biofuels as an alternative to traditional energy sources_james clark
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Green Chemistry:
Biofuels as an alternative To
Traditonal sources of energy
James Clark
Green Chemistry Centre of ExcellenceUniversity of York, UK
www.greenchemistry.net
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Chemicals including fuels traditionally rely on
non-renewable resources including fossil feedstocks
and especially petroleum
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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
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Elemental Sustainability
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We need Green Chemistryto make manufacturing more
efficientand based more on renewable
resources
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What is Green Chemistry?
SD
ECONOMIC
SOCIALENVIRONMENTAL
Energy
waste
Non-renewables
risk
cost REDUCE water
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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
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Moving towards moresustainable feedstocks
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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!
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Renewable Resources & Biorefineries
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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
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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
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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
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Chitin from Waste Seafood
Chitin
Disposal cost = £60-100/T
Seafood waste
Incineration
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pyrolysis hydrolysis
chemical products
syngas bio-oil char sugars
fermentation
platform molecules
fuels
+ platform molecules
polysaccharidesdirect use
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Feedstocks for biofuels
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Waste is tomorrows resource
We need to encourage the greater use of chemically rich waste as a resource
…and utilise it closer to home!
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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
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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
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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)
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Glycerol Uses and LimitationsGlycerol Uses and Limitations
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800 mTonne market size •Volatility of prices
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127 mTonne of FAME by 2016; 12.7mTonnes of biodiesel glycerol
ADDED VALUE CHEMICALS
Biodiesel glycerine; uses Biodiesel glycerine; uses
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Bioethanol Production
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Bioethanol as a Platform Molecules
BiomassSugarcane
Bioethanol
Bioethene
Biopolyethylene BioPVC
Polymerisation Chlorination/Polymerisation
Dehydration
(20 x 103 tpa capacity plant (<0.1% PE)
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Economically feasiblenew generation biofuel plants
will need a wider product portfolio including
“platform” molecules
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Chemical from lignocellulosics
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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
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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.
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Starbon® – a renewable mesoporous catalyst with
tunable properties
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31
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Starbon application: Acid catalysis directly on fermentation broths
Esterification of succinic acid.
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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
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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
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Thermochemical biomass conversions
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Microwave assisted
decomposition of biomass:
a new thermochemical route
to biofuels
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Microwave Enhancement of Biomass
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Why MW? Advantages of MW Heating
Rapid internal heating
Uniform heating
Instant control
Acceleration of reaction rate
Selective interaction with active
groups
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MW industrial application
Special ceramic production
Drying
Food industry
Polymerisation
Chemical
processing/synthesis
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–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
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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
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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
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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%)
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Continuous feed
Microwave energy volatiles
Continuous microwave processing of untreated biomass
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Creating a complete
supply chain:
from
Farm to Forecourt
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The multiproduct biorefinery of the future
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A model for a wheatstraw biorefinery
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A seaweed biorefinery
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How green is my product?
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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
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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’
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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
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• 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
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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.
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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.
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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.
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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.
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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
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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
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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
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Research
Industry
Networking
Education
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