Coal oxidation at low temperatures: oxygen

consumption,
oxidation products, reaction mechanism and
kinetic modelling
Haihui Wang, Bogdan Z. Dlugogorski, Eric M. Kennedy

Progress in Energy and Combustion Science 29 (2003) 487–513

Coverage
• Understanding of the problem
• Variables affecting the oxidation process
• Experimental methods adopted
• Oxygen consumption by coal and oxidation products
• Kinetic modelling of coal oxidation
• Conclusions and suggestions for future research
Introduction
• Coal Self ignition major problems in power plants and coal mines
• May lead to loss of calorific value by upto 15%
• In Australia alone two million tons of CO2 emitted in 1 year ( 1995-96)
• Low temp oxidation takes place due to
• Coal seams getting exposed to oxygen during open cast mining
• Open storage of Coal
• Transportation
• When left in coal mines and stack yards
Process of Oxidation
• Oxygen transported to coal
surface by convective
process
• Diffusion of oxygen into
pores
• Reaction between coal and
oxygen
• Release of Heat
Research Studies in Last 150 Years
• Transport of Oxygen to coal surface and pores
• Factors causing the oxidation and characteristics of the products
• Reaction mechanism and Chemical kinetics
• Heat release during oxidation
• Propensity of coal to low temperature combustion
• Prediction of potential hazard for a seam or stockpile to spontaneous
combustion
Variable affecting the oxidation process
• Pores in the coal Particle
• Pyrites
• Inherent Moisture
• History of Oxidation
• Particle Size
• Temperature
• Oxygen concentration
• Moisture in the gas medium
Experimental Methods
Slow oxidation of coal results in
• Consumption of O2 and oxidation of Coal
• Change in coal Mass and its chemical structure
• Change in Physical structure of coal
• Self heating of coal
Parameters that are studied in experimental methods:
• Oxidation rate
• Mass exchange
• Amount of heat evolution
• Nature and Concentration of gaseous products
• Concentration of Oxygen compounds at Coal Surface
Major Methods
• Thermogravimetric Analysis (TGA)
• DGT derived from TG plot
• Indicate mass loss with time or temperature
• Used for developing kinetic model for oxidation
• Shortcomings
• Isothermal and adiabatic calorimeter
• Used for measurement of minimum self heating temperature
• Differential thermal Analysis (DTA)
• Basket Heating
• Auto ignition temperature for different sizes and shapes
• Cross Point Temperature
• Chen’s method
• Isothermal low reactor and oxygen adsorption
• FTIR and XPS for formation of oxygenated compounds of pore surfaces.
Characteristics of oxygen consumption by
coal and oxidation products.
• Physical and Chemical Adsorption of oxygen at the coal surface.
• Physical Adsorption by weak forces and easily removed
• Chemical adsorption by stronger valance forces
• Physical adsorption can be multilayer chemical adsorption is is monlayer
• Physical adsorption prominent at lower temperatures
• Chemical adsorption releases significantly more heat
• Strong dependence on temperature
Reaction regimes of Coal Oxidation
• Three step Process
• External diffusion
• Internal diffusion and
• Chemical reaction
• External diffusion is much
faster than internal
• Water layer present may
hamper diffusion
• Rate of oxygen consumption
dependent on particle
size(upto few hundred
microns) later not Fig. A typical trend illustrating the effect of particle size on
dependent. the rate of oxygen consumption
Reaction regimes of Coal Oxidation
• Brownman & Frevik proposed two modes of oxidation
• Macropore oxidation – transport of O2 is rate determining
• Micropore oxidation- Overall oxidation is limited by chemical reaction.
• Role of inherent moisture
• May promote oxidation by formation of intermediate compounds
• Higher levels of water can block pore holes.
• Critical optimum range of level exists.
• It is postulated the critical level corresponds to monolayer distribution of
water on the internal surfaces of pores.
Gaseous products of oxidations
• Presence of hydrocarbons, CO2, H2O, N2 and H2 has been observed in
coal mining sites.
• In experimental set up generation of CxHy, N2 and H2 have not been
reported.
• Generation of CO2 and CO increase with increase of temperature
• With passage of time generation of CO2 reduces.
• Molar ratio of CO2 to CO is usually higher than unity. The ratio goes
on reducing as the temperature increases.
Kinetic Modelling
Mathematical description of oxygen consumption
• Winmill
∝ ( 0<n<1)
Conclusion and future Research Areas
• Coal oxidation at low temperature is a complex process, this results in
formation of gaseous and solid products. Factors such as temperature,
oxidation history of coal, particle size, moisture content affect it.
• There are two sets of reactions that take place- direct burn-off and
chemisorption. Kinetic models have been developed relate oxygen
consumption with reaction rates, oxidation time, temperature and
oxygen concentration.
• New areas of research suggested are:
• Role of inherent moisture
• Study of direct burn-off and chemisorption reactions
• Steps in chemisorption reaction
• Prediction of CO2 emissions from stockpiles and coal seams.