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Solid Fuels as CxHyOz molecules - thermodynamic and kinetic aspects

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Marek Sciazko Leszek Stępień

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 Solid Fuels as CxHyOz Molecules – Thermodynamic
and Kinetic Aspects
Marek ŚCIĄŻKO – Institute for Chemical Processing of Coal, Zabrze - Leszek STĘPIEŃ – AGH University
of Science and Technology, Krakow, Poland
Please cite as: CHEMIK 2013, 67, 5, 379–386
Introduction
Solid fuels, including primarily hard coal and lignite originated as
a result of physicochemical conversion of primary organic substance
under the influence of temperature, pressure and in a basically
anaerobic environment. This process, referred to as a metamorphism
phase, was accompanied by, inter alia: evolution of carbon dioxide,
water and methane. The higher conversion degree was achieved
by the original organic substance, the more ordered was coal structure
and increasingly larger domains of condensed aromatic structures.
Ultimately the fuel properties are decided by the temperature-time
history of conversion, manifesting itself in the elemental composition
expressed mainly by the C, H, O, N, and S content and additionally
by the ash content. To determine technological usability of coal
additional physicochemical analyses are sometimes performed, such
as: plasticity and caking ability, when coal is used in the coke making,
and volatiles, ash characteristic temperatures or the calorific value
in the case of power generation applications. Basically, results of
performed tests refer to a specific sample of coal and unfortunately
they cannot be catalogued like in the case of pure, structurally defined
chemical compounds. The thermodynamic potential of a substance is
defined by values of standard normal functions, including primarily the
enthalpy of formation, which reflects energy effects accompanying the
conversion. In the case of chemically unidentified structures, like in coal,
of varying composition, determination of the enthalpy of formation
requires slightly different testing procedures than in the case of pure
chemical substances. The knowledge of the enthalpy of formation value
of coal organic substance allows its comparison with others, but it is
also necessary for proper balancing of coal thermal conversions. The
coal structure formed in a peculiar georeactor has specific features
characterising the susceptibility to further conversions. In its nature,
the geochemical coalification of the original organic matter is an
inhibited pyrolysis and all technological directions of coal utilisation
have a nature of thermal processes that is during the first stage they are
related to its pyrolysis, in this case being a controlled and accelerated
continuation of reactions proceeding in the coal deposit. From this
point of view the defining of coal kinetic parameters may reflect the
effect of its geochemical conversions, taking into account characteristic
parameters of the chemical composition, and also allows determining
this technological usefulness. In particular, kinetic parameters of coal
will characterise its generally understood reactivity. However, in this
case we encounter an additional difficulty related to the influence of
coal heating rate on the course of thermal decomposition curves,
which is typical of reactions proceeding in a heterogeneous system.
To compare various coal fuels and in particular their behaviour in
processes of thermal conversion it is necessary to find a method for
determination of basic kinetic parameters taking into account the
heating rate variability and the lack of knowledge about the course of
elementary reactions. Possessing the information on both the enthalpy
of various coals formation and on kinetic parameters it is possible
to determine not only the state of organic substance metamorphic
conversions, but also to classify coals for technological purposes [1].
So the paper suggests a method for determination of the enthalpy of
coal formation and of its kinetic parameters, which are subsequently
used for their classification reflecting their structure and technological
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usability. The coal classification suggested from a thermodynamic
perspective has a nature of absolute scale, while the values of kinetic
parameters of coals analysed are right for the adopted pyrolysis model
and therefore the kinetic classification is relative.
Enthalpy of formation
The enthalpy of formation represents the energy result of the
course of reactions, which resulted in the considered product
formation. For pure substances the enthalpy of formation assumes
one defined value. Instead, because of a different chemical structure
of coal the enthalpy of formation to a large extent will depend on
the rank of coal and on the structure specific for a given coal. The
balancing of coal conversion processes may be carried out based on the
knowledge of the calorific value of coal and of its conversion products
or based on the method utilising the enthalpy of formation used in
chemical thermodynamics. The latter method provides also grounds
for commercial computer codes used for process computations (EES,
ChemCad, Aspen) [2, 3, 4]. Unfortunately, in the case of coal in those
codes it is assumed that it is a physical mixture of pure elements and
because of that the enthalpy of coal formation equals zero. Such an
approach is the source of major energy balance errors.
Thermal Effect of Reaction and Enthalpy of Formation
Calorimetrically determined heat of combustion of coal differs from
the sum of the enthalpy of combustion of the elements contained in
the coal substance being in the standard state. The difference existing
between these values is treated as a definition of the enthalpy of coal
formation. A negative value of the enthalpy of formation means that the
creation of specific organic structure CxHyOz caused a release of defined
amount of heat. Hence to bring this organic substance to decomposition
it is necessary to deliver an equivalent heat, which should be considered
in the energy balance of the considered coal conversion process.
