Creating Wealth from Waste:

High Value Materials and Chemicals from

Biowaste using Sustainable Technologies

Magdalena Titirici Queen Mary University of London

Benefits of the Chemical Industry

Chemical industry across the life cycle

Yet, we all hate chemicals !!!

Move towards a circular economy

We are running out of key elements

Location of scarce elements

So much ends up in waste

What do we do with our waste?

What a waste!!

• 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

Food and agricultural waste is everywhere too

Waste is tomorrows resource

We need to encourage the greater use of chemically rich waste as a resource

Sugars

Phenols

Proteins

Starch

Natural Dyes

Chitosan

Cellulose

Pectin

Hemicellulose

Waxes Lignin

Chitin

Alginic Acid

Lipids

Tannin

What´s in biowaste?

Palm oil waste

15.8 Mt/y Unripe coconut

husks 5 Mt/y

Cassava starch

228 Mt/y

30 Mt/y of

Agro-residues

382 t/y coffee

husks

1 Mt/y of

food waste Agro-residues

46 Mt/y

Spent coffee

grounds 3 Mt/y

Orange peels

12 Mt/y

FOOD WASTE IS EVERYWHERE

Petroleum

feedstock

Fuels

Solvent

Bulk chemicals

Plastics

Fibres

Fine chemicals

Oils

Petroleum Refinery

Solvent

Bulk chemicals

Plastics

Fibres

Fine chemicals

Oils

Biowaste

Biorefinery

Fuels

Getting off fossil fuels

Copyright David JC MacKay 2009. This electronic copy is provided, free, for personal use only. See www.withouthotair.com.

112 SustainableEnergy – without thehot air

big contribution from solar photovoltaics, we required half the areaPower per uni t l and

or wat er ar ea

Wind 2W/ m2

Offshore wind 3W/ m2

Tidal pools 3W/ m2

Tidal stream 6W/ m2

Solar PV panels 5–20W/ m2

Plants 0.5W/ m2

Rain-water

(highlands) 0.24W/ m2

Hydroelectricfacility 11W/ m2

Geothermal 0.017W/ m2

Table 18.10. Renewable facilities haveto be country-sized because allrenewables are so diffuse.

of Wales. To get a big contribution from waves, we imagined wavefarms covering 500km of coastline. To make energy crops with a big

contribution, we took 75% of the whole country.

Renewable facilities have to be country-sized because all renewables

are so diffuse. Table 18.10 summarizes most of the powers-per-unit-area that we encountered in Part I.

To sustain Britain’s lifestyle on its renewables alone would be very

difficult. A renewable-based energy solution will necessarily be largeand intrusive.

2. It’s not going to beeasy to make a plan that adds up using renewablesalone. If we are serious about getting off fossil fuels, Brits are goingto have to learn to start saying “yes” to something. Indeed to several

somethings.

In Part II I’ll ask, “assuming that we can’t get production from renew-ables to add up to our current consumption, what are the other options?”

Notes and further reading

page no.

104 UK average energy consumption is 125 kWh per day per person. I took this number from the UNDP Human Devel-

opment Report, 2007.

The DTI (now known as DBERR) publishes a Digest of United Kingdom Energy Statistics every year. [uzek2]. In

2006, according to DUKES, total primary energy demand was 244 million tons of oil equivalent, which corresponds to

130 kWh per day per person.

I don’t know the reason for the small difference between the UNDP number and the DUKES number, but I can explain

why I chose the slightly lower number. As I mentioned on p27, DUKES uses the same energy-summing convention

as me, declaring one kWh of chemical energy to be equal to one kWh of electricity. But there’s one minor exception:

DUKES defines the “primary energy” produced in nuclear power stations to be the thermal energy, which in 2006

was 9 kWh/ d/ p; this was converted (with 38% efficiency) to 3.4 kWh/ d/ p of supplied electricity; in my accounts,

I’ve focused on the electricity produced by hydroelectricity, other renewables, and nuclear power; this small switch in

convention reduces the nuclear contribution by about 5 kWh/ d/ p.

– Losses in the electricity transmission network chuck away 1% of total national energy consumption. To put it another

way, the losses are 8% of the electricity generated. This 8% loss can be broken down: roughly 1.5% is lost in the

long-distance high-voltage system, and 6% in the local public supply system. Source: MacLeay et al. (2007).

105 Figure 18.4. Data from UNDP Human Development Report, 2007. [3av4s9]

108 In the Middle Ages, the average person’s lifestyle consumed a power of 20 kWh per day. Source: Malanima (2006).

110 “I’mmore worried about the ugly powerlines coming ashore than I was about a Nazi invasion.” Source: [6f r j 55].

Switch to Renewable Energy

• Diffuse • Discontinuous

• Nuclear? • H2? • Fossil fuels with carbon capture and storage?

