COMMODITY CHEMICALS FROM RENEWABLE RAW MATERIALS

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

OTHER COMPOUNDS PREPARED FROM ETHYLENE AND PROPYLENE

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

SHORT REPORT TOPICS FOR WEDNESDAY

Polymers from renewable raw materials(Please, choose one of the following):1. Products from polyols2. Furfural3. Polyesters4. Polyamides