Bio-based Solvents: Applications and Markets

www.greenchemistry.netwww.york.ac.uk/res/s4

OO

O

O

O

OO

O

OO O O

O

O

OH

O

O

OH

OO

OH

[email protected]

Bio-Based SolventsApplications & Markets

www.achema.de/de/presse/www.aaechemie.com/html/aae_solvent_information.htmlen.european-bioplastics.org/multimedia/ www.plasticsportal.net/wa/plasticsEU/portal/show/content/products/biodegradable_plastics/ecovio

Lubricants

Solvents

Surfactants

Bio-based solvent market share = 1.5%Current capacity = 12.5%

265 million metric tonnes per year

20 MMT

Plastic

Solvent Market

www.greenchemistry.net

Cosmetics

Plastics industry

Metal cleaningAgroc

hemica

lsFo

od se

ctor

Dry cle

aningOther industries

Home cleaning

Adhesives

InksPaints/coatings

Pharma

Solvent is the major ingredient (the ‘wet’ bit if you were wondering)

Solvent is needed in manufacturing & processing

Solvent used for washing

Market: 20 MillionTonnes /year

ESIG data, 1997

Solvent Market


• Solvent use in adhesives has declined since the 1980’s.

• 6% of solvent use in 1990’s Europe attributed to the adhesives sector.

• Solvent-based adhesives made up 14% of European production in 1995 (25% in Asia).

• Many industries which use solvent-based adhesives have moved to regions with less restrictions. For example:

• Shoe making in Brazil, China, and India (e.g. polyurethane adhesives);

• rubber bonding;

• PVC pipe bonding;

• contact polychloroprene adhesives.

• Typical solvents for the adhesives sector are hydrocarbon (both aliphatic and aromatic) and ketone solvents (acetone and MEK).

Handbook of Solvents, Ed. Wypych, 1st edition (2001), page 848; Handbook of Adhesives and Sealants (Basic Concepts in High Tech Bonding, vol. 1), Ed. Cognard, 2005, page 93.

Solvents & Adhesives


REACHRegulation (EC 1907/2006)

ec.europa.eu/environment/chemicals/reach/reach_en.htm

Trichloroethylenesunset date: 21/04/2016

Solvent Regulation

www.greenchemistry.netecha.europa.eu/regulations/reach/authorisation/the-candidate-listecha.europa.eu/candidate-list-table

REACHRegulation (EC 1907/2006)

Substances of Very High Concern (SVHC)

An opportunity for bio-based solvents?

NO2

N

O

H N

O

ClCl Cl

OO

Br

NH

O

OO O

OO

O

ClCl

NO

OO

O

HOO

O

O

O

O

Solvent Regulation



Ionic liquids

Acids

Alcohols PolyolsOH

OH

OHOHOH

OH OHOH

OH

O

OH

O

OH

OH

O

OH

OO

OH

O

O

OH

HOOH

Protic solvents

OO

OH

OHHO OH N

OHCl:

Solvent mapping


Aprotic solvents

Amines

Dipolar aprotics

ChlorinatedHydrocarbon

Nitro

Ethers Ester Ketones

Nitriles

O

O

O

O O

O

O

O

O

O O

O

O

O

NH2

O

OO

O

O

O O

O

OO O O

O

O

S4 focus zones: hydrocarbons and dipolar aprotics

Solvent mapping


Case study 1. Problem: Solvent substitution necessarySafer, renewable hydrocarbon solvents from food waste

p-CymeneLimonene


>

>

Case study 1. Problem: Solvent substitution necessarySafer, renewable hydrocarbon solvents

G. Paggiola, A. J. Hunt, C. R. McElroy, J. Sherwood and J. H. Clark, Green Chem., 2014, 16, 2107.

OH

HO

O

O

O


OH

J. H. Clark D. J. Macquarrie and J. Sherwood, Chem. Eur. J., 2013, 19, 5174.

Ln[product selectivity]

Solvent inducedtautomerisation

O

O

O OH

O

O H2N

O

NH2Ph

O

H

NH

NH

Ph

Ph O

O

O

Case study 1. Problem: Solvent substitution necessarySafer, renewable hydrocarbon solvents


LimoneneIs it green?

