DOWN TO EARTH:

FUNDAMENTAL RESEARCH TODAY FOR CHEMICALS PRODUCTION TOMORROW COK Dept M2S Fac. Bio-Engineeering K.U.Leuven

Sustainable Chemistry based on Renewables: Why ? Facts: oil availability and prices over the years
Price

Petrochemical feedstock

2050

Year

Carbon is the chemical industrys backbone What if price is high and availability is low ?

Other Problems associated with oil chemistry Combating climate changes e.g., global warming; Reduction greenhouse gases and gases contributing to the depletion of ozone: N2O, CH4 and CO2 Independency of EU on carbon sources: (1) energy resources and (2) organic chemicals.
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Alternative energy sources

Coal (China and USA) Nuclear energy: uranium is most efficient way to transport energy, but what about waste and CO2 (mining, extracting, transport, building and decommissioning of power plant facility) Hydrogen economy (water, steam reforming, water gas shift) Renewable energy (wind, hydro, photovoltaic, solar thermal, geothermal) Biofuels (bioethanol, biodiesel and biogas)
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Rush to biofuels
EU biofuels targets : - 5.75% by 2010 - 20% by 2020 Bioethanol (benzine) Biodiesel (diesel)

sugar

Bioethanol
starch

From corn (USA) and sugar cane (Brasil) or from cereal grains (EU) Fermentation Cellulose (genetic engineered cellulase) Alex Farrell (Berkeley) recently published calculations in Science (2006) showing benefits of bioethanol as green fuel.
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Biodiesel

Fatty acid methyl esters (from triglyceride) with hudge formation of biogenic glycerol (low price !) O
OCH3

Diesel additive (%) or pure is compatible with existing technology Pure vegetable oil (triglyceride)
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Biofuels global: Realistic or not ?

All arable farmland required Increase of feed import food dependency Transport emission: climate change problems Bioethanol is not a green fuel (David Pimental, Cornell, 2006): carbohydrate-poor waste, water and fertilizer, less fuel energy in ethanol. B. Witholt (ETH, Zurich): energy collection and storage with biomass is less efficient than with photovoltaics:
50 - 200 kW / km2 for biomass vs. 15 000 kW / km for photovoltaics

On long run, it is not the solution, but ....

Cartoon

Chemicals and materials from renewables Natural gas instead of petroleum (short term): CH3OH from CH4 (Partial Oxidation) or CO and H2 from CH4 + CO2 (Dry Reforming) Use of renewables for downstream chemistries (long term) Oils and fats (direct use) Proteins Lignine Sugars, Starch, cellulose

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Challenge: Selective defunctionalisation protocols

O HO HO OH OH OH

Ethanol

Cellulose

Glucose

Selective C-H, C-C, C-O bond breaking How ?

Biorefinery as a source of platform molecules Chemocatalysis as interfase between these molecules and the end product 11

Biorefinery: platform molecules Fermentation using yeast, fungi or bacteria GM strains (?EU) to improve their suitability for technical use Some examples from classic biorefinery
Lactic acid, succinic acid and citric acid

Other biobased intermediate chemicals

Bio-ethanol from cellulose (Cargill) Amino acids for pharmaceutical industry, cosmetics and food industry from sucrose (and glucose) and ammonia (Degussa) - Lysine (essential AA) from vegetable oil (BASF) - Adipic acid (nylon) from glucose (DSM) 3-hydroxypropionic acid, 1,3-propanediol (polyester) from glucose (Cargill)
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Anti-knock agent ETBE (Degussa) ETBE or ethyl tertiary butyl ether

O

High octane, oxygen-rich fuel component Reaction between isobutene and bio-ethanol 250 000 tonnes per year
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3GT or polytrimethylene terephthalate (Cargill - DuPont) From terephthalate and 1,3-propanediol

O * O O
n*

Sorona Properties: softness, high power stretch, easy to dye Carpets, textile, automotive fabrics 15 50% green polyester, thus not biodegradable

Plastics from PLAs or polylactic acids (Cargill) Polylactid polymers

O HO OH H CH 3 * H
n*

CH 3

Biodegradable plastic: digestible to m.o. in contrast to conventional plastics Packaging and textiles
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The Challenge Ideally, biotechnology delivers cheap and sustainable building blocks from cellulose, whereas chemical (and enzyme) catalysis is the interfase between these molecules to the wanted products Selection of running projects
(1) Glycerol (2) Vegetable oils (and their methyl esters)
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Biogenic Glycerol
HO O O OH R OH
Propylene glycol

1,3-dioxolane derivative

OH
Propanol

O HO OR RO
Polyethers

R O HO
Glycerol

OH OH
Propylene

1,3-dioxane derivative

OR OH HO O O O
Glyceraldehyde Pyruvic aldehyde

OH O OR
Lactic acid (esters)

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Vegetable oils and their unsaturated fatty methyl esters

Lubricants, paint additives, biofuels, food, medical application, biosolvents, ...
HO OR O epoxide O O O OR OR OR OR O ketone R ether alkyl substituted 19 HO NHR

alcohol ether

amino ether