Bio-renewables:

A Sustainable Source of Chemicals

and Materials

James Clark

Green Chemistry Centre of Excellence

Chemistry Department

University of York, UK

www.greenchemistry.net

Petroleum

feedstock

Fuels

Solvent

Bulk chemicals

Plastics

Fibres

Fine chemicals

Petroleum Refinery

We know that our current fossil resources are not a

sustainable source of carbon

But its not only our carbon consumption

patterns that are not sustainable...

Fuels

Solvent

Bulk chemicals

Plastics

Fibres

Fine chemicals

Oils

Bio-refinery

Biomass

Don’t use food quality feedstocks!!

Our major challenge continues to be Carbon

Whats available from our existing food supply chains?

• • •

• •

• WORLD

• Rice husks 110 million T/yr

• Citrus peel residue 15.6 million T/yr

• Apple pomace 3-4.2 million T/yr

• Grape pomace 5-9 million T/yr

• Banana peels 9 million T/yr

• Kiwi residue 0.3 million T/yr

AFRICA

• Citrus waste 139,724 T/yr (South Africa)

• Cocoa pods 20 million T/yr (Ivory Coast)

• Cashew Shell Nut Liquid 20,000 T/yr (Tanzania)

U.S.A.

•Whey 43,091,275 T/yr

• Corn stover 80–100 million T/yr (dry basis)

California:

• Vegetable crop residue 1 million T/yr (dry basis)

• Tomato pomace 60,000 T/yr (dry basis)

• Nut shells & pits 40,000 T/yr

• Meat processing waste 65,000 T/yr (dry basis)

• Food scraps in MSW 1.6-2 million T/yr (dry basis)

E.U.

• Starch 8 million T/yr

• Tomato pomace 4 million T/yr

• Post manufacturing food waste 34 million T/yr

• Used cooking oil 0.7-1 million T/yr

• Surplus whey 13,462 T/yr

• Surplus wheat straw 5.7 million T/yr (UK)

• Bread surplus 680,000 T/yr (UK)

• Citrus waste 0.6 million T/yr (Spain)

ASIA

• Palm oil 15.8 million T/yr (Indonesia)

• Food waste 1.2 million T/yr (Hong Kong)

•-25MMT rice straw burned in open fields

(Vietnam)

•India??

MEDITERRANEAN BASIN

• Olive mill residue 30 million T/yr

BRAZIL

• Sugar cane bagasse 376.5

million T/yr

• Corn residue 41.7 million T/yr

• Cassava residue 51.6 million T/yr

• Rice straw 4.5 million T/yr

• Wheat straw 5.4 million T/yr

• Citrus residues 9.4 million T/yr

Food supply

chain residues

sugars phenols

collagen

starch

natural dyes

chitosan

cellulose

pectin

hemicellulose

waxes

films bio-adhesives

hydrogels

natural chelants

bio-solvents

chemical

monomers

nanocomposites

bio-surfactants

PVC replacements

Chemicals from food waste

Liquid fuels

cosmetic waxes

solid fuels

hydrophobes

lignin

Benign extraction

Extractables

Materials Chemicals

AD

DIN

G V

AL

UE

Biomass

Green, eg

supercritical

extraction

technologies

Green biochemical (eg fermentation)

and chemical (eg microwave)

Processing technologies

plus

Pre-processing

Eg pelletising

Fuels

Renewable Resources

and Materials

Microwave Chemistry

and Processing

Natural and Bio-derived

Solvents

Clean Synthesis and

Platform Molecules

Fro

m w

aste to w

ealth u

sing

Green

Chem

istry

Creating value from

waste polysaccharides

pyrolysis hydrolysis

chemical products

syngas bio-oil char sugars

fermentation

platform molecules

fuels

+ platform molecules

polysaccharides direct use

Surface Area < 1 m2g-1

Pore Volume < 0.002 cm3g-1

Food waste….