Different values of enthalpy of formation result basically from the
difference in the structure of coal organic substance. Taking into account
Polish coals classification [5] and a typical elemental composition of the
organic matter of coals quoted by Jasieńko after Roga [6], it is possible
to analyse a change of the atomic composition with increasing degree of
coalification taking into account three basic elements: C, H, and O, which
is presented in Figure 1. It is possible to notice that the greatest changes
are related to the involvement of oxygen atoms.
Fig. 1. Change in the atomic composition of various coal types (kmols
of atoms referred to 100 kg of organic matter)
• 383
 This fact was confirmed by results of experimental studies, in
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which 224 coal samples, originating from Russian [7], American [8] and
Polish [9] mines, were analysed. The enthalpy of formation dependence
on the oxygen fraction was determined based on these results, which is
presented in Figure 2. The regions of positive value can be distinguished
for the oxygen content below 4% and positive above.
Fig. 2. Enthalpy of coal formation vs. the oxygen content
The applied method for determination of the enthalpy of coal
formation consists in determination of the difference between
the enthalpy of coal component elements, being in standard state,
combustion reaction and calorimetrically determined heat of
combustion [10], which is expressed by equation (1).
DfH0 = DcH0 – (– Qs) (1)
where:
ΔcH0 – [kJ/kg daf] enthalpy of coal elements combustion
ΔfH0 – [kJ/kg daf] enthalpy of coal formation
Qs – [kJ/kg daf] calorimetric heat of coal combustion.
This method gives the same result in the case of elemental carbon,
and more precisely of its allotropic form of hexagonal graphite, for which
the standard enthalpy of formation is equal to zero. Thermodynamically
determined enthalpy of elements combustion reaction ΔcH0 is described
by relationship (2). The numerical coefficients in this equation were
calculated based on standard enthalpy of the combustion of elements
(C, H, S), and element fractions are given in percentages of dry matter:
DcH0 = –327.633Cdaf – 1417.892Hdaf – 92.768SCdaf, kJ/kg (2)
The difference between the calorimetric heat of coal combustion
(Qs>0) and the enthalpy of combustion of the constituents
(DcH0 <0) depends on the structure and elemental composition of
coal. It is therefore desirable to derive a correlation between the heat
of combustion and the enthalpy of the combustion reaction of coal
constituents. In general, such relationship may be expressed in the
form of the following equation:
– Qs = DcH0 f(θ) (3)
where: f(θ) is the function correcting the enthalpy of combustion
reaction which expresses the ratio of the absolute values of
combustion heat and of the enthalpy of the combustion reaction of
the constituents.
Based on the analysis of the effect of the individual elements on
the heat of combustion, an assumption was made that the correcting
function f(θ) depends on the oxygen concentration in coal Oddaf. As this
is an empirical function, it is expressed in the form of a power series.
f(θ) = 1+ a1θ + a2 θ2+ a3 θ3 + a4 θ4.... (4)
where θ is the oxygen content expressed in mass percentage.
384 •
The constant coefficients in equation (4) were determined
by correlating experimental data; the results obtained are listed
in Table 1.
Table 1
Coefficients of correcting equation (4)
Coefficient a1 a2 a3 a4
Value 4.852∙10 -3
-1.437∙10-3
8.467∙10-5
-1.66∙10-6
As a result of the model adopted, the enthalpy of coal formation
ΔfH0 is described by relationship (5) resulting from the combination of
equations (1) and (3).
DfH0 = DcH0 [1–f(θ)] (5)
The enthalpy of formation for any coal fuel may be calculated
after determination of elemental composition and then calculation of
the correcting coefficient described by the oxygen content function.
Calculations should be carried out for dry ash-free state. The results
obtained, if necessary, may be transposed to the actual conditions with
account taken of water or ash content. When elemental composition of
fuel and oxygen content are known, then model (5) enables calculation
of the value of standard enthalpy of coal formation. This was the basis
for drawing up a new thermodynamic classification of Polish coals,
which is shown in Figure 3.
Fig. 3. Thermodynamic classification of Polish coals [1]
As can be seen, the enthalpy of coking coals formation is nearly
zero. The enthalpy of anthracite formation is positive, though very low.
All other types of coal have negative enthalpies of formation and the
younger the coal the higher the absolute value of formation enthalpy.
