Creating Wealth from Waste: High Value Materials and Chemicals from Biowaste using Sustainable Technologies

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1 Creating Wealth from Waste: High Value Materials and Chemicals from Biowaste using Sustainable Technologies Magdalena Titirici Queen Mary University of London

2 Benefits of the Chemical Industry

3 Chemical industry across the life cycle Yet, we all hate chemicals!!!

4 Move towards a circular economy

5 We are running out of key elements

6 Location of scarce elements

7 So much ends up in waste

8 What do we do with our waste? What a waste!!

9 Food and agricultural waste is everywhere too 90 Mt of food waste generated every year in the EU (incl. industrial and household waste) or 179kg per capita in the UK, over 90% of the 5.7 Mt of commercial and industrial FW is discarded to landfill

10 Waste is tomorrows resource We need to encourage the greater use of chemically rich waste as a resource

11 What s in biowaste? Sugars Phenols Pectin Chitosan Chitin Starch Proteins Hemicellulose Cellulose Lignin Waxes Tannin Natural Dyes Alginic Acid Lipids

12 FOOD WASTE IS EVERYWHERE Agro-residues 46 Mt/y Spent coffee grounds 3 Mt/y 1 Mt/y of food waste Unripe coconut husks 5 Mt/y Orange peels 12 Mt/y 30 Mt/y of Agro-residues 382 t/y coffee husks Cassava starch 228 Mt/y Palm oil waste 15.8 Mt/y

13 Petroleum Refinery Fuels Solvent Bulk chemicals Plastics Petroleum feedstock Fibres Fine chemicals Oils

14 Biorefinery Fuels Solvent Plastics Biowaste Bulk chemicals Fine chemicals Fibres Oils

15 Getting off fossil fuels

16 voltaics, we required half the area n from waves, we imagined wave. To make energy crops with a big hole country. ntry-sized because all renewables rizes most of the powers-per-unit-. renewables alone would be very y solution will necessarily be large lan that adds up using renewables ting off fossil fuels, Brits are going s to something. Indeed to several Switch to Renewable Energy Power per unit l and or wat er ar ea Wind 2W/ m 2 Offshore wind 3W/ m 2 Tidal pools 3W/ m 2 Tidal stream 6W/ m 2 Solar PV panels 5 20 W/ m 2 Plants 0.5 W/ m 2 Rain-water (highlands) 0.24 W/ m 2 Hydroelectric facility 11 W/ m 2 Geothermal W/ m 2 Nuclear? Diffuse H 2? Table Renewable facilities have can t get production from Fossil renewtion, what are the other options? fuels with carbon capture and storage? to be country-sized because all Discontinuous Energy Storage renewables are so diffuse.

17 Materials in Historical Perspective 300 years ago humans used natural materials: stone, wood, bone, and natural fibbers Slowly our dependence changed and nonrenewable displaced renewables By the end of 20 century we became 100% addicted to non-renewables The resources from which materials are made exist only in a few countries 17

18 Conflict: Energy vs Materials World Energy Consumption: 500 EJ/year Materials & Chemicals Energy Making materials & chemicals consumes about 35% of the global energy Materials & chemicals today are derived from fossil fuels Energy today is from fossil fuels To build renewable energy we need materials & chemicals

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20 The Carbon Biorefinery Concept 6 RENEWABLE CHEAP LOW ENERGY IMPUT NO CO 2 EMISSIONS HTC Liquid: Chemicals HMF FA Basic chemicals Liquid fuels Green Solvents Polymers LA C self-generated pressure Solid: Carbon Functional materials Catalysts Electrode materials Adsorbents Solid fuels Titirici et al, Chem. Soc. Rev., 2015, 44, Titirici et al, Sustainable Carbon Materials via Hydrothermal processes, Wiley, 2013 Titirici et al, Energy and Environmental Science, 2012, 5, 6796

21 The Carbon Biorefinery Concept 5-10% Gas Phase 30-40% Liquid Phase 60-70% Solid Phase

22 Carbon Materials in Renewable Energy Fuel Cells H 2 Storage Batteries CARBON MATERIALS Suprercapacitors CO 2 Capture Water Splitting

23 Classical Carbon Materials Reduced Graphene Oxide Fullerenes Carbon Nanotubes CARBON MATERIALS Graphene Carbide-derived Carbons Carbon Onions