Porous polysaccharide-derived materials

Native Starch Expanded Starch

10 µm 2 µm

Surface Area > 180 m2g-1

Pore Volume > 0.5 cm3g-1

STARBONS®

An exciting new class of carbonaceous materials

Adjustable surface

energies and polarities

High mesoporocity and

surface areas

Readily functionalisable

with acid/base/metal

functionality

Excellent solvent stability

Good chemical and heat

resistance

Controllable electrical

conductivity

Formation of composites

and blends

Particulate/ monolithic

forms

Properties

Separation media

Catalysis

Absorbency

Water purification

Fuel cells

Applications

0.07 g/cm3

200C-0.12g/cm3 550C - 0.29 g/cm3

Now Starbon-technologies.ltd

Extraordinary range of properties

Heterogeneous Catalysis Applications

STARBON® C SERIES

• Works in aqueous and non aqueous systems and including fermentation broths

• Stable up to 260°C

• Make active and selective solid acids

• Make active solid bases

• Group loading 0.3 - 1.0 mmol/g

• Bind and stabilise nanometals

©2012 STARBON® TECHNOLOGIES LIMITED

Major platform molecules via fermentation

OHOH

O

O

OHOH

O

O

OHOH

O

O

OH

O

O

OOH

OO

OH

OHOH

O

ONH2

OH

O

NH2

O

OH

OOH

OH

OH

OH

OH

OH

O

OH OH

OHOH

OH

OH

OH

OH

OH OH

OH

OH

OH

OH

OH OH

O

OHOH

O

OOH

O O

OH

A very wide range of useful products

Clean

Synthesis

methods

Chromatographic Applications STARBON® S SERIES

• Separations that are difficult or impossible any other way

• High mesopore volume 0.48 to 0.60 cm3g-1

• High mesopore proportion 80%

• Average pore diameter 11 to 12 nm

• Hydrophilic or Hydrophobic options

• Available as small, regular <5 micron beads

©2012 STARBON® TECHNOLOGIES LIMITED

And also for separations…

STARBONS® for adsorbing small

organics Phenols:

OH OH

CH3

OH

F

OH

OMeOH

NH2

Phenol

o-Cresol

2-Fluorophenol

4-Methoxy

phenol

3-Aminophenol

Rate of adsorption:

Starbon® is sustainable, reusable and environmentally benign.

Extracting chemicals from

the surface of biomass

Extractables…….…Eco-waxes (Croda)

Biomass (agro/food/ forestry waste)

ScCO2 extraction Wax products

Cosmetic Products

Lignocellulose

- Strawboard

- Garden Mulch - Pulp & Paper

-Bioethanol -Electricity

Health Products

Semiochemicals

Renewable resource+CO2 extraction = EU “natural”

Plant waxes (surface chemicals)

Sterols/ Steryl esters OH

O

O

Esters

Resin acids

OH

O

Fatty acids

Glycerides

O

O

O

O

O

OCOOH

Chemicals from Agro residues using CO2

Extracted and fractionated using supercritical and liquid CO2

Cosmetics, surface coatings, health supplements…

But very limited as a reaction solvent

A Hunt et al, ChemSusChem, 2010, 306

Inorganic

Petroleum Biomass

Conventional

+

Neoteric

(e.g. Ionic

Liquids)

‘Natural’ solvents

CO2 + Water

Bio-solvents eg

Ethanol

Ethyl acetate

Ethyl lactate

2-MeTHF

limonene

Solvents

Greener Solvents the greatest process challenge?

2-Methyltetrahydrofuran- a case study

THF 2-MeTHF

Water miscible Immiscible

Higher peroxide formation Lower peroxide formation

Can be bio-derived Bio-derived

Solvent for organometallics Replacement for THF and DCM

‘Natural’ solvent

O O O O

D-Limonene p-Cymene

Amidation and Esterification in Bio-Solvents Using Silica as a “green Catalyst”

100 °C R

O

OH

Ph NH2

R

O

NH

Ph

R = 4-Phenylbutyl

50 °C

Pr

O

O

O

Pr

OHBu

Pr

O

OBu

R = 4-Phenylpropyl

Orange peel

J Sherwood et al, Green Chemistry 2012

Solvent Polarity Map (Aprotic)

1 2

9 8

4

7

5 6

3

The challenge is enormous!

