www.greenchemistry.netwww.greenchemistry.net
Green Chemistry:
Biofuels as an alternative
To
Traditonal sources of energy
J...
www.greenchemistry.netwww.greenchemistry.net
Chemicals including fuels
traditionally rely on
non-renewable resources
inclu...
www.greenchemistry.netwww.greenchemistry.net
Petroleum
feedstock
Fuels
Solvent
Bulk chemicals
Plastics
Fibres
Fine chemica...
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Elemental Sustainability
www.greenchemistry.netwww.greenchemistry.net
We need Green Chemistry
to make manufacturing more
efficient
and based more o...
www.greenchemistry.netwww.greenchemistry.net
What is Green Chemistry?
SD
ECONOMIC
SOCIAL
ENVIRONMENTAL
Energy
waste
Non-re...
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E C
W
Pre-
manufacturing Manufacturing
Product
delivery
Product
use
End of Li...
www.greenchemistry.netwww.greenchemistry.net
Moving towards more
sustainable feedstocks
www.greenchemistry.netwww.greenchemistry.net
Fuels
Solvent
Bulk chemicals
Plastics
Fibres
Fine chemicals
Oils
Bio-refinery...
www.greenchemistry.netwww.greenchemistry.net
Renewable Resources & Biorefineries
www.greenchemistry.netwww.greenchemistry.net
Extractables
(secondary metabolites
from straw) Materials
(primary metabolite...
www.greenchemistry.netwww.greenchemistry.net
Plant waxesPlant waxes
Sterols/ Steryl estersSterols/ Steryl esters
OH
O
O
Es...
www.greenchemistry.netwww.greenchemistry.net
Renewable biopolymers
Chitosan 1011 tpa soluble in acid, bead, films
fibres, ...
www.greenchemistry.netwww.greenchemistry.net
Chitin from Waste Seafood
Chitin
Disposal cost = £60-100/T
Seafood waste
Inci...
www.greenchemistry.netwww.greenchemistry.net
pyrolysis hydrolysis
chemical products
syngas bio-oil char sugars
fermentatio...
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Feedstocks for biofuels
www.greenchemistry.netwww.greenchemistry.net
Waste is tomorrows resource
We need to encourage the greater use of
chemicall...
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Adding value to Food WasteAdding value to Food Waste
FOOD
WASTE
-Anaerobic Di...
www.greenchemistry.netwww.greenchemistry.net
Production of BiodieselProduction of Biodiesel
O
O
R
R
O
R
O
O
O
OH
OH
OH
R
O...
Biodiesel Glycerol - a ready made opportunity
Solvay/Dow
0
20
40
60
80
100
120
140
160
2001 2002 2003 2004 2005 2006
US bi...
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Anaerobic digestion and FermentationAnaerobic digestion and Fermentation
 Pr...
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Glycerol Uses and LimitationsGlycerol Uses and Limitations
www.icis.com
800 m...
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127 mTonne of FAME by 2016;
12.7mTonnes of biodiesel glycerol
ADDED VALUE CHE...
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Bioethanol Production
www.greenchemistry.netwww.greenchemistry.net
Bioethanol as a Platform Molecules
Biomass
Sugarcane
Bioethanol
Bioethene
Bio...
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Economically feasible
new generation biofuel plants
will need a wider product...
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Chemical from lignocellulosics
www.greenchemistry.netwww.greenchemistry.net
Major platform molecules via fermentation
OH
OH
O
O
OH
OH
O
O
OH
OH
O
O
OH
O
...
www.greenchemistry.netwww.greenchemistry.net
SA as a Platform Molecules
• Can be produced from fermentation of sugars usin...
www.greenchemistry.netwww.greenchemistry.net
Starbon® – a renewable
mesoporous catalyst with
tunable properties
www.greenchemistry.netwww.greenchemistry.net
31
www.greenchemistry.netwww.greenchemistry.net
Starbon application:
Acid cat...
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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...
www.greenchemistry.netwww.greenchemistry.net
0
25
50
75
100
Ru Pt Pd Rh
5% M-Starbon-300
conversion selectivity butanediol...
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Thermochemical biomass
conversions
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Microwave assisted
decomposition of biomass:
a new thermochemical route
to bi...
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Microwave Enhancement of Biomass
www.greenchemistry.netwww.greenchemistry.net
Why MW? Advantages of MW Heating
Rapid internal heating
Uniform heating
In...
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MW industrial application
Special ceramic production
Drying
Food industry
...
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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...
www.greenchemistry.netwww.greenchemistry.net
Biomass
Microwave
processor
Energy
ExtractedExtracted
oiloil
ExtractedExtract...
www.greenchemistry.netwww.greenchemistry.net
Biomass
Microwave processing.
I. Solid char
35 % of total mass
58% of total e...
www.greenchemistry.netwww.greenchemistry.net
Microwave oil characteristics
1.Low water content
2.Low acid content.
