Robert Newton Marketing Manager

Green Chemistry & Engineering conference, Washington

25th June 2009

Standards for Green Solvents; an example using ionic liquids

© Bioniqs Ltd 2009

• Who are Bioniqs?

• Ionic Liquids – are they green?

• Econiqs green solvent standard

• Example using ionic liquids

• Where do we go from here?

Outline

© Bioniqs Ltd 2009

Who are Bioniqs?

• Pioneering commercialization of green solvents & ionic liquids

• Supplying solvent technology across industry

• Example markets; biomass extractions, waste recycling

• IP covering several million protic ionic liquids

• Proprietary ROSETTA solvent simulation database

© Bioniqs Ltd 2009

• Low-melting salts composed predominantly of ions

• Anion and cation can be selected for optimal performance

• Many millions of ionic liquid permutations can exist

• Excellent solvents for organic, inorganic, polymeric and biological molecules

NHO

O

OH NH+

HO

O

O-

UK Patent GB2412912US Pat. Pend. (10/599,694)

Ionic liquids

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What makes ILs green?

• Low vapour pressure (low-VOC)

• Low flammability

• Recyclable

• Biodegradability

• Low toxicity

• Sustainable

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And what doesn’t?

Are ionic liquids green?

YES NO

Are ionic solids green?

NaCl NaCN

YES NO

Are molecular solvents green?

H2O

YES NO

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So, are ionic liquids green?• It depends on the ions!

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So, are ionic liquids green?

• Ionic liquids initially suffered from ‘greenwashing’

• Widely reported as ‘green’ solvents based on low volatility and low flammability

• However, toxic and environmentally hazardous nature of some ILs soon became apparent

• Often the diversity of the ionic liquid field is overlooked

• Now biodegradable, low toxicity protic ionic liquids developed

• However, they often possess appreciable vapour pressures

© Bioniqs Ltd 2009

What led to the ‘greenwashing’?

• In common with many novel solvents ILs were overhyped.

• The whole spectrum of ILs were judged as one class of materials.

• The degree of ‘greenness’ varies from product to product

• Lack of accepted standard/criteria to define ‘green’

• Unrealistic expectations from the market

• Challenge for suppliers to overcome

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The econiqs Certification

• Preliminary benchmark to assess a solvent’s environmental credentials

• Originally developed in-house to evaluate Bioniqs products

• Customers often asked: “what do you mean by a ‘green’ solvent?”

• Accepted definitions tend to be lax;

“green solvents are defined as solvents that have minimal toxicity to humans and the environment where their toxicities are well understood” Nelson, W.M., Green Solvents for Chemistry; Perspectives and Practice, OUP Oxford 2003 pp91-92

• econiqs establishes a basic set of environmental and toxicological criteria for green solvents

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Criteria Standard

Biodegradable>98% biodegradable by mixed community of natural soil organisms within 14 days, as determined by HPLC and/or ion chromatography.

Sustainableall precursor materials used in manufacture are potentially available from sustainable, renewable feedstocks.

Non-mutagenic non-mutagenic as determined by the Ames test(Mutagenicity Index <2, Mutagenic Activity Ratio <2.5).

Low ToxicityDaphnia magna EC50 >250mg/L.

Green algae (Selanstrum capricornutum) ErC50 >100mg/L.

Green Solvent Benchmark

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Example – DMEA acetate

• Viscosity @ 25°C : 72cP

• Density @ 25°C : 1.02g cm-3

• Refractive index @ 25°C : 1.446

• ENT @ 25°C : 0.93

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Biodegradability

0123456789

10

0 12 24 36 48

Time (hours)

Conc

entra

tion

(mM

)

DMEAMEAEANH4

CH3

NH+

H3C OH

CH3

+H2NOH

+H3NOH

NH4+

70% degraded within 12 hours; 98% in 48 hours

>98% biodegradable by mixed community of natural soil organisms within 14 days, as determined by HPLC and/or ion chromatography.

Rontein, D.; Rhodes, D. & Hanson, A.D. (2003), Plant Cell Physiol. 44, 1185

Scarborough, G.A. & Nyc, J.F. (1967), J. Biol. Chem., 242, 238

N,N-DIMETHYLETHANOLAMINE

Phosphatidyl-N,N-dimethylethanolaminePhosphatidylethanolamine3-Phospho-L-Serine

3-Phosphohydroxypyruvate 3-Phosphoglycerate Glyceraldehyde-3-phosphate

D-Glucose-6-phosphateD-Glucose

CO2 + H2O

Photosynthesis

HexokinaseD-Fructose-6-phosphate

Phosphohexose isomerase

Aldolase

Phosphoglycerate kinase

Phosphoglycerate dehydrogenasePhosphoserine

transaminase/NH3

Phosphatase

Serine decarboxylase Phosphatidyl-DMEA N-

methyl transferase/SAM

ACETATE

Sustainabilityall precursor materials used in manufacture are available

from sustainable, renewable feedstocks.

© Bioniqs Ltd 2009

NH+

HO

O

O-

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Non-mutagenicnon-mutagenic as determined by the Ames test

(Mutagenicity Index <2,Mutagenic Activity Ratio <2.5).

DMEA acetate (mL/plate)

MI TA98 –S9 MI TA98 + S9 MI TA100 – S9 MI TA100 + S9

0.15 1.00 1.06 1.09 1.050.5 1.12 0.65 1.12 0.901.5 1.33 0.77 0.94 1.025 0.83 0.65 0.95 0.9615 1.00 0.82 1.10 1.13

• Mutagenicity Index (MI) – mean number of reversions induced by chemical divided by mean number of spontaneous reversions

• MI > 2 indicates a mutagenic effect

• MI = 0.90 and MAR = -0.24

• DMEA acetate is not mutagenic in bacteria and unlikely to be carcinogenic in mammals

© Bioniqs Ltd 2009

Low Toxicity

Daphnia magna EC50 >250mg/L.

Green algae (Selanstrum capricornutum) ErC50 >100mg/L.

DMEA acetate exhibited no growth inhibition/toxic effects at concentrations of 100mg/L.

Calculated EC50 (based on geometric mean) = 300mg/L.

Image courtesy of Microscopy-UK (http://www.microscopy-uk.org.uk)

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Green Solvent Standards: what next?

• econiqs is not designed to be a fully harmonized specification

• These are a preliminary set of criteria that we intend to develop

• Criteria that could be included:

Ozone depletion potential

Greenhouse gas contribution

Flammability

• econiqs has applicability to all classes of solvents

• Bioniqs is looking to work with industry to assist in establishing a green solvent standard

© Bioniqs Ltd 2009

Bioniqs Team:

Dr. Adam Walker, CEO & Co-Founder

Dr. Guy A. Hembury, Senior Scientist

Dr. Neil Sullivan, Commercial Advisor

Lauren Tate, Project Scientist

Gayle Fairless, Project Scientist

Contributions

Complement Genomics Ltd., Sunderland, UK

© Bioniqs Ltd 2009

Robert Newton

Marketing Manager

robert.newton@bioniqs.com

+44 (0)1904 561538

www.bioniqs.com

Bioniqs Limited, Registered in England and Wales under number 5304761. Registered Office: Heslington Hall, York, YO10 5DD, United Kingdom

“THANK YOU FOR YOUR ATTENTION”