Sustainable Solvent Polarity Map (Aprotic)

1 2

9 8

4

7

5 6

3

EtOAc

2-MeTHF

p-Cymene

Glutamic acid

derivatives

Limonene

Acetone

NEt3 ?

Bio-nitro ?

New from the GCCE:

Sustainable Solvents Selection Service- S4 In collaboration with Rafiq Gani and colleagues at DTU

Current solutions are limited

Thermochemical extraction from

and conversion of bulk biomass

Alternative methodologies…….

Biomass

Microwave

processor

Energy

Extracted

oil

Pyrolysis

Oil

Char

Wide range of feedstock

+ = Wide range of products

Flexibility of Microwave Parameters

(time, temperature, power)

Low Temperature

Microwave Treatment of Biomass

“The preparation of high-grade bio-oils through the controlled, low temperature microwave activation of wheat straw”. Bioresource

Technology (2009) 100(23),6064-6068..

Temperature of decomposition comparison

There is a correlation between temperature of phase transition in biopolymers

and temperature of MW pyrolysis

Torrefaction/biochar production by microwave and conventional slow pyrolysis – comparison of energy

Properties. GCB Bioenergy (2012), doi: 10.1111/gcbb.12021

Microwave Assisted Cellulose Hydrolysis

Sugars yield increases substantially in the

presence of microwave irradiation

Case studies and future biorefineries

60% of Orange Peel was transformed to valuable products

CHEMSUSCHEM, 2012, 5 (9), 1694-1697

A new OPEC-

Orange Peel Exploitation Company

Solid char 35 % of total mass

58% of total energy

Biomass

Microwave Processing

Aqueous fraction 31% of total mass

5% of total energy

Market:

Bio-alcohol

Transport fuel

Gas fraction 14% of total energy

Market:

PowerStation

Co-firing

Power generation 10% of total energy

Microwave Biorefinery Flow Chart

Sugars and Bio-oil 22 % of total mass

23% of total energy

Market:

Chemicals

Green and Sustainable furniture Bio-based composite materials for structural and furniture applications

Overall good metrics for sustainability, greener products,

waste avoidance and low environmental impact manufacturing

Never accept waste, e.g. using the bottom ashes….

Now on a slow

Boat from China!

J Dodson et al, RSC Advances, 2011, 523

Using the bottom ashes to make catalysts

MCM 41

Surface area 1043 m2/g

pore volume 1.12 cm3/g

J Dodson et al, J Mat Chem in the press

We burn an increasing amount of biomass

and other biomass in our power stations

and its rich in metals and silica

We need to think about more than Carbon…..

Elemental unsustainability

H. L Parker, et al, Nano-palladium catalysts directly from plants, Submitted

The Phytocat Project

A G8-Funded collaboration between York, Yale and UBC

• Research

• Industry collaboration

• Education, including

development of teaching and

promotional materials

• Networking with all chemical

stakeholders

Activity Areas

The Centre’s Activities can be groups into 4 areas:

Green Chemistry at York

We are interested in all things chemical

A collaboration between the Green Chemistry Centre and

the Centre for Novel Agricultural Products

www.biorenewables.org

Continuous microwave processor. 30 kg/h

Green Chemistry at York is growing fast!

Food waste valorisation for sustainable

chemicals, materials and fuels (EUBIS)

TD1203

Working Group 1:

Pre-treatment and extraction

Working Group 2:

Bioprocessing

Working Group 3:

Chemical processing

Working Group 4:

Technical and sustainability (policy) analysis

Research

Industry

Networking

Education

www.greenchemistry.net