Kinetics of Solid Fuels Decomposition Reaction
Coal is a complex solid substance and therefore in kinetic modelling
we use a simplified approach, allowing however representing the
actual conditions. Thermal conversions of coal with chemical structure
difficult to define and texture changing during the conversion make
that many model approaches originated so far, taking into account the
reaction order, autocatalytic and diffusion effects as well as structural
changes [11]. Various points of view on the pyrolysis kinetics may be
found in the literature; however, the basis for all analyses consists of
a decomposition reaction model, proceeding in accordance with the
following notation, presenting as a result an individual irreversible
reaction of thermal decomposition of coal:
k
Coal ⎯→ Xvolatiles +(1–X)char (6)
In the literature this notation is frequently considered
oversimplified, because it skips significant intermediate stages of
coal decomposition, including primarily the consecutive and possibly
parallel nature of the decomposition reaction of primary coal tar
(metaplast) postulated already by Van Krevelen [12]. Because of
nr 5/2013 • tom 67
that many forms of kinetic equation have been formulated, dividing
also the pyrolysis into individual stages [13]. However, a comparison
of various schemes of coal organic matter decomposition course
leads to a conclusion that irrespective of the path for final products
achieving, the notation expressed by relationship (6) reflects the final
result of pyrolysis. As a result, numerous authors approximate the
process of coal decomposition by the first order reaction proceeding
evenly throughout the particle volume [14, 15]. In such a case the
volatiles evolution rate can be described by the relationship:
(7)
Where: at time t→ ∞ the amount of evolved volatiles
V approaches V0daf. It is assumed that the reaction rate constant is
described using a classical Arrhenius law in the form of:
k= k0exp (–E/RgT) (8)
The adoption of the above approach allows determining averaged
values of activation energy E and the frequency factor k0 for the
studied pyrolysis range. These values were determined based on
results of thermogravimetric studies carried out at the Institute for
Chemical Processing of Coal. Pyrolysis of coals of various coalification
degrees was carried out on a laboratory scale using a LECO TGA-
501 thermogravimetric analyser, using samples weighing 1–5 g. The
instrument measures changes of mass at 0.00025 g sensitivity of the
balance. The studies were carried out in a nitrogen atmosphere at the
heating rates of 5 K/min, 20 K/min, 40 K/min and 99 K/min and at the
following final temperatures: 450, 550, 600, 650, 700, 750, 800, 850
and 900°C. Pyrolysis was carried out for coal samples preliminary dried
to a constant mass, at the temperature of 105°C [1]. Both the activation
energy and the frequency factor were determined using the method of
error minimisation between the measured data of mass (volatiles) loss
and the model equation. Values of activation energy for various coal
types and at various heating rates are presented in Figure 4.
Fig. 4. Activation energy versus coal grade and heating
rate – m, K/min
Similar results were obtained for the frequency factor taking into
account the influence of heating rate. A detailed analysis allowed finding
the relationship between volatiles content in coal, its heating rate
and appropriate kinetic parameters. Equations (9) and (10) present
appropriate correlations.
E= [–204.61n(m) – 267.2] •V0daf + [11023.21n(m) + 15775.0] (9)
1n(k0)= [–0.035ln(m) – 0.029] •V0daf + [3.0571n(m) – 8.265] (10)
Assuming the above model equations the simulation calculations
were performed for the “Zofiówka” coal for various heating rates
m = 5, 15, 50 and extrapolated for 1000 K/min and the results are
presented in Figure 5. It is possible to notice that an increase in the
nr 5/2013 • tom 67
heating rate moves appropriate mass loss curves to the right. Because
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of that to compare kinetic properties of individual coals it is necessary
to indicate a reference heating rate. Assuming that this rate is 5 K/min
we obtain the relationship between kinetic parameters and volatiles
content in coal, presented in Figure 6. So it is possible to use the
presented methodology for solid fuels classification.
Fig. 5. The influence of the heating rate m K/min on the yield
of volatiles for “Zofiówka” coal
Fig. 6. Activation energy and frequency factor versus volatile contents
for studied coals at m=5 K/min
Conclusions
A general methodology for the calculation of enthalpy of
formation and respective kinetic parameters was proposed for fuels
characterized by undefined chemical formula. Taking that into account
the study resulted in a suggestion for coal classification models from
thermodynamic and kinetic perspective, reflecting its structure and
technological usability.
A uniform method for determination of the enthalpy of coal
formation has been developed, which is related to the heat of
combustion and to the enthalpy of combustion reaction of constituent
elements of coal, either calculated as the difference between these
values or expressed by model (5). As a result of kinetic analysis of
experimental data, correlations have been prepared taking into
account both the influence of the coal type and of the heating rate on
the change of kinetic parameters, i.e. the activation energy and the
frequency factor. The results obtained shows that between V0daf and
kinetic parameters E and k0 there are roughly linear relationships. The
developed methodology is helpful for comparative studies between
various solid fuels of CxHyZy type.
Acknowledgements
Work performed under task of research No. 3 funded under the Agreement
NCBiR No. SP/E/3/7708/10 and within AGH in Krakow statutory work
No. 11.11.210.213.
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