The determination of the specific heat capacity of coal

science • technique

based on literature data

Bartosz LEŚNIAK, Łukasz SŁUPIK, Grzegorz JAKUBINA – Institute for Chemical Processing of Coal,
Zabrze, Poland

Please cite as: CHEMIK 2013, 67, 6, 560-571

Introduction unit weight. These values ​​are ​​intensive, which means that they are
The optimization of chemical processing of coal requires a lot not dependent on the amount, but the type of material, as well as
of research and analysis. Understanding the phenomena, that occur physical conditions of heating.
during the process of coal gasification or pyrolysis, allow to control In the case of coal at elevated temperatures irreversible changes of
them in such a way, as to achieve the best results, which is the highest carbonaceous material associated with the release of volatile matter:
quality product with minimal energy consumption and no emissions coal → solid carbonaceous material+released volatiles. For this
into the environment. Increasingly, for this purpose, mathematical reason, determination of the specific heat capacity of coal as a function
models of the process are used. The model of process in the coke oven of temperature is a complex one.
chamber is being constructed at the Institute for Chemical Processing Using the following formula for calculating the specific heat
of Coal and realized within the framework of a key project “Smart capacity of the coal charge in the temperature range of 100–300oC
coke plant fulfilling requirements of best available techniques”. The was proposed by Hoffherr [3]:
coupled numerical model of thermal-hydraulic processes occurring
during the carbonization of coal in the coke oven chamber includes
diffusive, convectional and radiative heat transfer, as well as flow (1)
of the gas in porous material which the coal is. In addition the
evaporation and condensation of moisture are also included as well
as the release of volatiles and additional effects, which are derivative where:
of pyrolysis, such as a change of the charge density, transverse cp(100–300 °C) – specific heat capacity at constant pressure in the
shrinkage and formation of the plastic layer and its movements. To be temperature range 100–300oC, kcal/kg/K*
able to simulate the most reliably coupled processes of the heat V – volatile matter content on the dry, ash-free basis, %
daf

and mass exchange with chemical reactions occurring at the same t – temperature, oC.
time, is necessary to know the changes in various parameters with
increasing of temperature. One of the basic parameters necessary Above this range of temperature, the correlation cp=f(t) for the
to describe the accumulation element of discretized energy equation coal can be extrapolated similarity to graphite, using the regression:
is the specific heat capacity. Mathematical modeling of coking coal
process comes up with a number of difficulties. In the case of complex (2)
organic matter such as coal, we have to deal with the structure of
unidentified chemical compounds that are also contaminated with where:
a mineral substance. Thus, even the selection of the necessary cp(300–1100 °C)– specific heat capacity at constant pressure in the
thermodynamic parameters of the coked coal model represents temperature range 300–1100 oC, kcal/kg/K*
a number of questions. Theoretically, it is possible to obtain a part f0,f1,f2,f3,f4 – coefficients of equation
of data by laboratory tests. However, due to the limited possibility t – temperature oC.
of obtaining the sufficiently wide spectrum of data in this way, these
parameters are usually given in different correlations that capture For the determination of the specific heat capacity of coal, approach
the series of known characteristics of coal. One of the relevant presented by Kirov was used by Eisermann [4]: coal is separated into the
thermodynamic parameters of coal, which is the component of following component substances: fixed carbon, primary volatile matter
physical internal energy is the heat capacity. The value of the specific (released at lower temperatures), secondary volatile matter (released
heat capacity of any substance depends mainly on temperature [1]. at higher temperatures), ash and moisture. Assumed, that the volatile
In the case of coal, its carbon content, the moisture content, volatile matter in a dry, ash-free basis exceeding 10% should be considered
matter, and the composition and content of ash have great influence as the primary, and up to 10% as the secondary volatile matter. For
on the specific heat capacity value. Specific heat capacity of coal example, if the coal contains 26% volatile matter in the dry, ash-free
usually increases with moisture content, decreases with carbon basis that means that the primary volatile matter is 16%, and 10% is
content and increases with volatile matter content [2]. the secondary. If the volatile matter content is less than 10%, there are
only the secondary volatiles. The specific heat capacity of fixed carbon
Specific heat capacity of coal as a function of temperature in the dry, ash-free basis according to Eisermann proposition can be
and volatile matter calculated by the following equation:
Heat capacity is the quantity of heat required to change the
temperature of substance by a given amount. The international SI unit (3)
of heat capacity is J/K. This value is dependent on the amount of the
substance. Derivatives values include molar heat capacity, which is where:
the heat capacity per mole of the pure substance and the specific heat cpF – fixed carbon specific heat capacity at constant pressure on dry,
capacity (more properly referred to as a mass specific heat capacity ash-free basis, kJ/kg/K*
and less accurately the specific heat), which is the heat capacity per T – temperature, K