3.Low a...
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Continuous
feed
Microwave energy
volatiles
Continuous microwave processing of...
www.greenchemistry.netwww.greenchemistry.net
Creating a complete
supply chain:
from
Farm to Forecourt
www.greenchemistry.netwww.greenchemistry.net
The multiproduct biorefinery of the future
www.greenchemistry.netwww.greenchemistry.net
A model for a wheatstraw biorefinery
www.greenchemistry.netwww.greenchemistry.net
A seaweed biorefinery
www.greenchemistry.netwww.greenchemistry.net
How green is my product?
www.greenchemistry.netwww.greenchemistry.net
Carbon Footprinting products
•Quantify the emissions across the product suppl...
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Environmental footprinting
Indicator of resource consumption and waste absorp...
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York, the University and Green Chemistry at York
 Top 5 UK-ranked Chemistry ...
www.greenchemistry.netwww.greenchemistry.net
• Research
• Industry collaboration
• Education, including
development of tea...
www.greenchemistry.netwww.greenchemistry.net
Microwave Chemistry
Science Leader Dr Duncan MacQuarrie
This brings together ...
www.greenchemistry.netwww.greenchemistry.net
Clean Synthesis and
Platform Molecules
Science Leader Dr Simon Breeden
Very m...
www.greenchemistry.netwww.greenchemistry.net
Renewable Materials
Science Leader Dr Avtar Matharu
For us this means the phy...
www.greenchemistry.netwww.greenchemistry.net
Natural Solvents
Science Leader Prof Ray Marriott
We are interested in superc...
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NORSC
Combining the expertise of the
leading Northern England Universities
to...
www.greenchemistry.netwww.greenchemistry.net
Networking Projects:
Green Chemistry Network
• Est. 1998 with
funding from th...
www.greenchemistry.netwww.greenchemistry.net
Pre – HE: Education and Outreach
Aims
• To excite young people about chemistr...
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Research
Industry
Networking
Education
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Biofuels as an alternative to traditional energy sources_James Clark

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  • Currently produced via the reduction and hydrolysis of maleic anhydride.
    110 g l-1 achieved using pure sugars and nutrients/minerals. Colin Webb’s group in manchester can produce SA from wheat as a generic feedstock (supplying nutrients and minerals as well as sugars) – but to lower concentrations (around 40 g l-1)
    Production amounts are limited as the microorganisms naturally producing SA are intolerant to high concentrations of acids (they either die or cease growth). As a result, the broth is typically neutralised with the addition of bases such as ammonium, sodium or potassium hydroxide. This thus produces the SA in the succinate salt form, upon which upstream acidification processing is applied, adding further cost to the production of the organic acid.99 Various separation methods such as EDBM38 could be used to increase the SA concentration but, for the preliminary experiments shown here, the SA was typically prepared as 13% by mass concentration (0.118g of SA in 0.8ml H2O).
  • Biofuels as an alternative to traditional energy sources_James Clark

    1. 1. 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
    2. 2. www.greenchemistry.netwww.greenchemistry.net Chemicals including fuels traditionally rely on non-renewable resources including fossil feedstocks and especially petroleum
    3. 3. www.greenchemistry.netwww.greenchemistry.net 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
    4. 4. www.greenchemistry.netwww.greenchemistry.net Elemental Sustainability
    5. 5. www.greenchemistry.netwww.greenchemistry.net We need Green Chemistry to make manufacturing more efficient and based more on renewable resources
    6. 6. www.greenchemistry.netwww.greenchemistry.net What is Green Chemistry? SD ECONOMIC SOCIAL ENVIRONMENTAL Energy waste Non-renewables risk cost REDUCE water
    7. 7. www.greenchemistry.netwww.greenchemistry.net 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
    8. 8. www.greenchemistry.netwww.greenchemistry.net Moving towards more sustainable feedstocks
    9. 9. www.greenchemistry.netwww.greenchemistry.net 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!
    10. 10. www.greenchemistry.netwww.greenchemistry.net Renewable Resources & Biorefineries
    11. 11. www.greenchemistry.netwww.greenchemistry.net 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
    12. 12. www.greenchemistry.netwww.greenchemistry.net 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
    13. 13. www.greenchemistry.netwww.greenchemistry.net 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
    14. 14. www.greenchemistry.netwww.greenchemistry.net Chitin from Waste Seafood Chitin Disposal cost = £60-100/T Seafood waste Incineration
    15. 15. www.greenchemistry.netwww.greenchemistry.net pyrolysis hydrolysis chemical products syngas bio-oil char sugars fermentation platform molecules fuels + platform molecules polysaccharides direct use
    16. 16. www.greenchemistry.netwww.greenchemistry.net Feedstocks for biofuels
    17. 17. www.greenchemistry.netwww.greenchemistry.net Waste is tomorrows resource We need to encourage the greater use of chemically rich waste as a resource …and utilise it closer to home!
