THE PROBLEMMany organic chemicals are being synthesized from nonrenewable petroleum and natural gasAfter use they end up as CO2 or remain in the environmentMaking 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)
COMMODITIES VS FINE CHEMICALS
http://upload.wikimedia.org/wikipedia/commons/7/78/Fine_Chemicals,_Commodities_and_Specialties.jpg
TOP LARGEST-VOLUME CHEMICALS PRODUCED IN THE US FROM FOSSIL FUELS
•Ethylene
•Ammonia
•Propylene
•Methyl tert-butyl
ether
•Ethylene dichloride
•Nitric acid
•Ammonium nitrate
•Benzene
•Urea
•Vinyl chloride
•Ethylbenzene
•Styrene
•Methanol
•Carbon dioxide
•Xylene
•Formaldehyde
•Terephtalic acid
•Ethylene oxyde
•Toluene
•P-xylene
•Cumene
•Ethylene glycol
•Acetyc acid
•Phenol
•Propylene oxide
•Butadiene
•Carbon black
•Isobutylene
•Acrylonitrile
•Vinyl acetate
•Acetone
•Butyraldehyde
•Adipic acid
•Nitrobenzene
•BPA
OLEFINS AND CHEMICALS DERIVED FROM THEM: DEHYDRATION OF ETHANOL
http://www.chematur.se/sok/download/Ethylene_rev_0904.pdf
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)
PRODUCTION OF ETHYLENE FROM RENEWABLE SOURCES
Ni Cr /phosphine
Low density polyethylene
catalyst
Cu/zeolite
Styrene (vinyl benzene)
W/Mo
PropyleneAlso from:Isopropyl alcoholCarbohydrate hydrolysisEthylene+COPropionic acid
ALCOHOLS AND CARBOXYLIC ACIDS1. 1,3 – propanediol from glucose/glycerol (biocatalysis)
Poly(trimethylene terephthalate), Sorona ™ by DuPont
ALCOHOLS AND CARBOXYLIC ACIDS2. Ethylene, propylene, and butadiene glycols from sorbitol
Other catalyst Ru/Sn with NaOH (94% conversion)
ALCOHOLS AND CARBOXYLIC ACIDS3. Ethyl acetate by dehydrogenation of ethanol
Use:Solvent and diluentlow costlow toxicityagreeable 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 fruitsChemistry laboratory: extractions and separations
Less cost effective compare to esterification
ZSM-5
Conditions: high temperature (but below 250˚C) and Cu catalyst
ALCOHOLS AND CARBOXYLIC ACIDS4. 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
ALCOHOLS AND CARBOXYLIC ACIDS5. Adipic acid from glucose
http://3.bp.blogspot.com/-2toYsqzEGS4/UDL4Xkol-hI/AAAAAAAAAAA/83K2zcwtDYY/s1600/Screen%2Bshot%2B2010-09-16%2Bat%2B10.27.10%2BPM.png