Solvent Safety Health Environment Conclusion

Limonene 4 2 7 Problematic

n-Hexane 8 7 7 Hazardous

p-Cymene 4 5 5 Problematic

Toluene 5 6 3 Problematic

D. Prat et al., Green Chem., 2016, 18, 288.

CHEM21 selection guide of classical- and less classical-solvents


Renewable Citrus Products Association LCA* (cradle-to-gate)http://www.renewablecitrus.org/sites/renewablecitrus.org/files/LCA%201-6-13.pdf

Global warming potential (left):

Less good in ‘habitat alteration’and ‘eutrophication’ indicators due to direct land use changeand fertiliser/agrochemicals

Tap

wat

er

Lim

onen

e

Ora

nge

oil

Nap

htha

Ker

osen

e

Xyl

enes

Ben

zene

Tolu

ene

Ethy

l ben

zene

Ace

tone

DC

M

Perc

(steam distillation)

(vacuum distillation)

LimoneneIs it sustainable?

http://www.renewablecitrus.org/sites/renewablecitrus.org/files/LCA%201-6-13.pdf




Case study 2. Opportunity: New alternative solventsA bio-based alternative for dipolar aprotic solvents

Image credit:Andrew Hunt


O

O

O

CYRENE


Polarity plotcredit: Laurianne Moity



Three dimensional structure

Combination of functionality



NN R Br

NN R

Br

Can replace dipolar aprotic solvents



Applications in materials science


Open-bio is developing test methods and recommendations for European standards describing bio-based content, biodegradation, recycling strategies, as well as labelling and procurement tools, and evaluating social acceptance. www.biobasedeconomy.eu/research/open-bio

• Our goal is to assist the growth of the European bio-based product market.

• Started in November 2014 as a 3 year EC-funded FP7 project.

Bio-based product standardisation


co-normative research

pre-normative researchResearch

results

TC 411normative action

Questions

Answers

Answers



Performance Bio-based content

HSE Sustainability

Bio-based solventsCEN/TS 16766

At least 25% bio-based carbon• Class A: ≥95%• Class B: ≥50%• Class C: ≥25%

Provide data but no threshold values:• Polarity• Volatility• Colour

• Density• Viscosity

No harsher than REACH and GHS/CLP

No extra barriers for bio-based solvents

Sustainable biomass must be used, and optionally the

production phase assessed



How to unify these ‘green’ EU economic strategies?

Circular economy (general legislated targets)

ec.europa.eu/environment/circular-economy/index_en.htm

Reduce food waste and

marine litter

Increase recycling and re-use of municipal

waste to 65%

Maximum landfilling

rate of 10%

Bio-based economy (standardised product descriptions)

www.biobasedeconomy.eu

Biomass

Products

Some end-of-life

requirements for certain products




Recirculated:Returned to use within a certain timeframe by an anthropogenic process and/or a natural process.

Open-Bio D3.4 Definitions for renewable elements and renewable molecules

Cycles

Renewable:Comes from renewable resources and is returned to use within a certain timeframe by a natural process.

Returned to use within a certain timeframe by an anthropogenic process.

Recyclable:

Reusable:Returned to use within a certain timeframe without modification to the parent article or loss of performance.

Report available online at http://www.biobasedeconomy.eu/research/open-bio/publications


Bio-based Recirculated SustainableComplex with many relevant

criteria

Hugely challenging to

implement

Describes biomass

utilisation

Environmental impact is not considered

Incorporates full life cycle coverage

Easily validated and understood

Increasing complexity

How does ‘recirculation’ fit within bio-basedproduct standardisation?


Fossil reserves

Not recirculated

Bio-based carbon

Fossil carbonC

CSustainability criteria (EN 16751)

Bio-based content(CEN/TS 16640)

Biomass sustainability(e.g. PEFC ST 1003) &waste feedstocks(e.g. ISCC PLUS 260-05)

End-of-life options:•Mechanical recycling•Chemical recycling•Biodegradation

Vertical standards (e.g. CEN/TS 16766)and ecolabels

C

C

renew looprecycle loop

reuse loop


[email protected]/profile/James_Sherwood2

http://www.slideshare.net/JamesSherwood2blogs.rsc.org/gc/author/sherwoodj

http://www.york.ac.uk/res/s4/twitter.com/S4_Solvents www.york.ac.uk/chemistry/research/green

Science

Bio-based Solvents: Applications and Markets