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 Excellence
University of York, UK
www.greenchemistry.net

Chemicals including fuels
traditionally rely on
non-renewable resources
including fossil feedstocks
and especially petroleum

Petroleum
feedstock
Fuels
Solvent
Bulk chemicals
Plastics
Fibres
Fine chemicals
Oils
Petroleum Refinery
20% of the oil imported to the EU goes into chemical manufacturing
and over 90% of all organic chemicals are made from oil

Elemental Sustainability

We need Green Chemistry
to make manufacturing more
efficient
and based more on renewable
resources

What is Green Chemistry?
SD
ECONOMIC
SOCIAL
ENVIRONMENTAL
Energy
waste
Non-renewables
risk
cost REDUCE water

E C
W
Pre-
manufacturing Manufacturing
Product
delivery
Product
use
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 more
sustainable feedstocks

Fuels
Solvent
Bulk chemicals
Plastics
Fibres
Fine chemicals
Oils
Bio-refinery-all the carbon we need
Biomass=
eco-sound
bioresources
straws,
food waste,
forestry waste,
grasses….all
sources of
renewable
carbon
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)
CHEMICALPOTENTIAL
TECHNOLOGIES
ADDINGVALUE
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 estersSterols/ Steryl esters
OH
O
O
EstersEsters
Resin acidsResin acids
OH
O
Fatty acidsFatty acids
GlyceridesGlycerides
O
O
O
O
O
O
COOH

Renewable biopolymers
Chitosan 1011 tpa soluble in acid, bead, films
fibres, 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
polysaccharides
direct 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 Waste
FOOD
WASTE
-Anaerobic Digestion
-Fermentation
-Added value products
and applications
BIOFUEL MARKET
UK and Europe
Compostation
(Farm facility)
Food Processing
(300tonne/week)
Land spread
Food
Co-product
Oil
(20% yield)
Biofuel Production
Dryer
High Temperature
130o
C
£350-400/tonne
EXPECTED
CURRENTLY

Production of BiodieselProduction of Biodiesel
O
O
R
R
O
R
O
O
O
OH
OH
OH
R
O
MeO
+
+
3MeO
H
(Cat=NaOMe)
T=60-70o
C
(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 biodiesel
consumption
Milliongallons
OH
OH
OH
Cl
O
Glycerol
co-
product
New Solvay Process
Epichlorohydrin
Surfaces, plastic
etc
= old
route to
glycerol

Anaerobic digestion and FermentationAnaerobic 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; usesBiodiesel glycerine; uses

Bioethanol Production

Bioethanol as a Platform Molecules
Biomass
Sugarcane
Bioethanol
Bioethene
Biopolyethylene BioPVC
Polymerisation Chlorination/Polymerisation
Dehydration
(20 x 103
tpa capacity plant (<0.1% PE)

Economically feasible
new generation biofuel plants
will need a wider product
portfolio including
“platform” molecules

Chemical from lignocellulosics

Major platform molecules via fermentation
OH
OH
O
O
OH
OH
O
O
OH
OH
O
O
OH
O
O
O
OH
OO
OH
OH
OH
O
ONH2
OH
O
NH2
O
OH
O
OH
OH
OH
OH
OH
OH
O
OH OH
OH
OH
OH
OH
OH
OH
OH OH
OH
OH
OH
OH
OH OH
O
OH
OH
O
OOH
O O
OH
A very wide range of useful products
Clean
Synthesis
methods

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
O
O
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
%YieldofCompound1
KF Loading of KF/Al 2O3 /mmolg
-1
Derivitisation of unsaturated platform molecules-
Michael reaction routes to complex structures
KF-alumina much more
Reactive than other solid bases

0
25
50
75
100
Ru Pt Pd Rh
5% M-Starbon-300
conversion selectivity butanediol selectivity butyrolactone
OH
OH
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

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
ExtractedExtracted
oiloil
ExtractedExtracted
oiloil
PyrolysisPyrolysis
OilOil
PyrolysisPyrolysis
OilOil
CharCharCharChar
Wide range of
feedstock
+ = Wide range of
products
Flexibility of Microwave
Parameters
(time, temperature, power)
Low temperature !
Microwave Processing of Biomass

Biomass
Microwave processing.
I. Solid char
35 % of total mass
58% of total energy Organic oil
IV. Aqueous fraction I
31% of total mass
5% of total energyWater
treatment
III. Organic fraction:
10% of total mass
13% of total energy
II. Sugars
Aqueous fraction II
12% of total mass
10% of total energy
Market:
Bio-alcohol
Market:
Transport fuel
V. Gas fraction
14% of total energy
Microwave processing of biomass
Market:
PowerStation
Power generation
10% 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 Department
Times 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 greater
realisation of the economic potential of
products developed from bio-resources
 One of Europes finest medieval cities
 Top 100 World- and Top 10 UK-ranked
University
Times Good University Guide 2009
York

• 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:
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 Materials
Science 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 Solvents
Science 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.

NORSC
Combining the expertise of the
leading Northern England Universities
to provide sustainable chemistry
solutions to industry
NORSC
Combining the expertise of the
leading Northern England Universities
to provide sustainable chemistry
solutions to industry
MUSC
The Chemical Industries Association
and the Green Chemistry Centre
working together to create new
green and sustainable supply chains
for chemical products
MUSC
The Chemical Industries Association
and the Green Chemistry Centre
working together to create new
green and sustainable supply chains
for chemical products
Anglo-French
collaboration
chemicals from biomass
using green chemistry
and white biotechnology
Anglo-French
collaboration
chemicals from biomass
using green chemistry
and white biotechnology
Green Chemistry and the Consumer
Green chemistry solutions for
the retailer and producer
Green Chemistry and the Consumer
Green chemistry solutions for
the retailer and producer
Green Chemistry networks worldwide
Greece, Portugal, Cyprus, Japan, USA,
Korea, Brazil……..
Green Chemistry networks worldwide
Greece, 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

Recommended

Recommended

More Related Content

What's hot

What's hot (20)

Similar to Biofuels as an alternative to traditional energy sources_James Clark

Similar to Biofuels as an alternative to traditional energy sources_James Clark (20)

More from IMDEA Energia

More from IMDEA Energia (20)

Recently uploaded

Recently uploaded (20)

Biofuels as an alternative to traditional energy sources_James Clark

Editor's Notes