24 Classical Carbon Materials PROBLEMS (-) Derived from fossil fuels (i.e. CNTs) (-) Unpredictable properties ( i.e. CNTs) (-) Difficulties in up-scale synthesis (i.e. single wall CNTs, graphene) (-) High energy-consuming or harsh techniques are required for their synthesis (i.e. high energy-cvd, laser-ablation for CNT; harsh: Hummer s method-go)

25 Titirici et al, Sustainable Carbon Materials via Hydrothermal processes, Wiley, 2013 Carbon Materials from Waste

26 Carbon Nanostructures from Carbohydrates Titirici, Kubo, White et al, Chem. Mater. 2013, 25, Titirici, Kubo, White et al, Chem. Mater. 2011, 23, Titirici, Brun et al ChemSusChem, 2013, 6, Titirici, White et al J. Mater. Chem., 2009, 19,

27 Powders Morphology Control Monoliths Titirici, White, Clark et al, ChemSusChem, 2014, 7,

28 Lignin-derived Carbon Fibres ELECTROSPINNING When a sufficiently high voltage is applied to a liquid droplet, the body of the liquid becomes charged Electrostatic repulsion counteracts the surface tension and the droplet is stretched At a critical point a stream of liquid erupts from the surface and a charged liquid jet is formed

29 Applications in Renewable Energy Li-S Battery CE

30 Na Ion Batteries

31 Na vs Li Na is equally distributed E 0 (Na+/Na) = -2.71V vs standard hydrogen electrode

32 HTC Hollow Spheres 20 nm 20 nm Stable at 1000 o C Uniform wall (ca. 20 nm) Turbostratic-type carbon

33 Electrodes for Na-ion Batteries Anodes in Na-Ion Batteries Cycle Voltammetry Rate Performance 1.39 V (d) 0.36V Titirici, Tang, White et al, Adv. Energ. Mater , 873

34 HTC in Fuel Cells PEMFC cathode ORR O 2 + 4H + + 4e - H 2 O O 2 + 4H + + 2e - H 2 O 2 H 2 O 2 + 2H + + 2e - 2H 2 O ORR at Cathode needs improvement Slow reaction kinetics Expensive Pt catalyst Poor catalyst stability

35 Platinum Resources

36 Platinum Resources

37 Platinum Resources Pt DEPLETION

38 Natural Templates Using crustacean waste- in situ hard tempalting with CaCO 3 High Volume Food Waste Chitin ---- Nitrogen / Carbon source CaCO Sacrificial template HTC of Shrimp/Lobster Shell waste Porous Carbons/Chiral Carbons

39 Lobster-derived HTC

40 Intensity (a.u.) XPS NITROGEN DOPED CARBON N-6 N-Q N-O ev-pyridinic-n (N-6, 40.4%) Binding Energy (ev) C1s ev-quaternary-n (N-Q; 53.7%) ev-pyridine-n-oxides (N-O; 5.9 %) C1s: % O1s: 4.73 % N1s: 6.11 % O1s N1s Binding Energy (ev)

41 Current (ma cm -2 ) Current (ma cm -2 ) ORR Performance RDE, LSV 1600 rmp scan rate of 10 mv s M KOH 0.5 M H 2 SO V to -1 V 1 V to -0.2 V N-CC Pt/C N-CC Pt/C Potential (V vs. Ag/AgCl) Potential (V vs. Ag/AgCl)

42 The Carbon Biorefinery Concept 5-10% Gas Phase 30-40% Liquid Phase 60-70%Solid Phase

43 Chemicals from biomass

44 % Yield HTC Liquid Phase C ,37 14,51 17,33 27, ,88 1,03 1,62 1,71 2,04 5, Water 10% HCl 2% NaOH Solid Yield (%) LA Yield (%) HMF Yield (%) Formic Yield (%) Acetic Acid (%) GVL (%) Acidic conditions lead to higher LA Yield NaOH slows down HTC process, leading to higher HMF yields LA from different precursor LA Yield from HTC Cellulose % H2SO4 24 hours Water 10% HCl 2% NaOH 5 0 Glucose Cellulose Rye Straw Hours

45 Similar properties to FAME Addition to biodisel to improve the cold flow properties Can be use in fragrance industries Levulinic Acid

46 The Carbon Biorefinery Concept 5-10% Gas Phase 30-40% Liquid Phase 60-70%Solid Phase

47 CO 2 to fuels CO 2 Utilization

48 CO 2 Utilization

49 Use waste, stimulate a circular economy Use green chemistry at every life cycle step Green chemical industry and products