Renewable ResourcesThe first step in Greening the

Lifecycle of Chemical Products?

Professor James H ClarkClean Technology Centre

www.greenchemistry.net

Benefits of the Chemical IndustryBenefits of the Chemical

Industry

Danger!

Pollution

DiseaseDepletion of

natural resources

Waste Disposal

Land Fill

Toxic Emissions

Accidents

Cancer

CHEMISTRY – A Dirty Word!

Life Cycle Assessment for Chemical Products

Life Cycle Assessment for Chemical Products

E C

W

Pre-manufacturing Manufacturing Product

deliveryProduct

use End of Life

E C

W

E

W

E C

W W

E

Recycle Remanufacture Refurbish

Environment

Public Relations

Future

Waste Disposal

Production

Depletion of natural resources

Raw material inefficiencies

Plant utilisation inefficiencies

Higher production costs

Fines Pollution Clean up costs Recruitment difficulties

Attitudes of workforce

Energy inefficiencie

s

Emissions Health and safety issues

Attitude of Neighbours

Local planning restrictions

Tougher legislation

Increased cost of technology to stay

in business

Increased cost of raw materials

through depletion

Containers

Transport

Late shipment By-product generation

Less competitive pricing

Poor customer relations

Loss of business

Increased costs of disposal

COSTS OF WASTE

What is Green Chemistry?

• Green chemistry is the design of chemical products and processes that reduce or eliminate the use and generation of hazardous substances

• Discovery and application of new chemistry/ technology leading to prevention/reduction of environmental, health and safety impacts at source

New drivers for Green Chemistry• Legislation

– REACH (Registration, Evaluation and Authorisation of Chemicals)• all chemicals used in Europe

– ROHS (Restriction on the use of Hazardous Substances)• heavy metals, chromate, (some) polybrominated compounds

– COMAH (Control of Major Accident Hazards)• storage of chemicals

– Detergents– Electronic and Electrical equipment

• The Market– Increasing price of oil– Increasing price of key commodity chemicals

Subject to major new legislation

Examples of Green Chemistry in PracticePolymer – Clay

nanocomposites asflame retardants

(electronicsmanufacturers?)

specific processes(e.g. ibuprofen,cyclohexanone)biosynthesis of

lactic acid(Cargill Dow)

DegradablePolyethylene(Symphony)

PLA(Cargill Dow)

Green Chemistryprocess metrics

(GSK)

Chitin (crabshell)based adsorbents

(Carafiltration)

Pre-manufacturing Manufacturing Product

DeliveryEnd of LifeProduct

Use

Biodegradablechelant (Octel)

supercriticalcarbon dioxide

for hydrogenation(Thomas Swan)

clean pharmaceuticalsynthesis (severalcompanies)

Catalystrental

(Johnson Matthey)

solid acids in Friedel Craftsreactions (Rhodia, UOP, Contract Catalysts)

Recent Progress in R & D: ExamplesLasers to exciteperoxocarbonate

as a bleachVOC-free solvents(e.g. ionic liquids)bagasse lignin and

vegetable oils aswood adhesives Tannic acid

fixing agentsBiocatalysisapplied tospecialitychemicals

Intensive processing(e.g. microreactors)

Citric and aminoacids as corrosion

inhibitors

Pre-manufacturing Manufacturing End of LifeProduct

UseProductDelivery

Novelexpanded

biomaterials(Chromatography, etc)

alternativeenergy sources(e.g. microwave)

reusable catalysts

(e.g. solid acids)calcium/cerium

pigments

baroplastics plasticsmodified withcarbohydrates

Petroleumfeedstock

Fuels

Solvent

Bulk chemicals

Plastics

Fibres

Fine chemicals

Oils

Petroleum RefineryPetroleum Refinery

Bio-refineryBio-refinery

Fuels

Solvent

Bulk chemicals

Plastics

Fibres

Fine chemicalsGrain

Oils

Bio-refinery conceptExtraction of

2° metabolites

ThermochemicalProcesses

CombinedHeat & Power

Sugar Production

Residues

Gas & Liquid

FuelsChemicals& Materials

Bio & Chemical processing

Gas & Liquid

Sugar feedstocks

Biomass

Biomass Utilisation in 20402.8 x 109 ha available

0.8 x 109 ha available fornon-foods

2.0 x 109 ha for food production for 10 bn people

@40t ha-1 a-1

32 x 109 t a-1

+ forests+ wastestreams

50 x 109 t a-1

of biomass

Green Chemistry, 1999, 1, 1071 x 109 t a-1

for organics> 40 x 109 t a-1

for energy

= 2 x 1020 J a-1

Producing Chemicals from Renewable Resources

Advantages•Conservation of fossil resources•Renewable resources are CO2 neutral

•Raw materials are non-toxic

•Products are biodegradable

Disadvantages•Renewable raw materials are expensive

•New Technology is required

•Logistics and infrastructure of business are not in place

Renewable Resource-readily available

- low cost and value for other applications-safe and easy to handle and prepare

Chemical/Material Extraction-based on benign methods

-efficient and selective-low energy demandFermentation/Pyrolysis

-low environmental impact

-selective to useful platform molecules

-utilisation of residues/benign disposalChemical/Material Modification

-based on benign methods-efficient and selective

-moderate cost for significant added value

Green Chemical Product-green and sustainable across life cycle

- non toxic and non hazardous-Cost effective wrt substitutes

-biodegradable and/or recyclable-Legislation compliant and REACH-resistant?

