 Ghent Belgium

2017 Melbourne 2016 Sichuan University 2013 University of Delhi Chengdu, China From the old to the new: A future Sustainable Chemical Industry

Old chemical industry

New green chemical industry

https://vimeo.com/296840340/6669378d09 Industry Education

www.greenchemistry.net

Research Networking