Carbon Dioxide Carbon Dioxide and the Consumerand the Consumer

Micell Technologies

Carbon Dioxide (COCarbon Dioxide (CO22))

Natural, cheap, plentiful (too much of it!)Natural, cheap, plentiful (too much of it!) 0.04% of atmosphere and apparently rising!0.04% of atmosphere and apparently rising!

Available in >99.9% pure form, £70/$110 per 25kg.Available in >99.9% pure form, £70/$110 per 25kg. By-product of brewing, ammonia synthesis, combustionBy-product of brewing, ammonia synthesis, combustion Non-toxic and properties well understoodNon-toxic and properties well understood

asphyxiant at high concentrations (excludes oxygen from asphyxiant at high concentrations (excludes oxygen from lungs)lungs)

Non-flammableNon-flammable Easily removed and recycled, and can be disposed of with no net Easily removed and recycled, and can be disposed of with no net

increase in global COincrease in global CO22

O C O O C O

The Consumer PerspectiveThe Consumer Perspective

All will have heard of carbon dioxideAll will have heard of carbon dioxide Has been widely used in consumer applications Has been widely used in consumer applications

for many years (carbonated beverages)for many years (carbonated beverages) Supply chain and related technology already Supply chain and related technology already

established.established. Relatively good image for consumerRelatively good image for consumer

‘‘Natural’Natural’• Probably not thought of as a ‘chemical’Probably not thought of as a ‘chemical’

Non-toxic (asphyxiant at high concentrations)Non-toxic (asphyxiant at high concentrations) Renewable, non-petrochemical sources availableRenewable, non-petrochemical sources available Definite benefits over potential alternativesDefinite benefits over potential alternatives

•

SOLID

GAS

LIQUID

SUPERCRITICALFLUID

Triplepoint

Criticalpoint

•

Pre

ssur

e (b

ar)

Temperature (ºC)

74

31.1ºC-56.3ºC

5.1

Phase diagram for pure CO2

© Monterey Bay Aquarium Research Institute© Monterey Bay Aquarium Research Institute

-78 ºC

1

•

SOLID

GAS

LIQUID

SUPERCRITICAL

FLUID

Triplepoint

Criticalpoint

•

Pre

ssur

e (b

ar)

Temperature (K) 303

74

•

SOLID

GAS

LIQUID

SUPERCRITICAL

FLUID

Triplepoint

Criticalpoint

•

Pre

ssur

e (b

ar)

Temperature (K) 303

74

•

SOLID

GAS

LIQUID

SUPERCRITICAL

FLUID

Triplepoint

Criticalpoint

•

Pre

ssur

e (b

ar)

Temperature (K) 303

74

•

SOLID

GAS

LIQUID

SUPERCRITICAL

FLUID

Triplepoint

Criticalpoint

•

Pre

ssur

e (b

ar)

Temperature (K) 303

74

SCFs are intermediate between liquids and gasesSCFs are intermediate between liquids and gases

Solid Liquid

Supercritical Fluid Gas

What has carbon dioxide What has carbon dioxide ever done for us?ever done for us?

Current consumer related Current consumer related applications of COapplications of CO22 technology technology

Carbonated drinksCarbonated drinks Leavening agents in bakingLeavening agents in baking Solvent extractionSolvent extraction Surface coatingSurface coating Fumigation (1% in air will eliminate pests in greenhouses)Fumigation (1% in air will eliminate pests in greenhouses) Dry cleaningDry cleaning Surface cleaningSurface cleaning WeldingWelding pH control (e.g. effluent streams, pulp and paper mills)pH control (e.g. effluent streams, pulp and paper mills) Refrigeration (dry ice, mechanical systems)Refrigeration (dry ice, mechanical systems) Fire extinguishersFire extinguishers Life jacketsLife jackets Main raw material for photosynthesis (with water)!Main raw material for photosynthesis (with water)!

The Future?The Future?

http://www.nasa.gov/vision/earth/technologies/harvestingmars.html

Dry Cleaning using CODry Cleaning using CO22 Current methods use perchloroethyleneCurrent methods use perchloroethylene

1.5 Million tons used per year (North America) 1.5 Million tons used per year (North America) Hazardous air pollutant and suspected carcinogenHazardous air pollutant and suspected carcinogen Contaminates drinking water suppliesContaminates drinking water supplies Contributes to photochemical smogContributes to photochemical smog <5% recycled<5% recycled Requires heating to remove solvent residuesRequires heating to remove solvent residues Characteristic odourCharacteristic odour Use of PERC in EU to be phased out by 2007Use of PERC in EU to be phased out by 2007

Cl

Cl

Cl

Cl

Dry Cleaning using CODry Cleaning using CO22• New process uses liquid CONew process uses liquid CO22

• Requires surfactant (recycled)Requires surfactant (recycled)

• No unpleasant odoursNo unpleasant odours• No heat required for drying – energy efficient and kinder on clothesNo heat required for drying – energy efficient and kinder on clothes• Possible tax credits and reduced regulatory monitoringPossible tax credits and reduced regulatory monitoring• Utilises same COUtilises same CO22 used by food and drink distributors used by food and drink distributors

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T. Sarbu, T. Styranec and E.J. Beckman, Nature, 2000, 405, 165.

