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Concentrate! Green and Orange Don't Always Clash
James Sherwood
University of York
www.greenchemistry.net
Green Chemistry at York
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Renewable Materials
Microwave Processing
Clean Synthesis
& Platform Molecules
Natural Solvents & Biolubricants
Training,
Education and
Networks
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12 Principles of Green Chemistry
2. Maximise incorporation of materials
7. Use renewables
3. Lower toxicity
4. Design
safer chemicals
12. Accident prevention
11. Monitor
and analyse
1. Waste prevention better than clean-up
5. Don’t use solvents!
9. Use catalysis
8. No protecting group chemistry
6. Minimise energy
10. Design for degradation
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E-Factor =Mass of waste /g
Mass of product /g
Industry Annual production /kT
E-factor Total waste /kT
Oil refining >1000 0.1 1000
Bulk chemicals 10-1000 1-5 100
Fine chemicals 0.1-10 5-50 10
Pharmaceuticals 0.001-1 25-100 1
M. Lancaster in ‘Introduction to Green Chemistry’, RSC, Cambridge, 2002.
Principle 1 of Green Chemistry:Waste prevention
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Principle 2 of Green Chemistry:Maximise incorporation of materials
Atom economy /% =RMM of product
RMM of reactants
OO O
4.5 O2 2 H2O 2 CO2
44.1%
OO O
3 O2 3 H2O
64.5 %
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O
OH
HO
HO
OH
OH
O
HO
O
OH
Principle 7 of Green Chemistry:Use renewable feedstocks
OO O
Non-oxygenated
Highly-oxygenated
Pyrolysis
Fermentation
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Use catalysis (carefully!)
Principle 9 of Green Chemistry:
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Copper (Cu)
Courtesy of Dr Mike PittsSustainability Manager
170 kg of copper associatedwith each European person
This is double our ‘allowance’
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Elements in a Mobile Phone
Source: Basel Convention, 2006; Lindholm (Nokia report), 2003
Courtesy of Dr Mike PittsSustainability Manager
Roughly 40 different elements
H, Li, Be, C, N, O, F, Al, Si, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Br, Sr, Y, Zr, Ru, Pd, Ag, Cd, In, Sn, Sb, Ba, Ta, W, Pt, Au, Hg, Pb, Bi, Nd.
A mobile phone weighing 100 g contains:
13.7 g of copper
0.189 g of silver
0.028 g of gold
0.014 g of palladium
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www.greenchemistry.nethttp://www.youtube.com/watch?v=T5zO5IwwQ6w
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A new OPEC: Orange Peel Exploitation Company
50% juice 50% waste
Valorisation of a million ton scale pre-consumer waste to bio-chemicals, bio-materials and bio-fuels.
BIO-CHEMICALS
8,069,705 T/y of waste orange peels
available in Brazil
BIO-FUELS
BIO-MATERIALS
Bio-ethanol
Bio-solvents
Chars
Liquid fuelsSugars
Water purificationSeparations
Natural fragrance chemicals
Chemical intermediates
Acid catalysts
Catalysis
Clean Synthesis Technology Platform
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www.greenchemistry.nethttp://www.bbc.co.uk/news/science-environment-14933631http://www.independent.co.uk/news/science/turn-orange-peel-into-plastic-its-not-as-crazy-as-it-sounds-2354916.htmlhttp://www.forbes.com/sites/eco-nomics/2011/09/20/orange-peels-could-be-made-into-biodegradable-plastic/http://www.express.co.uk/posts/view/271979/Is-orange-peel-new-superfuel
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Orange (Citrus) Waste
http://faostat.fao.org/site/339/default.aspx
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Orange (Citrus) Waste
Global orange productionP
rod
uct
ion
(M
MT
)
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Orange (Citrus) Waste
Brazilian food production
Pro
du
ctio
n (
MM
T)
Pro
du
ctio
n (
$1 b
illio
n)
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50% waste
Orange (Citrus) Waste
50% juice
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50% juice
Plastics Catalysts
Solvents
Nano-materials
Orange (Citrus) Waste
Fuels
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www.greenchemistry.netM. Pourbafrani et al., Biores. Tech., 2010, 101, 4246.
Orange Fuels
Chemical feedstock Fuel
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Microwave Technology Platform
Microwave activation of biomassdevelopment of an alternative method of
decomposing biomass
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50% juice
Plastics Catalysts
Solvents
Nano-materials
Orange (Citrus) Waste
Fuels
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www.greenchemistry.netL. Pfaltzgraff et al., Green Chem., 2013, 15, 307.
Micro-waves
Hexane wash
Ethanol crash LimonenePectin
Orange mush
Limonene extraction method 1:Microwave energy
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www.greenchemistry.nethttp://www.youtube.com/watch?v=DjkG7Pt5mgE
Limonene extraction method 2:Supercritical fluid extraction
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Eco-waxesCharles Jackson Farms - Botanix - Croda - L’Oreal - Processum
“Natural” products are very desirable…they need to be:
- derived from natural resources
- extracted using “natural” solvents (H2O, EtOH, CO2)
- modified only be “natural” methods (biocatalysis)
Wheat straw scCO2 extraction Wax products Cosmetics
Natural Solvents Technology Platform
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Natural Products (body lotion)
Aqua, Glycerin, Alcohol Denat., Cetearyl Alcohol, Isopropyl Palmitate, Glyceryl Stearate Citrate, Octyldodecanol, Argania Spinosa Kernel Oil, Glyceryl Glucoside, Sodium Carbomer, Methylisothiazolinone, Phenoxyethanol, Linalool, Limonene, Citronellol, Benzyl Alcohol, Butylphenyl Methylpropional, Alpha-Isomethyl Ionone, Geraniol, Parfum.
http://www.nivea.co.uk/products/body-care/pure-and-natural/pure-and-natural-body-lotion
Aqua, Glycerin, Alcohol Denat., Cetearyl Alcohol, Isopropyl Palmitate, Glyceryl Stearate Citrate, Octyldodecanol, Argania Spinosa Kernel Oil, Glyceryl Glucoside, Sodium Carbomer, Methylisothiazolinone, Phenoxyethanol, Linalool, Limonene, Citronellol, Benzyl Alcohol, Butylphenyl Methylpropional, Alpha-Isomethyl Ionone, Geraniol, Parfum.
