Development of Sustainable Processes from the conversion of Renewable raw materials to

Platform Chemicals

Outline• Summary of the attempts for establishing

processes based on renewables• Crop conversion and biorefineries• Metrics for assessing the viability of

biorefineries

• Are we looking for the first time at the production of chemicals from renewable resources?

• What has happened before?

1900 2005? ? ?

1920’s Chemurgy

1900 2005? ?

• Chemurgy 1920’s – Development of non-food uses of

existing crops– Development of new farm commodities– Profitable application of agricultural

wastes and residues

• 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

Henry Ford

November 1940

Thomas Edison

Herbert Hoover

Source: (Finlay, 2003 Journal of Industrial Ecology 7:33-46)

• Reasons for Chemurgy demise

– Governmental withdraw of support

– Economics of coal and petroleum

1970’s Oil Crisis

?1900 2005

1920

• Oil crisis 1970 • Causes

– Middle East governments conflict with foreign oil production companies

– Cut down in production of fossil fuels• Solution

– Political solution

1975 PROALCOOL

?1900 2005

1920

• 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

• Beneficial outcomes– Reduction of oil imports– Creation a local market which found

applications– Flexible production between sugar and

ethanol • Barriers to overcome

– Trade regulations

Rate of resources exploitation caused an apparent conflict between the interests of economic development and the interests of environment

?1900 2005

1920 1970

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

1992 Earth Summit

•Rio Declaration

•Agenda 21

•Framework Convention on Climate Change

1994United Nations Framework Convention on Climate Change

19201900 2005

1970

• UNFCCC – Recognise an existing environmental

problem– Set the objective of stabilising

greenhouse gas concentrations– Encourage scientific research on climate

change

Carbon dioxide concentration in the atmosphere

(parts per million by volume)

Source: (NFCCC, 2003 www.unfccc.org)

• Kyoto Protocol 1997– Stabilize emissions– Assigns a national target to each

country– Three mechanisms:

• Emissions Trading• Joint Implementation• Clean Development Mechanism

2005

19201900

1970

• 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

• How can we structure the efforts to produce chemicals from renewables?

Maximise the use of the crop

Processing

EnergyContent

Crop

Chemicals

Final goods

Carbon dioxide

Biomass Program (DOE)Biomass Program (DOE)

Source: http://www.eere.energy.gov/biomass/

• BiorefineryFeedstock mixture + process mixture products

Fuels

Solvent

Plastics

Fine chemicals

Petroleumfeedstock

Fuels

Solvent

Bulk chemicals

Plastics

Fibres

Fine chemicals

Oils

• Choice for feedstock– Green grasses– Lignocellulosic

materials– Cereals– …

• Choice for chemicals– Ethanol– Organic acids– Amino acids– …

Cereal grainThe most intensive crops are based on starch.10 times more chemical energy is stored as cereal grain starch than as sucrose

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,

Petroleumfeedstock

Fuels

Solvent

Bulk chemicals

Plastics

Fibres

Fine chemicals

Oils

Grain

Solvent

Fuels

Bulk chemicals

Plastics

Fibres

Fine chemicals

Oils

Source: Top Value Added Chemicals from Biomass (DOE)

• 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

• Metrics for assessing the viability of biorefineries– Platform potential– Processing potential– Transformability

• 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

• 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

• 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

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

Derivatives

Platform potential

A S

Figure from: (DOE, 2004 Top Vaule Added Chemicals from Biomass)

• 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

Processing potential

Figures from: (DOE, 2004 Top Vaule Added Chemicals from Biomass)

• 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

Transformability

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)