Biofuels as an alternative to traditional energy sources_James Clark

www.greenchemistry.netwww.greenchemistry.net

Green Chemistry:

Biofuels as an alternative To

Traditonal sources of energy

James Clark

Green Chemistry Centre of ExcellenceUniversity of York, UK

www.greenchemistry.net


Chemicals including fuels traditionally rely on

non-renewable resources including fossil feedstocks

and especially petroleum


Petroleumfeedstock

Fuels

Solvent

Bulk chemicals

Plastics

Fibres

Fine chemicals

Oils

Petroleum Refinery

20% of the oil imported to the EU goes into chemical manufacturingand over 90% of all organic chemicals are made from oil


Elemental Sustainability


We need Green Chemistryto make manufacturing more

efficientand based more on renewable

resources


What is Green Chemistry?

SD

ECONOMIC

SOCIALENVIRONMENTAL

Energy

waste

Non-renewables

risk

cost REDUCE water


E C

W

Pre-manufacturing Manufacturing

Productdelivery

Productuse

End of Life

E C

W

E

W

E C

W W

E

RefurbishRemanufactureRecycle

From ‘cradle’ to ‘grave’

We must apply green chemistry across the whole life-cycle


Moving towards moresustainable feedstocks


Fuels

Solvent

Bulk chemicals

Plastics

Fibres

Fine chemicals

Oils

Bio-refinery-all the carbon we need

Biomass=eco-soundbioresourcesstraws,food waste,forestry waste,grasses….allsources of renewablecarbon

And use whats close to home!


Renewable Resources & Biorefineries


Extractables(secondary metabolites

from straw) Materials(primary metabolites –

starch, cellulose)

Bulk Chemicals((Bio)chemical processing of

bulk materials/residues)

CH

EM

ICA

L P

OT

EN

TIA

LT

EC

HN

OL

OG

IES

AD

DIN

G V

AL

UE

Biomass

Benign Extraction Methods

Separation/Purification

Green Chemical Transformation

Expansion Methods

Green Chemical Modification

Composites

Selective Fermentation

Controlled Pyrolysis

Extraction Technology

(Bio)platform molecules

Green Chemistry/technology


Plant waxesPlant waxes

Sterols/ Steryl Sterols/ Steryl estersesters

OH

O

O

EstersEsters

Resin acidsResin acids

OH

O

Fatty acidsFatty acids

GlyceridesGlycerides

O

O

O

O

O

OCOOH


Renewable biopolymers

Chitosan 1011 tpa soluble in acid, bead, filmsfibres, amine functionality

Starch 1011 tpa partial solubility poly glucose. Complex structure

Cellulose 1012 tpa poly glucose very long chain. Very stable fibrous structure

Silica 1022 tonnes highly rigid 3-D structure. Readily functionalised. High surface area


Chitin from Waste Seafood

Chitin

Disposal cost = £60-100/T

Seafood waste

Incineration


pyrolysis hydrolysis

chemical products

syngas bio-oil char sugars

fermentation

platform molecules

fuels

+ platform molecules

polysaccharidesdirect use


Feedstocks for biofuels


Waste is tomorrows resource

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

…and utilise it closer to home!


Adding value to Food WasteAdding value to Food WasteFOOD

WASTE

-Anaerobic Digestion-Fermentation-Added value productsand applications

BIOFUEL MARKETUK and Europe

Compostation(Farm facility)

Food Processing(300tonne/week)

Land spread

Food Co-product

Oil (20% yield)

Biofuel ProductionDryer

High Temperature130oC

£350-400/tonne

EXPECTED

CURRENTLY


Production of BiodieselProduction of Biodiesel

O

O

R

R

OR

O

O

O

OH

OH

OH

R

O

MeO+

+3MeOH

(Cat=NaOMe)

T=60-70oC

(R=C17)

3

127 mTonne of FAME by 2016

Glycerol

Biodiesel

Biodiesel Glycerol - a ready made opportunity Solvay/Dow

0

20

40

60

80

100

120

140

160

2001 2002 2003 2004 2005 2006

US biodieselconsumption

Mill

ion

gal

lon

s

OH

OH

OH

ClO

Glycerol co-product

New Solvay Process

Epichlorohydrin

Surfaces, plastic etc

= old route to glycerol


Anaerobic digestion and Fermentation Anaerobic digestion and Fermentation

Promising results in fermentation of crude glycerol to valuable products

High interest in Anaerobic digestion, Handling of heterogeneous waste Added value obtained from gasification

.

