development of sustainable processes from the conversion ... rosete sergio.pdfdevelopment of...
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Development of Sustainable Processes from the conversion of Renewable raw materials to
Platform Chemicals
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Outline• Summary of the attempts for establishing
processes based on renewables• Crop conversion and biorefineries• Metrics for assessing the viability of
biorefineries
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• Are we looking for the first time at the production of chemicals from renewable resources?
• What has happened before?
1900 2005? ? ?
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1920’s Chemurgy
1900 2005? ?
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• Chemurgy 1920’s – Development of non-food uses of
existing crops– Development of new farm commodities– Profitable application of agricultural
wastes and residues
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• Reasons for Chemurgy emergence– Access to the German patents of chemical
processes – International trade tensions– Agriculture surplus– Examples for processes run on renewables– Prediction that the world petroleum reserves
might be exhausted in a few decades
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Henry Ford
November 1940
Thomas Edison
Herbert Hoover
Source: (Finlay, 2003 Journal of Industrial Ecology 7:33-46)
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• Reasons for Chemurgy demise
– Governmental withdraw of support
– Economics of coal and petroleum
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1970’s Oil Crisis
?1900 2005
1920
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• Oil crisis 1970 • Causes
– Middle East governments conflict with foreign oil production companies
– Cut down in production of fossil fuels• Solution
– Political solution
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1975 PROALCOOL
?1900 2005
1920
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• Reasons for PROALCOOL emergence– Energetic crisis– Surplus of sugar cane and its price
variations– Prediction that the world petroleum
reserves might be exhausted in a few decades
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• Beneficial outcomes– Reduction of oil imports– Creation a local market which found
applications– Flexible production between sugar and
ethanol • Barriers to overcome
– Trade regulations
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Rate of resources exploitation caused an apparent conflict between the interests of economic development and the interests of environment
?1900 2005
1920 1970
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1987 United Nations
“Sustainable development is development that meets the needs of the present without compromising future generations to meet their own needs”
Brundtland Comission
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1992 Earth Summit
•Rio Declaration
•Agenda 21
•Framework Convention on Climate Change
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1994United Nations Framework Convention on Climate Change
19201900 2005
1970
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• UNFCCC – Recognise an existing environmental
problem– Set the objective of stabilising
greenhouse gas concentrations– Encourage scientific research on climate
change
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Carbon dioxide concentration in the atmosphere
(parts per million by volume)
Source: (NFCCC, 2003 www.unfccc.org)
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• Kyoto Protocol 1997– Stabilize emissions– Assigns a national target to each
country– Three mechanisms:
• Emissions Trading• Joint Implementation• Clean Development Mechanism
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2005
19201900
1970
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• We must recognise:– There is an environmental problem
associated to the consumption of fossil fuels– We are still predicting that… “The world
petroleum reserves might be exhausted in a few decades”
– Processes based on renewables can serve as a tool to obtain sustainability
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• How can we structure the efforts to produce chemicals from renewables?
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Maximise the use of the crop
Processing
EnergyContent
Crop
Chemicals
Final goods
Carbon dioxide
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Biomass Program (DOE)Biomass Program (DOE)
Source: http://www.eere.energy.gov/biomass/
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• BiorefineryFeedstock mixture + process mixture products
Fuels
Solvent
Plastics
Fine chemicals
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Petroleumfeedstock
Fuels
Solvent
Bulk chemicals
Plastics
Fibres
Fine chemicals
Oils
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• Choice for feedstock– Green grasses– Lignocellulosic
materials– Cereals– …
• Choice for chemicals– Ethanol– Organic acids– Amino acids– …
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Cereal grainThe most intensive crops are based on starch.10 times more chemical energy is stored as cereal grain starch than as sucrose
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Milled Bran Milled Endosperm Germ
Grain
Aleurone layer
Protein: 18%Vitamins: Niacin, Pantothenicacid, Pyridoxine, Thiamine, Riboflavin, Betaine
Pentosans: 25%Cellulose: 21%Crude fiber: 10%Protein: 13%Phytate: 4%Starch: 8%Total sugar: 5%Reducing sugars: 4%Lipid: 4%Vitamins:: Choline, Inositol, Niacin, Tocopherols, Pantothenic acid, p-Aminobenzoic acid,Thiamine, Riboflavin,Folic acid, Biotin:
Starch: 70%Protein: 10%Phytate: 0.5%Vitamins: Inositol, Niacin, Tocopherols, Pantothenic acid, Pyridoxine, Thiamine, Riboflavin, p-Aminobenzoic acid, Folic acid, Biotin
Protein: 25%Total sugar: 17%Raffinose: 7%Lipid: 12%Phytate: 2%Vitamins:: Inositol, Niacin, Pyridoxine, Pantothenic acid, Thiamine, Riboflavin, p-Aminobenzoic,
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Petroleumfeedstock
Fuels
Solvent
Bulk chemicals
Plastics
Fibres
Fine chemicals
Oils
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Grain
Solvent
Fuels
Bulk chemicals
Plastics
Fibres
Fine chemicals
Oils
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Source: Top Value Added Chemicals from Biomass (DOE)
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• 14 Platform chemicalsNo. Carbon
atoms3 3-hydroxy propionic acid and glycerol4 1,4-diacids (succinic, fumaric and malic),
aspartic acid and3-hydrobutyrolactone
5 glutamic acid, itaconic acid, levulinic acidand xylitol/arabinitol
6 2,5-furan dicarboxylic acid, glucaric acidand sorbitol
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• Metrics for assessing the viability of biorefineries– Platform potential– Processing potential– Transformability
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• Platform potential: assess the number of conversion routes from sugars to the platform chemical and the number of derivatives from the platform chemical to final product.
Fermentation
Enzymatic conversion
Chemical
Platform Derivativeschemical
modification
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• Processing potential: accounts for the possibility of the platform chemical to be further processed towards simpler compounds in terms of structure and composition.
Processing
Cereals
Platform ChemicalEnergyContent
(ΔH combustion)
Derivatives
Carbon dioxide
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• Transformability: accounts for the atom efficiency of the transformation and the energetic and material requirements
Crop Production
Crop Processing Bioconversion
Product Recovery
M W E M W E M W E M W EM: materials; W: water; E: energy
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Routes from sugars
Aspartic acid Succinic acid
• Chemical amination offumaric acid with ammonia
• Fermentation• Enzymatic conversion
• Fermentation
OHOH
O
O
OHOH
O
O
NH2
Platform potential
AS
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Derivatives
Platform potential
A S
Figure from: (DOE, 2004 Top Vaule Added Chemicals from Biomass)
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• Numbers of conversion routes from sugarsAspartic acid (3) > Succinic acid (1)
• DerivativesSimilar group of derivatives
• Platform potential for aspartic acid is higher than succinicacid
AS
A S
A S
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Processing potential
Figures from: (DOE, 2004 Top Vaule Added Chemicals from Biomass)
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• Sorbitol has a higher processing potential than glycerol because the latter can be produced from the former
Processing potential
Processing
EnergyContent
Sorbitol
Glycerol
Propanol
Carbon dioxide
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Transformability
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1990
– Learn from the successes and failures of their predecessors
– Optimise the biorefinierieswith the assessment from the metrics proposed
– Establish the virtue of biorefineries in their own right (environmentally,
How to generate sustainable development with biorefineries?
socially and economically)