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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