(Double Green UK)


Glycerol Uses and LimitationsGlycerol Uses and Limitations

www.icis.com

800 mTonne market size •Volatility of prices


127 mTonne of FAME by 2016; 12.7mTonnes of biodiesel glycerol

ADDED VALUE CHEMICALS

Biodiesel glycerine; uses Biodiesel glycerine; uses


Bioethanol Production


Bioethanol as a Platform Molecules

BiomassSugarcane

Bioethanol

Bioethene

Biopolyethylene BioPVC

Polymerisation Chlorination/Polymerisation

Dehydration

(20 x 103 tpa capacity plant (<0.1% PE)


Economically feasiblenew generation biofuel plants

will need a wider product portfolio including

“platform” molecules


Chemical from lignocellulosics


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

CleanSynthesismethods


SA as a Platform Molecules• Can be produced from fermentation of sugars using E. coli and Actinobacillus succinogenes (Satake Centre, University of Manchester)• Up to 110 g l-1 concentrations have been achieved.


Starbon® – a renewable mesoporous catalyst with

tunable properties


31


Starbon application: Acid catalysis directly on fermentation broths

Esterification of succinic acid.


O

O

O R

R

O

O O

O

OO

O

OO

R

OO

R

H BASE

O

O

O R

R

O

O O

DMI

BASE

1

R = Me or OMe

0

10

20

30

40

50

60

70

80

0.5 2 5 10 20 No Catalyst KF -

spraydried

0 - neutral

alumina

% Y

ield

of C

ompo

und

1

KF Loading of KF/Al 2O3 / mmol g-1

Derivitisation of unsaturated platform molecules-Michael reaction routes to complex structures

KF-alumina much moreReactive than other solid bases


0

25

50

75

100

Ru Pt Pd Rh

5% M-Starbon-300

conversion selectivity butanediol selectivity butyrolactone

OHOH

O

O

Starbon-metal/aqueous ethanol/H2

Starbon-nanometal catalysis under fermentation conditions


Thermochemical biomass conversions


Microwave assisted

decomposition of biomass:

a new thermochemical route

to biofuels


Microwave Enhancement of Biomass


Why MW? Advantages of MW Heating

Rapid internal heating

Uniform heating

Instant control

Acceleration of reaction rate

Selective interaction with active

groups


MW industrial application

Special ceramic production

Drying

Food industry

Polymerisation

Chemical

processing/synthesis


–1.5 of oil

18 Kg of wheat straw = 6.7 Kg of char 5.7 Kg of oil+

Larger Scale Trial Wheat straw @ 30 Kg/hr


Biomass

Microwave processor

Energy

ExtractedExtractedoiloil

ExtractedExtractedoiloil

Pyrolysis Pyrolysis OilOil

Pyrolysis Pyrolysis OilOil

CharCharCharChar

Wide range offeedstock

+ = Wide range ofproducts

Flexibility of Microwave Parameters

(time, temperature, power)

Low temperature !

Microwave Processing of Biomass


Biomass

Microwave processing.

I. Solid char35 % of total mass58% of total energy Organic oil

IV. Aqueous fraction I31% of total mass 5% of total energyWater

treatment

III. Organic fraction:10% of total mass13% of total energy

II. SugarsAqueous fraction II12% of total mass10% of total energy

Market:Bio-alcohol

Market:Transport fuel

V. Gas fraction14% of total energy

Microwave processing of biomass

Market:PowerStation

Power generation10% of total energy

Market:Pharmaceutics


Microwave oil characteristics

1.Low water content

2.Low acid content.

3.Low alkali metals content.

4.The high yields of fermentable

sugars:

- Levoglucosan (up to 50%)

- Levoglucosanone (up to 25%)


Continuous feed

Microwave energy volatiles

Continuous microwave processing of untreated biomass


Creating a complete

supply chain:

from

Farm to Forecourt


The multiproduct biorefinery of the future


A model for a wheatstraw biorefinery


A seaweed biorefinery


How green is my product?


Carbon Footprinting products •Quantify the emissions across the product supply chain and express as a carbon equivalent

•Base on a Product Unit (defined as an item that can be purchased by the consumer; the unit includes the industrial packaging in which it is sold)

•Supply chain goes from material to disposal but not including emission in-store or in use by the consumer

•Analysis should include all processes used in transformation of the raw material

•GHG emission can be through direct release into the atmosphere at the process site on through consumption of energy (with an appropriate conversion factor); mass balance is used to calculate waste per step which then has to be equated to CO2 equivalent emission, e.g. via

energy per unit weight


Environmental footprinting

Indicator of resource consumption and waste absorption transferred onto the basis of biologically productive land

Consumption category:

• energy use

• built environment

• food

• forestry

Convert into global hectares as ‘the annual productivity of one hectare of biologically productive land or sea with world average productivity’