Extractables(secondary metabolites

from straw)

Materials(primary

metabolites –starch, cellulose)

CH

EMIC

AL

POTE

NTI

AL

Bulk Chemicals((Bio)chemical

processing of bulk materials/residues)

TEC

HN

OLO

GIE

SA

DD

ING

VALU

E

WHEAT

Selective Fermentation

Controlled Pyrolysis

Extraction Technology

(Bio)platform molecules

Green Chemistry/technology

Benign Extraction Methods

Separation/Purification

Green Chemical Transformation

Expansion Methods

Green Chemical Modification

Composites

Metabolites

Sterols/ Sterols/

Steryl estersSteryl estersOH

OH

O

Fatty acidsFatty acids

GlyceridesGlycerides OO

O

O

OO

O

O

Wax estersWax esters

AlkanesAlkanes

OHFatty alcoholsFatty alcohols

Solvent Extraction

PIGMENTS

POLAR LIPIDSLIPIDS

FREE SUGARSSUGARS

PHENOLIC

ACIDS

WAXES

Eco-efficient SolventsEco-efficient SolventsVolatile organic solvents

No Solvent Supercriticalfluids

Water solvent Ionic liquids

Avoidance

Environmentallybenign and safe

Easily separable and safe

Zero Volatility

Greener alternatives

Extract and Wax Yield

% Dry Matter% Dry Matter

0.84

0.36

0.43

0.740.84

0.04

0

0.2

0.4

0.6

0.8

1

1.2

hexane neat CO2 40°C/10MPa neat CO2 60°C/20MPa neat CO2 80°C/30MPa

CoCo--extractivesextractives

waxwax

SolventSolvent

Platform MoleculesWheat (e.g. poor quality whole grain)

Pre-treatment

Bioconversion to glucose concentrateSolid residues (uses?)

Bioconversion to succinic acid

OH

O

O

OH

R2N

O

O

NR2

R2O

O

O

OR2

Microwave activation amidation

N OO

R

Solvent-free cyclisation

Metal-catalysed reduction N O

R

Some easily accessible Platform Molecules

CO2HHO2C

OH

CO2H

OCO2H

CO2HHO2C O CHOOH

CHOMeO

succinic acid lactic acid levulinic acid

adipic acidClean

Synthesis

Methods

A very wide range of useful products

Some Newer Clean Technologies

Catalysis

Process Intensification Solventless

Reactions

Product Design and Life Cycle Assessment

Renewable Feedstocks

Alternative Solvents

Innovative Engineering

Adding Value to Starch

Issues to be Resolved

Efficient routes toplatform molecules

Pre-manufacturing Manufacturing End of LifeProduct

UseProductDelivery

Problem generic areas(oxidations, reductions,

Friedel-Crafts reactions, etc.)

Substitutes for numerous key components (flame retardants,

dyes, adhesives, primers,antioxidants, etc.)

Greater involvementof retailers in

green chemistry

Routine measuringof product toxicity

and environmental impact

Clean synthesison platform molecules

to give added valueproducts

Addressing customerconcerns in an

understandable way

GMissues

Benign extractionmethods for valuablesecondary metabolites

Encouraging“green purchasing”

Reducing the pricemargin between renewables and petrochemicals

Include considerationsof sociological issuesassociated with mining(e.g. Tantalum)

Simplerformulationsthat avoidhazardous

componentsGreenerpackaging

Genuine, quickbiodegradationor suitable fordeconstructionand recycling

Greater public awareness of the importance of Green Chemistry

A lifecycle approach to chemistry research/broader metrics

Tantalum From Cradle to Grave

(various compositions)Tantalum Ore

Ta, Nb complex fluorides+ other impurities (Si, Fe, Ti, U…)

HF/H2SO4/∆

(i) Filter (ii) Solvent extract (MiBK)

Pure Ta + Nb complexes in solution

Further processing

(Nb recovered via Nb2O5)K2TaF7 or Ta2O5 or TaCl5Molten Na/∆

Alternative via C/Al reduction of Ta2O5 or H2 reduction of TaCl5

Ta metal powder or wires

Disassemble?Electronic Products

General Public

Schools11-19 year old resource book (RSC)A - level (16 - 18) websiteTeacher Training courses Talks at schools

UndergraduateText book Practicals LecturesTutorials and Workshops

Postgraduate

MRes courseEuromasters courseWorldwide University NetworkOverseas eventsCrystal Faraday

Training and awareness Courses:(with Crystal Faraday)

Continuing Professional Development

R Soc and RI ExhibitionsBAAS EventsLocal EventsPublic Lectures

Educational Developments

??

Past

Future

Present

The Future Chemical Industry