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 In turn, the specific heat capacity of primary and secondary volatile

science • technique
matter can be calculated by the following equations: (10)

(4) where:
cp – specific heat capacity, kJ/kg/K*
Vdaf– volatile matter on dry, ash-free basis
T – temperature, K
(5)
a(T), b(T), c(T), d(T) – coefficients defined by the following polynomials:

where: (11)
cpV1, cpV2 – specific heat capacity of primary and secondary volatile
matter, kJ/kg/K* (12)
T – temperature, K.
(13)
The total specific heat of coal in the dry, ash-free basis is the sum
of the above components: (14)

(6) In turn, Postrzednik [9], on the basis of the literature data concerning
the measurements and research of the specific heat of coal, developed
where: the following correlation to determinate the specific heat capacity of
cp – the specific heat capacity of coal on dry, ash-free basis, kJ/kg/K* coal as a function of the temperature and volatile matter content on
F,V1,V2 – mass fraction in dry, ash-free basis, respectively of fixed carbon, dry, ash-free basis:
primary and secondary volatile matter. for t ≤ 100 oC

Recently, the correlation for the determination of the dependence (15)
of the specific heat capacity of coal most often quoted in the literature
[5÷7] is based on Merrick’s model [8]. This model, based on Einstein’s where:
quantum theory of solids, describes the specific heat of coal as a function cp(t) – the specific heat capacity of coal at constant pressure in dry,
of temperature T, the molar mass of coal substance ash-free basis, J/kg/K*
M and Einstein characteristic temperature θ: Vdaf – volatile matter content in dry, ash-free basis, %.

(7) for 100 oC < t ≤ 300 oC

(16)
where:
c – specific heat capacity, J/kg/K*
R – the gas constant 8314, J/kmol/K* where:
T – temperature, K t – temperature, oC
M – the molar mass c0,c1 – coefficients defined by the following formulas:
θ1, θ2 – Einstein’s characteristic temperature respectively equal 380 K
and 1800 K. (17)
The value is determined by the following function:
(18)

(8) for 300 oC < t ≤ 1100 oC

(19)
The reciprocal of average molar mass can be determined by:
where:
(9) d0,d1,d2 – coefficients defined by the following formulas:

where: (20)
yi – the mass fraction of carbon, hydrogen, oxygen, nitrogen and
sulfur in dry, ash-free basis, (21)
μi – atomic weights of elements C,H,O,N,S (12, 1, 16, 14, 32)
(22)
To determine the specific heat capacity of coal, Richardson [5]
applied differential scanning calorimetry (DSC). Measurements
for 26 different coals in the temperature range of 300–600K were Ballast impact on the specific heat capacity of coal
made. Based on that data, polynomial correlations describing the The main components of coal are combustible, ash and moisture.
specific heat of coal as a function of the temperature and volatile The resultant specific heat capacity of coal is the weighted average of
matter were developed: components mass fraction [5]:

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 Table 1
science • technique
(23) Coal used for verified correlation to determine its specific
heat properties

Mo- Volatile Car- Hydro- Nitro- Oxy-

where: Coal Ash Sulfur
isture Matter bon gen gen gen
cp – the specific heat capacity of coal, J/kg/K*
  Wa Aa Va Ca Ha Na Sca Oda
wi – mass fraction of coal components,
cpi – the specific heat of coal components, J/kg/K* Bobrek-Centrum 3.4 22.3 26.3 60.90 4.20 0.90 0.30 8.00

Janina 11 9.0 28.2 63.92 4.68 0.75 0.83 9.82

Due to the fact that combustible is the main component of
coal, to determine its specific heat exact determination is required. Jas-Mos 0.8 6.6 20.9 84.26 4.34 1.23 0.33 2.44
The specific heat of ash and moisture can take approximate values.
According to Postrzednik [9], value of the specific heat of ash is Krupiński 1.5 9.5 32.9 75.50 4.78 1.41 0.71 6.60
respectively 950 J/kg/K*.
Pniówek 1.1 6.9 26.2 81.97 4.68 1.39 0.66 3.30
In the Kirov approach [4], applied also by Merrick [8], the specific
heat capacity of ash contained in the coal is determined according to: Zofiówka 0.8 7.3 22.5 83.01 4.44 1.24 0.55 2.66

