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Title: Mechanism of formation of oil by the hot aqueous alkaline digestion of cellulose

Abstract

The overall mechanism of cellulose converson in hot aqueous alkali appears to be one of degradation through glucose to low molecular weight saccharinic acids, dihydroxybutyric acid, glycolic acid, and carbonyl products such as acetone, acetaldehyde, formaldehyde, and similar compounds. Although the products identified in the present report were fairly complex furans, carbocyclic ketones, unsaturated hydrocarbons, and aromatic compounds, nevertheless, in most cases, they could have been formed from simple carbonyl compounds through a series of condensations involving carbanion intermediates. It is conceivable that residual alkali in the oil during acetone extraction could have given rise to diacetone alcohol as an artifact. This is refuted by examination of an aqueous residue which was extracted with diethyl ether and which was never exposed to any acetone: Compounds derived from diacetone alcohol (such as mesityl oxide or 4-methyl-3-penten-2-one) were also identified in the diethyl ether extract of the aqueous phase. Other compounds were identified in the oil acetone extract which could not have been derived from acetone or diacetone alcohol, but which could have been formed from other carbonyl compounds by the same mechanism. Hence, diacetone alcohol is a genuine product of cellulose conversion although apparently not an intermediate in further synthesis ofmore » other products. The further reaction of the postulated cyclic intermediates, and the route to formation of unsaturated hydrocarbons of high molecular weight is intended to be the next subject of investigation in the current work. The fundamental difference in the mechanism of cellulose conversion to oil by pyrolysis and by aqueous alkaline digestion predicted by theory is therefore confirmed. Pyrolysis products may be explained generally by carbonium ion and free radical reactions (in fact, cellulose decomposition is acid-catalyzed), while in aqueous alkali, nucleophilic carbanion reactions are favored.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Battelle Pacific Northwest Labs., Richland, WA (USA)
OSTI Identifier:
6226833
Report Number(s):
PNL-SA-6485(Rev.); CONF-771266-1
DOE Contract Number:  
EY-76-C-06-1830
Resource Type:
Conference
Resource Relation:
Conference: Thermochemical conversion of biomass seminar, Golden, CO, USA, 1 Dec 1977; Other Information: Portions of document are illegible
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; CELLULOSE; THERMOCHEMICAL PROCESSES; PYROLYTIC OILS; CHEMICAL COMPOSITION; AQUEOUS SOLUTIONS; CHEMICAL REACTION KINETICS; CHEMICAL REACTION YIELD; SODIUM CARBONATES; ALKALI METAL COMPOUNDS; CARBOHYDRATES; CARBON COMPOUNDS; CARBONATES; DISPERSIONS; FUELS; KINETICS; MIXTURES; OILS; ORGANIC COMPOUNDS; OTHER ORGANIC COMPOUNDS; OXYGEN COMPOUNDS; POLYSACCHARIDES; REACTION KINETICS; SACCHARIDES; SODIUM COMPOUNDS; SOLUTIONS; SYNTHETIC FUELS; YIELDS; 090122* - Hydrocarbon Fuels- Preparation from Wastes or Biomass- (1976-1989); 140504 - Solar Energy Conversion- Biomass Production & Conversion- (-1989)

Citation Formats

Molten, P. M., Miller, R. K., Donovan, J. M., and Demmitt, T. F.. Mechanism of formation of oil by the hot aqueous alkaline digestion of cellulose. United States: N. p., 1977. Web.
Molten, P. M., Miller, R. K., Donovan, J. M., & Demmitt, T. F.. Mechanism of formation of oil by the hot aqueous alkaline digestion of cellulose. United States.
Molten, P. M., Miller, R. K., Donovan, J. M., and Demmitt, T. F.. 1977. "Mechanism of formation of oil by the hot aqueous alkaline digestion of cellulose". United States. https://www.osti.gov/servlets/purl/6226833.
@article{osti_6226833,
title = {Mechanism of formation of oil by the hot aqueous alkaline digestion of cellulose},
author = {Molten, P. M. and Miller, R. K. and Donovan, J. M. and Demmitt, T. F.},
abstractNote = {The overall mechanism of cellulose converson in hot aqueous alkali appears to be one of degradation through glucose to low molecular weight saccharinic acids, dihydroxybutyric acid, glycolic acid, and carbonyl products such as acetone, acetaldehyde, formaldehyde, and similar compounds. Although the products identified in the present report were fairly complex furans, carbocyclic ketones, unsaturated hydrocarbons, and aromatic compounds, nevertheless, in most cases, they could have been formed from simple carbonyl compounds through a series of condensations involving carbanion intermediates. It is conceivable that residual alkali in the oil during acetone extraction could have given rise to diacetone alcohol as an artifact. This is refuted by examination of an aqueous residue which was extracted with diethyl ether and which was never exposed to any acetone: Compounds derived from diacetone alcohol (such as mesityl oxide or 4-methyl-3-penten-2-one) were also identified in the diethyl ether extract of the aqueous phase. Other compounds were identified in the oil acetone extract which could not have been derived from acetone or diacetone alcohol, but which could have been formed from other carbonyl compounds by the same mechanism. Hence, diacetone alcohol is a genuine product of cellulose conversion although apparently not an intermediate in further synthesis of other products. The further reaction of the postulated cyclic intermediates, and the route to formation of unsaturated hydrocarbons of high molecular weight is intended to be the next subject of investigation in the current work. The fundamental difference in the mechanism of cellulose conversion to oil by pyrolysis and by aqueous alkaline digestion predicted by theory is therefore confirmed. Pyrolysis products may be explained generally by carbonium ion and free radical reactions (in fact, cellulose decomposition is acid-catalyzed), while in aqueous alkali, nucleophilic carbanion reactions are favored.},
doi = {},
url = {https://www.osti.gov/biblio/6226833}, journal = {},
number = ,
volume = ,
place = {United States},
year = {1977},
month = {1}
}

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