Green Chemistry Centre of

Excellence, University of York.

The study and development of an integrated & additive-free orange peel

biorefinery (Project “OPEC”)

York: city of Romans, Vikings and Kings (as well as Green Chemists)

The University of York

And now with a new, second campus doubling the footprint

Green Chemistry

Green Chemistry Centre of Excellence

World-leading Green Chemistry Centre dedicated to creating genuinely sustainable supply chains for chemical and related products

€40M grants /

investment in 2012-14

new buildings new

staff and research.

Biorenewables

Development Centre Green Chemistry Centre

Ideas

Speculative Research Discovery

Focussed Research

Industrial Collaboration

Applied Research

Commercialproducts

Two current EPSRC platform type grants Deputy director of CO2Chem

Lead EPSRC project on phytomining TSB project on valorising food

waste WasteValor

Coordinator COST action on food waste utilization

Partner in 4 EU FP7 grants including Chem21IMI and Cyclic CO2R

Starbons spin-out based on EPSRC and TSB funding

Includes unique industrial engagement facility

• 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 and especially

turning waste and by-products into chemicals and with the capability

to demonstrate the most promising technologies at larger scale….

• Biorenewables Feedstock Development Unit sources,

evaluates and develops plants, algae and fungi as

production systems for high value chemicals and

materials.

• Biorenewables Process Development Unit allows pre-

treatment, extraction, processing and separation of

biorenewable feedstocks on an industrial scale.

• Biorenewables Business Development Unit engages

with relevant industrial organisations to identify

business opportunities and help companies develop

new economically viable products and processes.

A €10M project funded by the EU and UK Government

Continuous microwave processor. 30 kg/h

Hydrothermal unit now being designed

Fuels

Solvent

Bulk chemicals

Plastics

Fibres

Fine chemicals

Oils

Bio-refinery

Biomass

Don’t use food quality feedstocks!!

Instead of a problem, waste

can become tomorrows resource

But we must use green technologies to properly achieve

The Circular Economy

• • •

• •

•

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)

• 25 millon T rice straw burned in open

fields (Vietnam)

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

2014=European year of Food Waste

1.3 bn MT edible waste

3? bn MT inedible FSCW

(several)bn MT renewable forestry

Food Supply Chain Waste

as a renewable feedstock

Food supply

chain waste

sugars phenols

collagen

starch

phytochemicals

chitosan

cellulose

pectin

hemicellulose

elastin

films

bio-adhesives

hydrogels

natural chelants

bio-solvents

alcohols

chemical

monomers

cellulose nanocrystals

nanocomposites

PVC replacement materials

PHAs

Benign extraction

activated carbon

antioxidant

lubricant fuel additives

bio-surfactants

fatty acids

bio-fuels

amino acids

syn-gas

terpenes

S. K. C. Lin et. al., Energy & Environmental Science, 2013, 6, 426-464.

F. R. Marin et al., Food Chemistry, 2007, 100, 736-741.

M. Pourbafrani et. al., Bioresource Technology, 2010, 101, 4246-4250.

Waste orange peel as a biorefinery feedstock

50 wt% peel waste

contains:

3.8% D-limonene

4.5% flavonoids

20-30% pectin

9.57% sugars

1. Food industry

2. Food supply chain

waste

3. WASTE BIOREFINERY

4. Marketable, sustainable

& bio-derived products

Integrated

microwave

waste

biorefinery

50% waste

31.2 million T/y of

citrus fruits are

processed globally

yielding

15.6 million T of

citrus peel waste

OPEC attributes

The OPEC process should present the following attributes:

• allow the extraction of a maximum of chemical components,

• avoid the use of a drying and pre-treatment stage,

• avoid the use of acid and other additives

• avoid or limit the use of solvent to food grade solvents only

• be scalable and flexible even for other biomass

OPEC History

Idea Laboratory explorations Patents and publications

Larger lab scale External evaluation of products

Major industry funding Additional govt funding

Proving at demonstrator scale (new rig) Pilot plant

Distributed bio-refineries worldwide

Our preferred technology is

Microwave activation

V Budarin et al, Energy and Environmental Science, 2011, 471

Microwaves can deconstruct complex

natural materials

Sugars yield increases substantially in the

presence of microwave irradiation

Alice Fan et al, J.Amer.Chem.Soc, 2013, 11728

The OPEC process

Orange

peel

residue 2.

