The spontaneous combustion
of the sulfur
concentrate is the main hazard faced in ore storage bins. To understand
the thermodynamic characteristics of spontaneous combustion of the
sulfur concentrate and test whether the kinetic compensation effects
are present in the spontaneous combustion process of the sulfur concentrate,
typical sulfur concentrate samples were selected as the research object,
and thermogravimetric experiments were carried out under an air atmosphere
at heating rates of 5, 10, and 15 K/min. On this basis, the contributions
of different reaction models to the mass change during the spontaneous
combustion of the sulfur concentrate, as well as the thermodynamic
model and kinetic compensation effect, are analyzed. The results show
that solid-phase combustion contributes the most to mass loss among
different mechanisms of the reaction between the sulfur concentrate
and oxygen. The contributions of reaction models to mass loss are
affected by the different heating rates, and the contribution of solid-phase
combustion to mass loss increases with increasing heating rates. The
Malek method is used to obtain the kinetic model of the spontaneous
combustion of the sulfur concentrate, and its mechanism function changes
from a chemical reaction model to a three-dimensional diffusion model.
There is a kinetic compensation effect in the spontaneous combustion
process of the sulfur concentrate, and the level of the kinetic compensation
line may be one of the bases for distinguishing the spontaneous combustion
tendency of the sulfur concentrate.
Oil sludge (OS) is an organic solid waste in the petrochemical industry and
improper treatment of OS will cause environmental pollution. Pyrolysis is an
effective way to realize its resource reuse. In order to understand the
pyrolysis behavior and thermodynamic characteristics of OS, four OS samples
from storage tanks were used as the research object, and pyrolysis
experiments were carried out at heating rates of 5, 10, and 15?/min under a
nitrogen atmosphere. The kinetic parameters of pyrolysis of OS are
calculated by three equal conversion methods (Friedman method (FR),
Flynn-Wall-Ozawa method (FWO) and Distributed activation energy model
(DAEM)), and the most possible thermodynamic models for the main pyrolysis
phase were analyzed and discussed by introducing the Malek method. The
results show: High heating rate can promote the pyrolysis of OS; In the
pyrolysis stage, the apparent activation energy increases with the increase
of the conversion rate. The apparent activation energy calculated by the FR
method is more reliable. The average apparent activation energies of the
four OS are 221.23, 84.71, 94.67 and 116.56 kJ/mol, respectively. The
apparent activation energy and the pre-exponential factor are positively
correlated, indicating that there is a kinetic compensation effect in the
pyrolysis process. The thermodynamic models of the four OS samples are all
three-dimensional diffusion models, but their integral functions are
different. The research results can provide theoretical support for the
industrialization, harmlessness and resource utilization of OS pyrolysis.
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