The chemistry of British bituminous coals : an assessment of phase transfer catalysed reactions in the determination of coal structure

  • Shaun Burke

Student thesis: Doctoral ThesisDoctor of Philosophy

Abstract

Three British bituminous coals, (Gedling, Cresswell, and Cortonwood Silkstone)
were selected for study. Procedures were developed, using phase transfer catalysts (PTC's), to degrade the solvent insoluble fractions of the coals. PTC's are of interest because they have the potential to bring about selective high conversion reactions, under mild conditions, (often in the past, severe reaction conditions have had to be used to degrade the coals, this in turn resulted in the loss of much of the structural information).
We have applied a variety of physical and chemical techniques to maximise the
amount of structural information, these include, elemental analysis, 1H-NMR,
13C-CPMAS-NMR, GPC, GC-MS, FTIR spectroscopy, DRIFT spectroscopy, and gas
adsorption measurements.
The main conclusions from the work are listed below:-
( 1 ) PTC O-methylation; This reaction removes hydrogen bonds within the coal matrix by 'capping' the phenolic groups. It was found that the polymer-like matrix
could be made more flexible, but not significantly more soluble, by O-methylation. I.E. the trapped or 'mobile' phase of the coals could be removed at a faster rate after this reaction had been carried out.
( 2 ) PTC Reductive and Acidic Ether Cleavage; The three coals were found to
contain insignificant amounts of dialkyl and alkyl aryl ethers. The number of diaryl
ethers could not be estimated, by reductive ether cleavage, (even though a high
proportion of all three coals was solublised). The majority of the ethers present in the coals were inert to both cleavage methods, and are therefore assumed to be heterocyclic ethers.
( 3 ) Trif!uoroperacetic Acid Oxidation; This oxidant was used to study the
aliphatic portions of the polymer-like macromolecular matrix of the coals. Normally this reagent will only solublise low rank coals, we however have developed a method whereby trifluoroperacetic acid can be used to degrade high rank bituminous coals.
( 4 ) PTC/Permanganate Oxidation; This reagent has been found to be much
more selective than the traditional alkaline permanganate oxidation, with a lot more structural information being retained within the various fractions. This degradative method therefore has the potential of yielding new information about the molecular structure of coals.
Date of AwardMay 1988
LanguageEnglish
SupervisorAnn Jarvie (Supervisor)

Keywords

  • bituminous coals
  • phase transfer catalysis
  • degradation
  • organic structures
  • instrumental methods of analysis

Cite this

The chemistry of British bituminous coals : an assessment of phase transfer catalysed reactions in the determination of coal structure
Burke, S. (Author). May 1988

Student thesis: Doctoral ThesisDoctor of Philosophy