O( )m( )nO O

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J.L. Kendall, D.A. Canelas, J.L. Young and J.M. DeSimone, Chem. Rev., 1999, 99, 2663.

Dry Cleaning using CODry Cleaning using CO22

Hangers (Micell, NC), Hangers (Micell, NC), DryWash (Global Technologies, CA)DryWash (Global Technologies, CA)

Related technology also used for degreasing Related technology also used for degreasing (e.g. metal parts), semiconductor photoresist (e.g. metal parts), semiconductor photoresist removal and spin coating.removal and spin coating.

Franchises now operating in SwedenFranchises now operating in Sweden ICI and Linde now major playersICI and Linde now major players

Chem. Eng. NewsChem. Eng. News, Sept. 2 2002. p12., Sept. 2 2002. p12.

Micell Technologies

Spray coating using COSpray coating using CO22

Union Carbide, Unicarb TechnologyUnion Carbide, Unicarb Technology Replaces 40-90% of VOCs with COReplaces 40-90% of VOCs with CO22.. Widespread applicationWidespread application

• Coatings on aerospace partsCoatings on aerospace parts• Adhesion promoters on plasticsAdhesion promoters on plastics

FoodFood• Chocolate biscuitsChocolate biscuits• Barrier coatingsBarrier coatings• AdditivesAdditives

Chem. Eng. NewsChem. Eng. News, June 14 1999, 77 (24), 13., June 14 1999, 77 (24), 13.

Extraction using scCOExtraction using scCO22

Extensively used for ‘natural’ Extensively used for ‘natural’ coffee decaffeination; alternative coffee decaffeination; alternative uses CHuses CH22ClCl22 (also tea)(also tea)

Extraction of Hops for BrewingExtraction of Hops for Brewing Many other extraction processesMany other extraction processes

Often use liquid rather than Often use liquid rather than supercritical COsupercritical CO22..

SpicesSpices Essential oils and fragrancesEssential oils and fragrances

Simple product isolation by Simple product isolation by evaporation, to 100% dryness.evaporation, to 100% dryness.

No solvent residues or effluentNo solvent residues or effluent

COCO22 Refrigeration Refrigeration Many refrigeration plants currently use fluorine-Many refrigeration plants currently use fluorine-

containing volatile organic compounds which are containing volatile organic compounds which are environmentally persistent and have significant environmentally persistent and have significant global warming potentialglobal warming potential

Ammonia also used although is toxic and has Ammonia also used although is toxic and has very strong smellvery strong smell

COCO22 is rapidly emerging as a viable alternative is rapidly emerging as a viable alternative Area of intense activity for variety of applications Area of intense activity for variety of applications

(large scale refrigeration, automobile air (large scale refrigeration, automobile air conditioning, heat pumps, domestic use).conditioning, heat pumps, domestic use).

COCO22 Refrigeration Refrigeration Large scale units now Large scale units now

in operation.in operation. ASDA distribution ASDA distribution

centres in Falkirk and centres in Falkirk and Skelmersdale (2003)Skelmersdale (2003) Amongst the biggest Amongst the biggest

temperature controlled temperature controlled buildings in the UK buildings in the UK (412,000m(412,000m33))

Nestle Coffee freeze Nestle Coffee freeze drying plant in Hayes, drying plant in Hayes, completed in Jan 2002completed in Jan 2002

www.star-ref.co.uk

Chemical SynthesisChemical Synthesis

Fluoropolymer synthesisFluoropolymer synthesis Dupont $275M facilityDupont $275M facility Replaces CFCs used previously (now Replaces CFCs used previously (now banned by Montreal Protocol)banned by Montreal Protocol)

Initially used for fluorinated Initially used for fluorinated ethylene-propylene and perfluoroalkoxy ethylene-propylene and perfluoroalkoxy resinsresins

Easy polymer isolation and drying, and Easy polymer isolation and drying, and minimal wasteminimal waste

S.L. Wells amd J. DeSimone, Angew. Chem. Int. Ed., 2001, 40, 518.S.L. Wells amd J. DeSimone, Angew. Chem. Int. Ed., 2001, 40, 518.

Would a consumer prefer to purchase Would a consumer prefer to purchase a common pharmaceutical product a common pharmaceutical product (e.g. aspirin) prepared using CO(e.g. aspirin) prepared using CO22 as a as a

solvent rather than more harmful solvent rather than more harmful VOCs?VOCs?

How much extra would they be How much extra would they be prepared to pay?prepared to pay?

ConclusionConclusion

COCO22 already has widespread application with already has widespread application with more areas under developmentmore areas under development

Very favourable profile for consumer Very favourable profile for consumer applicationsapplications

Relatively high pressure and energy use may be Relatively high pressure and energy use may be an issue and needs to be balanced, but can be an issue and needs to be balanced, but can be minimisedminimised

Has potential as real green technology of the Has potential as real green technology of the future, as well as the presentfuture, as well as the present

Use and exploitation of COUse and exploitation of CO22 can only increase. can only increase.

c.m.rayner@leeds.ac.ukc.m.rayner@leeds.ac.uk

http://http://www.chem.leeds.ac.uk/People/Rayner.htmlwww.chem.leeds.ac.uk/People/Rayner.html