    18. 18. www.greenchemistry.netwww.greenchemistry.net 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
    19. 19. www.greenchemistry.netwww.greenchemistry.net 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
    20. 20. 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
    21. 21. www.greenchemistry.netwww.greenchemistry.net 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)
    22. 22. www.greenchemistry.netwww.greenchemistry.net Glycerol Uses and LimitationsGlycerol Uses and Limitations www.icis.com 800 mTonne market size •Volatility of prices
    23. 23. www.greenchemistry.netwww.greenchemistry.net 127 mTonne of FAME by 2016; 12.7mTonnes of biodiesel glycerol ADDED VALUE CHEMICALS Biodiesel glycerine; usesBiodiesel glycerine; uses
    24. 24. www.greenchemistry.netwww.greenchemistry.net Bioethanol Production
    25. 25. www.greenchemistry.netwww.greenchemistry.net Bioethanol as a Platform Molecules Biomass Sugarcane Bioethanol Bioethene Biopolyethylene BioPVC Polymerisation Chlorination/Polymerisation Dehydration (20 x 103 tpa capacity plant (<0.1% PE)
    26. 26. www.greenchemistry.netwww.greenchemistry.net Economically feasible new generation biofuel plants will need a wider product portfolio including “platform” molecules
    27. 27. www.greenchemistry.netwww.greenchemistry.net Chemical from lignocellulosics
    28. 28. www.greenchemistry.netwww.greenchemistry.net 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
    29. 29. www.greenchemistry.netwww.greenchemistry.net 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.
    30. 30. www.greenchemistry.netwww.greenchemistry.net Starbon® – a renewable mesoporous catalyst with tunable properties
    31. 31. www.greenchemistry.netwww.greenchemistry.net 31 www.greenchemistry.netwww.greenchemistry.net Starbon application: Acid catalysis directly on fermentation broths Esterification of succinic acid.
    32. 32. www.greenchemistry.netwww.greenchemistry.net 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
    33. 33. www.greenchemistry.netwww.greenchemistry.net 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
    34. 34. www.greenchemistry.netwww.greenchemistry.net Thermochemical biomass conversions
    35. 35. www.greenchemistry.netwww.greenchemistry.net Microwave assisted decomposition of biomass: a new thermochemical route to biofuels
    36. 36. www.greenchemistry.netwww.greenchemistry.net Microwave Enhancement of Biomass
    37. 37. www.greenchemistry.netwww.greenchemistry.net Why MW? Advantages of MW Heating Rapid internal heating Uniform heating Instant control Acceleration of reaction rate Selective interaction with active
    38. 38. www.greenchemistry.netwww.greenchemistry.net MW industrial application Special ceramic production Drying Food industry Polymerisation Chemical processing/synthesis
    39. 39. www.greenchemistry.netwww.greenchemistry.net –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
    40. 40. www.greenchemistry.netwww.greenchemistry.net 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
    41. 41. www.greenchemistry.netwww.greenchemistry.net 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
    42. 42. www.greenchemistry.netwww.greenchemistry.net 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%)
    43. 43. www.greenchemistry.netwww.greenchemistry.net Continuous feed Microwave energy volatiles Continuous microwave processing of untreated biomass
    44. 44. www.greenchemistry.netwww.greenchemistry.net Creating a complete supply chain: from Farm to Forecourt
    45. 45. www.greenchemistry.netwww.greenchemistry.net The multiproduct biorefinery of the future
    46. 46. www.greenchemistry.netwww.greenchemistry.net A model for a wheatstraw biorefinery
    47. 47. www.greenchemistry.netwww.greenchemistry.net A seaweed biorefinery
    48. 48. www.greenchemistry.netwww.greenchemistry.net How green is my product?
    49. 49. www.greenchemistry.netwww.greenchemistry.net 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
    50. 50. www.greenchemistry.netwww.greenchemistry.net 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’
    51. 51. www.greenchemistry.netwww.greenchemistry.net 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
    52. 52. www.greenchemistry.netwww.greenchemistry.net • 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
    53. 53. www.greenchemistry.netwww.greenchemistry.net 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.
    54. 54. www.greenchemistry.netwww.greenchemistry.net 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.
    55. 55. www.greenchemistry.netwww.greenchemistry.net 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.
    56. 56. www.greenchemistry.netwww.greenchemistry.net 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.
    57. 57. www.greenchemistry.netwww.greenchemistry.net 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
    58. 58. www.greenchemistry.netwww.greenchemistry.net 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
    59. 59. www.greenchemistry.netwww.greenchemistry.net 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
    60. 60. www.greenchemistry.netwww.greenchemistry.net Research Industry Networking Education www.greenchemistry.net

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