1. Commodity chemicals from renewable raw materials

2. The problem
Many organic chemicals are being synthesized from nonrenewable petroleum and natural gas
After use they end up as CO2 or remain in the environment
Making future more sustainable = Finding ways to produce these chemicals from renewable sources
Need to revisit old methods based on fermentation – with new advances they might be cheaper and more efficient, and greener
What should be avoided:
-carcinogens and toxic chemicals
-energy-intensive processes (if alternatives are possible)

3. Commodities vs fine chemicals

4. Top largest-volume chemicals produced in the US from fossil fuels
Ethylene
Methanol
Butadiene
Ammonia
Carbon dioxide
Carbon black
Propylene
Xylene
Isobutylene
Methyl tert-butyl ether
Formaldehyde
Acrylonitrile
Terephtalic acid
Vinyl acetate
Ethylene dichloride
Ethylene oxyde
Acetone
Nitric acid
Toluene
Butyraldehyde
Ammonium nitrate
P-xylene
Adipic acid
Benzene
Cumene
Nitrobenzene
Urea
Ethylene glycol
BPA
Vinyl chloride
Acetyc acid
Ethylbenzene
Phenol
Styrene
Propylene oxide

5. Olefins and chemicals derived from them: Dehydration of ethanol
Reaction temperature ~450˚
Catalysts:
SynDolTM (MgO-Al2O3/SiO2)
Silicotungsten acid in MCM-411 zeolite
Na2O-doped Mn2O3/Al2O3
and others..
(99% conversion)
1960 – first plant build by Solvay Group of Brazil – 20MT/day (6700MT/year)

6. Production of Ethylene From renewable sources
Low density polyethylene Ni
Cr /phosphine
W/Mo
catalyst
Propylene
Also from:
Isopropyl alcohol
Carbohydrate hydrolysis
Ethylene+CO
Propionic acid
Cu/zeolite
Styrene (vinyl benzene)

7. Other compounds prepared from ethylene and propylene

8. Alcohols and carboxylic acids
1,3 – propanediol from glucose/glycerol (biocatalysis)
Poly(trimethylene terephthalate), Sorona ™ by DuPont

9. Alcohols and carboxylic acids
2. Ethylene, propylene, and butadiene glycols from sorbitol
Other catalyst Ru/Sn with NaOH (94% conversion)

10. Alcohols and carboxylic acids
3. Ethyl acetate by dehydrogenation of ethanol
Less cost effective compare to esterification
Conditions: high temperature (but below 250˚C) and Cu catalyst
Use:
Solvent and diluent
low cost
low toxicity
agreeable odor
- circuit boards cleaners
- some nail varnish removers
- decaffeination of coffee beans and tea leaves
- an activator or hardener in paints
Present in confectionery, perfumes, and fruits
Chemistry laboratory: extractions and separations
ZSM-5

11. Alcohols and carboxylic acids
Succinic Acid, Succinic Anhydride, and Maleic Anhydride from anaerobic fermentation of carbohydrates
- Precursor to some specialized polyesters
A component of some alkyd resins
Acidity regulator in food and beverage, and pharmaceutical industry
Food additive and dietary supplement (biological metabolite, Krebs cycle)
Phthalic Anhydrade synthesis

12. Alcohols and carboxylic acids
5. Adipic acid from glucose

15. Short report topics for Wednesday
Polymers from renewable raw materials
(Please, choose one of the following):
Products from polyols
Furfural
Polyesters
Polyamides