York, the University and Green Chemistry at York

Top 5 UK-ranked Chemistry DepartmentTimes Online Good University Guide 2008

World-leading Green Chemistry research centre dedicated to creating genuinely sustainable supply chains for chemicals

World-leading centre of excellence in plants and microbes leading to a greaterrealisation of the economic potential ofproducts developed from bio-resources

One of Europes finest medieval cities Top 100 World- and Top 10 UK-ranked UniversityTimes Good University Guide 2009

York


• Research

• Industry collaboration

• Education, including development of teaching and promotional materials

• Networking with all chemical stakeholders

Activity AreasThe Centre’s Activities can be groups into 4 areas:

The York Green Chemistry Centre….The York Green Chemistry Centre….we want to make a differencewe want to make a difference


Microwave Chemistry

Science Leader Dr Duncan MacQuarrie

This brings together our long-standing interest in microwave-assisted chemistry with our more recent interest in the conversion of biomass (eg forestry and agricultural wastes, food waste, etc)

to useful products. With substantial funding from ERDF, Carbon Trust, METRC and industry we are starting major new projects

on fast pyrolysis for the production of liquid fuels, high calorific value chars and chemical intermediates.

A major part of this is the design and build of new continuous microwave processors, with the final semi-scale prototype to be

located outside the GCC.


Clean Synthesis and Platform Molecules

Science Leader Dr Simon Breeden

Very much our root area with interests covering the use of solid catalysts and alternative solvents to

“green” reactions.

Recently we have become especially interested in doing clean synthesis starting from molecules and

mixtures derived from biomass (eg using fermentation broths).

We have funding in this area from industry, EPSRC, METRC, and GSK.


Renewable MaterialsScience Leader Dr Avtar Matharu

For us this means the physical and chemical modification of natural abundant materials and especially polysaccharides.

Projects include Starbons (new carbonaceous materials derived from starch), new “bio-boards” made entirely of green and sustainable components, novel switchable adhesives, new

intumescent flame retardants, and PVC replacements.

Funding comes from industry, EPSRC, DEFRA and TSB. The area is supported by state-of-the-art thermal analysis, infrared

spectroscopy and extrusion equipment.


Natural SolventsScience Leader Prof Ray Marriott

We are interested in supercritical and liquid carbon dioxide as an extraction, fractionation and

reaction medium with projects covering areas such as the extraction of waxes from agricultural

and food waste for personal care (and other) applications, and the synthesis of flavour and aroma molecules using in-situ biocatalysis.

Funding comes from the University, METRC and industry. We have excellent supercritical fluid

extraction facilities and access to scale-up facilities.


NORSCCombining the expertise of the

leading Northern England Universitiesto provide sustainable chemistry

solutions to industry

NORSCCombining the expertise of the

leading Northern England Universitiesto provide sustainable chemistry

solutions to industry

MUSCThe Chemical Industries Association

and the Green Chemistry Centreworking together to create new

green and sustainable supply chainsfor chemical products

MUSCThe Chemical Industries Association

and the Green Chemistry Centreworking together to create new

green and sustainable supply chainsfor chemical products

Anglo-French collaboration

chemicals from biomassusing green chemistry

and white biotechnology

Anglo-French collaboration

chemicals from biomassusing green chemistry

and white biotechnology

Green Chemistry and the ConsumerGreen chemistry solutions for

the retailer and producer

Green Chemistry and the ConsumerGreen chemistry solutions for

the retailer and producer

Green Chemistry networks worldwideGreece, Portugal, Cyprus, Japan, USA,

Korea, Brazil……..

Green Chemistry networks worldwideGreece, Portugal, Cyprus, Japan, USA,

Korea, Brazil……..

Promoting awareness and facilitating, education, training and practice

of green chemistry worldwide

Promoting awareness and facilitating, education, training and practice

of green chemistry worldwide


Networking Projects:Green Chemistry Network

• Est. 1998 with funding from the Royal Society of Chemistry

• One of the largest international networks of this type in the world

• International membership

• Excellent forum for information exchanges and collaboration


Pre – HE: Education and Outreach

Aims

• To excite young people about chemistry and the positive impact it can have.

• To enable young people to critically engage with ideas and solutions

Impacts/areas of work

• lots of projects and funding at key stage 2

- Discovery Days, Countryside Days, Science Days in Primary Schools

- High awareness about environment at young age, interest and enthusiasm

• opportunities at GCSE/A level stage


Research

Industry

Networking

Education

www.greenchemistry.net

Biofuels as an alternative to traditional energy sources_James Clark

Technology

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