MW

treatment

100-130 °C

Orange

peel

residue 1.

Wet

WOP

MW assisted

steam distillation

800-1200 W

D-limonene

1.09%

Soxhlet

ethanol

extraction

Flavonoids

6.13%

Pectin

5.95%

• Flavour & fragrance • Electronics • Platform molecule

• Broad spectrum of biological activity

• Food applications • Cosmetics • Pharmaceutical L. A. Pfaltzgraff et. al., Green Chemistry, 2013, 15, 307-314.

MASD: 95.38% D-limonene

25 minutes

0.93 kWh No solvent required

Steam distillation: 84.27% D-limonene

5 hours 4.32 kWh

H2O required

D-limonene extraction

Polymethoxy flavonoids extraction

• The HPLC and ESI data

show the presence of highly methoxylated

flavonoids.

• Ethanol treatment yields these in a purer form than conventional methods.

ESI spectrum of the

flavonoids identified in the

ethanol soxhlet extract.

Hesperidin extraction

-0.1

0

0.1

0.2

0.3

0.4

0.5

550105015502050255030503550

Inte

nsi

ty

Wavenumber (cm-1)

Sample SO1e

Hesperidin commercial

Extraction

Temp.

(°C)

Yield

(%) Mw (Da) Mn (Da)

PI

(Mw/Mn) DE (%)

CU201 - 232,250 198,840 1.17 -

S. Aldrich - 125,600 100,100 1.26 -

100 1.24 303,500 175,725 1.80 68

110 5.95 251,917 149,333 1.68 66

120 21.67 250,750 120,030 2.16 69

130 15.97 172,733 39,745 4.35 69

Acid-free pectin extraction

Gel test of

A) commercial pectin and B) MW extracted

pectin at pH 2 using

0.75% pectin and 70%

sucrose.

A) B)

Successfully tested at Fraunhoffer Institute

Conclusion

Successful extraction of pectin using a low temperature (below 150 °C), acid-free microwave hydrothermal treatment,

successful microwave assisted D-limonene extraction under

solvent-less conditions,

integration of both pectin and D-limonene extraction in an

integrated microwave process potentially fit for continuous

processing together with

the extraction of flavonoids and sugars for additional revenue.

OPEC Development Team

-York team – JHC (PI), Julen Bustamente (Manager), senior technician,

research students, head of BDC Development Chemistry, head of

Microwave Technology Platform, other senior staff

-Consultant process engineer

-Sairem microwave

-German company sponsor (OP bio-refinery)

- 3rd Party collaborators (inc PepsiCo)

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

200+ partners from 30+ countries

And now outside Europe including Brazil!

Working with the best scientists, technologists and other experts

BIOVALEBUSINESSDEVELOPMENTTEAMnetworking,businesssupport,monitoring,repor ng

SUPPLYCHAINDEVELOPMENT

Bio-basedSupplyChain

Ini a vefundingscheme

R&D,INNOVATION

Open-accesstechnologyfacili es,innova onsupport

TRAINING

Appren ceshipsmentoring,short

courses,post-graduatetraining

TRADE&INVESTMENT

Onlineportal,trademissions,

interna onalconferences,socialmedia

BUSINESSGROWTHSPACE

BioHubbusinessgrowthspace,

Ferabusinessspace

Academicknowledge

base

Policymakersandfunders

BioValeManagementteam

Industry&Agriculture

Looking to the future….

Biovale – a new industry-facing initiative

locally grown but globally ambitious

Green Chemistry at York