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Limonene extraction method 3:Steam distillation
Industries are built on distillation (essential oils) and
cold pressing (vegetable oil)
16 kg of flavedo = 1 litre of orange oil
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Limonene p-CymeneLimonene p-Cymene
Pd/C
Clay
Orange Solvent
Pd/C
Clay
Steam distillation
or scCO2
or μW
10.09 g 8.87 g
1.48 g
0.79 g
=(Mass in – Mass out) /g
Mass out /g
= = 0.3912.36 g – 8.87 g
8.87 g
E-Factor =Waste /g
Product /g
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Solvent
Yield 74% 74% 34%
Orange Solvent
J. H. Clark, D. J. Macquarrie and J. Sherwood, Green Chem., 2012, 14, 90.
OH
O
H2NNH
O
Amidation
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Orange Solvent
H
O
H2N NH2
O
O O
O
OH O
O
NH
NH
O
O
O
-2 H2O
Biginelli reaction
Dipolar solvents
Hydrocarbon
solvents
J. H. Clark, D. J. Macquarrie and J. Sherwood, CAEJ, 2013.
Solvent
Yield 59% 66%
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50% juice
Plastics Catalysts
Solvents
Nano-materials
Orange (Citrus) Waste
Fuels
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Orange Catalysts
H2SO4
SOH
O
O
Pd/C
Limonene p-Cymene p-Cymene-α-sulfonic acid
Solvent Solvent Catalyst
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Orange Catalysts
Br
H
O
O
O
Br
Catalyst Yield
73%
73%S
OHO
O
SO3H
J. H. Clark et al., Cat. Today, 2012, 190, 144.
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50% juice
Plastics Catalysts
Solvents
Nano-materials
Orange (Citrus) Waste
Fuels
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Adjustable surface energies and polarities
High mesoporocity and surface areas
Readily functionalisable
Good chemical and heat resistance
Controllable electrical conductivity
Properties
Separation media
Catalysis
Absorbency
Water purification
Fuel cells
Applications
Increasing cooking temperature
Make it hot
Make it dry
Make it wet
Renewable Materials Technology Platform
STARBONS®
An exciting new class of carbonaceous materials
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Orange Materials
“Pectin-Derived Porous Materials” R. J. White, V. L. Budarin and J. H. Clark, Chem. Eur. J., 2010, 16, 1326. © Wiley Interscience publishing.
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Orange Materials
O
H
HO
H
HO
H
OH
OHHH
OH
O
OH
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Orange Materials
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50% juice
Plastics Catalysts
Solvents
Nano-materials
Orange (Citrus) Waste
Fuels
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Orange Plastics
O
O O
O
O
O
O
O
HOOH
OO
H
OH
O
HOOH
HOOH
Poly(ethylene terephthalate) or PET
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Orange Plastics
Ethylene glycol synthesis (petrochemical)
O OH
OHO
HOOH
Terephthalic acid synthesis (petrochemical)O OH
OHO
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Orange Plastics (Coca-Cola since 2009)
http://www.coca-cola.co.uk/environment/coca-cola-eco-plastics-recycling-joint-venture.html
“It is the first ever fully recyclable PET plastic beverage bottle made partially from plants. The material looks and functions just like traditional PET plastic, but has a lighter footprint on the planet and its scarce resources.”
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Orange Plastics
O
O O
O
O
O
O
O
Bio-derived segment
HOOH
OH
Bio-ethanol Bio-ethylene glycol
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Orange Plastics (Pepsi, pilot stage)
Photo credit: PR NEWSWIRE
http://www.pepsico.com/PressRelease/PepsiCo-Develops-Worlds-First-100-Percent-Plant-Based-Renewably-Sourced-PET-Bott03152011.html
“PepsiCo's "green" bottle is 100 percent recyclable and ... is made from bio-based raw materials, including switch grass, pine bark and corn husks. In the future, the company expects to broaden the renewable sources used to create the "green" bottle to include orange peels, potato peels, oat hulls and other agricultural by-products from its foods business”
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Orange Plastics
Limonene p-Cymene Terephthalic acid
O OH
OHO
Pd/C HNO3
KMnO444
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Orange Plastics
31.2% of mass from ethylene glycol
O
O O
O
O
O
O
O
68.8% of mass from terephthalic
acid
Σ(RMM of atoms from biomass)
Σ(RMM of polymer)‘Natural’ content /% =
‘Natural’ carbon /% =Σ(no. of atoms from biomass)
Σ(no. of atoms in polymer)
80% of carbon atoms
20% of carbon atoms
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Concentrate! Green and Orange Don't Always Clash
Thanks to: Prof. James Clark, Dr. Duncan Macquarrie, Dr. Thomas Farmer, Lucie Pfaltzgraff.