Energy Storage

• 300 years ago humans used natural materials: stone, wood, bone, and natural fibbers

• Slowly our dependence changed and non-renewable 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

Materials in Historical Perspective

World Energy Consumption: 500 EJ/year

• 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

Materials & Chemicals

Energy

Conflict: Energy vs Materials

Liquid: Chemicals

Solid: Carbon

Basic chemicals Liquid fuels Green Solvents Polymers

Functional materials Catalysts Electrode materials Adsorbents Solid fuels

HMF

LA

FA

HTC

Titirici et al, Chem. Soc. Rev., 2015, 44, 250-29 Titirici et al, Sustainable Carbon Materials via Hydrothermal processes, Wiley, 2013 Titirici et al, Energy and Environmental Science, 2012, 5, 6796

200-300 C self-generated pressure

• RENEWABLE • CHEAP • LOW ENERGY IMPUT • NO CO2 EMISSIONS

6

The Carbon Biorefinery Concept

≈ 60-70% Solid Phase

≈ 30-40% Liquid Phase

≈ 5-10% Gas Phase

The Carbon Biorefinery Concept

CARBON MATERIALS

Batteries

Water Splitting

H2 Storage

Fuel Cells

CO2 Capture

Suprercapacitors

Carbon Materials in Renewable Energy

CARBON MATERIALS

Carbon Nanotubes

Carbon Onions

Fullerenes

Graphene

Carbide-derived Carbons

Reduced Graphene

Oxide

Classical Carbon Materials

(-) 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)

PROBLEMS

Classical Carbon Materials

Carbon Materials from Waste

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

Titirici, Kubo, White et al, Chem. Mater. 2013, 25, 4781-4790 Titirici, Kubo, White et al, Chem. Mater. 2011, 23, 4882−4885 Titirici, Brun et al ChemSusChem, 2013, 6, 701 – 710 Titirici, White et al J. Mater. Chem., 2009, 19, 8645–8650

Carbon Nanostructures from Carbohydrates

Morphology Control

Powders

Monoliths

Titirici, White, Clark et al, ChemSusChem, 2014, 7, 670-689

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

Applications in Renewable Energy

Li-S Battery

CE

Na Ion Batteries

Na is equally distributed

E0 (Na+/Na) = -2.71V vs standard hydrogen electrode

Na vs Li

• Stable at 1000 oC

• Uniform wall (ca. 20 nm)

• Turbostratic-type carbon

20 nm

20 nm

HTC Hollow Spheres

(d)

1.39 V

0.36V

Cycle Voltammetry Rate Performance

Titirici, Tang, White et al, Adv. Energ. Mater. 2012 2, 873

Electrodes for Na-ion Batteries

Anodes in Na-Ion Batteries

HTC in Fuel Cells

O2 + 4H+ + 4e- H2O

O2 + 4H+ + 2e- H2O2

H2O2 + 2H+ + 2e- 2H2O

ORR ORR at Cathode needs improvement

• Slow reaction kinetics

• Expensive Pt catalyst

• Poor catalyst stability

cathode

PEMFC

Platinum Resources

Platinum Resources

Pt DEPLETION

Platinum Resources

High Volume Food Waste

• Chitin ---- Nitrogen / Carbon source

• CaCO3 ---- Sacrificial template

HTC of Shrimp/Lobster Shell waste

Porous Carbons/Chiral Carbons

Using crustacean waste-”in situ” hard tempalting with CaCO3

Natural Templates

Lobster-derived HTC

1000 800 600 400 200 0

396 398 400 402 404

N-ON-Q

Inte

nsity (

a.u

.)

Binding Energy (eV)

N-6

C1s: 89.16 %

O1s: 4.73 %

N1s: 6.11 %

O1s N1s

C1s

Inte

nsity (

a.u

.)

Binding Energy (eV)

NITROGEN DOPED CARBONS

• 398.6 eV-pyridinic-N (N-6, 40.4%) • 400.9 eV-quaternary-N (N-Q; 53.7%) • 402.7 eV-pyridine-N-oxides (N-O; 5.9 %)

XPS

-0.8 -0.6 -0.4 -0.2 0.0 0.2-5

-4

-3

-2

-1

0

Curr

ent

(mA

cm

-2)

Potential (V vs. Ag/AgCl)

N-CC

Pt/C

-0.2 0.0 0.2 0.4 0.6 0.8-4

-3

-2

-1

0

Curr

ent

(mA

cm

-2)

Potential (V vs. Ag/AgCl)

N-CC

Pt/C

RDE, LSV 1600 rmp

0.1 M KOH 0.5 M H2SO4

ORR Performance

0.2 V to -1 V 1 V to -0.2 V

scan rate of 10 mV s-1

≈ 60-70%Solid Phase

≈ 30-40% Liquid Phase

≈ 5-10% Gas Phase

The Carbon Biorefinery Concept

Chemicals from biomass

0

10

20

30

40

50

60

70

80

2 4 6 24 2 4 6 24 2 4 6 24

Water 10% HCl 2% NaOH

5,82

14,51 17,33

21,37

27 27,49 24 24,88

1,03 1,62 1,71 2,04

Glucose@180°C

Solid Yield (%) LA Yield (%) HMF Yield (%)

Formic Yield (%) Acetic Acid (%) GVL (%)

0

10

20

30

40

2 4 6 24

% Y

ield

Hours

LA Yield from HTC Cellulose

Water

10% HCl

2% NaOH

0

5

10

15

20

25

30

35

Glucose Cellulose Rye Straw

30.3 27.2

14.7

LA from different precursor

6% H2SO4 24 hours

Acidic conditions lead to higher LA

Yield

NaOH slows down HTC process, leading to higher HMF yields

HTC Liquid Phase

Levulinic Acid

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

≈ 60-70%Solid Phase

≈ 30-40% Liquid Phase

≈ 5-10% Gas Phase

The Carbon Biorefinery Concept

CO2 Utilization

CO2 to fuels

CO2 Utilization

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