Concentrate! Green and orange don't always clash

www.greenchemistry.net

Concentrate! Green and Orange Don't Always Clash

James Sherwood

[email protected]

University of York


Green Chemistry at York

2


Renewable Materials

Microwave Processing

Clean Synthesis

& Platform Molecules

Natural Solvents & Biolubricants

Training,

Education and

Networks

3


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

4


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

5


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 %

6


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

7


8

Use catalysis (carefully!)

Principle 9 of Green Chemistry:


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

12

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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Global orange productionP

rod

uct

ion

(M

MT

)

15



Brazilian food production

Pro

du

ctio

n (

MM

T)

Pro

du

ctio

n (

$1 b

illio

n)

16


50% waste


50% juice

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50% juice

Plastics Catalysts

Solvents

Nano-materials


Fuels

18

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

20


50% juice

Plastics Catalysts

Solvents

Nano-materials


Fuels

21

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

22

www.greenchemistry.nethttp://www.youtube.com/watch?v=DjkG7Pt5mgE

Limonene extraction method 2:Supercritical fluid extraction

23


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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http://images.google.co.uk/imgres?imgurl=www.easisites.co.uk/housepics/bale_of_straw.gif&imgrefurl=http://www.easisites.co.uk/page.html?SiteID=jcjeffery&View=2&h=300&w=300&sz=19&tbnid=TLADCzXMl8wJ:&tbnh=111&tbnw=111&prev=/images?q=bale+++straw&start=260&hl=en&lr=&ie=UTF-8&oe=UTF-8&sa=N












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


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


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.

35


Orange Materials

O

H

HO

H

HO

H

OH

OHHH

OH

O

OH

36


Orange Materials

37


50% juice

Plastics Catalysts

Solvents

Nano-materials


Fuels

38


Orange Plastics

O

O O

O

O

O

O

O

HOOH

OO

H

OH

O

HOOH

HOOH

Poly(ethylene terephthalate) or PET

39


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.”

41


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


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.

Science

Concentrate! Green and orange don't always clash