(24)
For each of examined coals, the specific heat capacity on dry,
ash-free basis were calculated at the given temperature. Changes in
where:
the specific heat capacity of the combustible in the coal on dry, ash-
cpA – the specific heat of ash, kJ/kg/K*
free basis, as a function of temperature in the range of 300 to 600 K
T – temperature, K.
are shown in Figures 2÷5. Assuming that there are no changes of
However, Tomeczek [6] on the basis of the tested samples,
carbonaceous material in this range of temperature, the composition
established the following formula for the specific heat capacity of
of coal does not change. The specific heat capacity depends only on the
mineral matter (ash):
temperature and basic parameters of coal. In Figures 3÷5 the lines that
show the change of the specific heat capacity on the graph for Janina
(25)
coal coincide with the lines for Bobrek-Centrum coal.

where:
cpA – the specific heat of ash, kJ/kg/K*
t – temperature, oC.
Values ​​obtained according to the above formulas are shown in
Figure 1. In the case of formula proposed by Tomeczek the specific
heat capacity of the ash are up to 900 K almost twice as high as in
the case according to the formula proposed by Kirov. For formula
proposed by Tomeczek, at about 900 K temperature can be observed
a maximum. At higher temperatures the value ​​of the specific heat
decline and in the a temperature of 1500 K achieve the same value as
for the function proposed by Kirov.

Fig. 2. Specific heat capacity of examined coal calculated

by Merrick’s formula

Fig. 1. Specific heat capacity of ash as a function of temperature

according to [4] and [6]

Analysis of selected correlations to determine the specific

heat capacity of coal
The analysis of correlation for several coals with different properties
Fig. 3. Specific heat capacity of examined coal calculated
shown in Table 1 was made.
by Kirov’s formula

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 function proposed by Richardson, impact of this coal parameters on

science • technique
the specific heat capacity is quite the opposite. Furthermore, the
values of specific heat capacity, calculated from Richardson’s function​​
for temperature range to 600 K are much higher than those calculated
on the basis of other functions. This difference is showed on the basis
of the specific heat capacity change of “Janina” coal calculated by the
different functions (Fig.6)
In the case of functions proposed by Kirov and Postrzednik, it can
also be noted that the volatile matter has a greater impact on specific
heat than the carbon content. While in the case of the function proposed
by Merrick, carbon content has greater impact than volatile matter.
In the Figures 7÷9 the results of the same functions in the
temperature range from 300 to 1300 K are presented. It was assumed
that, in this temperature the decomposition of coal material occurs and
is connected with the change of the volatile matter content. Because of
dissimilarity, Richardson’s function is not included in these charts.
For the determination of change taking place in the coal, the
Fig. 4. Specific heat capacity of examined coal calculated simulation calculations using the model of pyrolysis developed
by Richardson’s formula
by Ściążko [10] were made. This model allows to calculate the change
of the efficiency of each evolved volatile matter component for any coal
and for any arbitrary heating rate. According to the author’s thesis, the
efficiency of a particular component is proportional to the amount of
volatile matter, and the closing model equations is the mass balance
of elements. Definitively, the generalized model of pyrolysis allows
to calculate kinetic parameters of the overall volatile matter and its
components and to determine the amount of exuded volatile matter
and its component at a given temperature. As a result of simulations,
the properties of chars obtained from each coals in the temperature
range from 500 to 1300 K were obtained.

Fig. 5. Specific heat capacity of examined coal calculated

by Postrzednik’s formula

Fig. 7. The specific heat capacity of examined coals change as

a function of temperature calculated by Merrick’s correlation

Fig. 6. The specific heat capacity of Janina coal calculated

by different functions

The results obtained for examined coals, as it is apparent from the

following diagrams, are different depending on the considered functional
describing the change of the specific heat capacity as a function of the
selected parameters. However, the specific heat capacity increases
with the volatile matter content and decreases with carbon content
for the Kirov’s and Postrzednik’s function, which is consistent with Fig. 8. The specific heat capacity of examined coals change as
the previously presented Speight’s publication [2]. In the case of the a function of temperature calculated by Kirov’s correlation

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science • technique

Fig. 9. The specific heat capacity of examined coals change as

a function of temperature calculated by Postrzednik’s correlation

As it is apparent from the presented diagrams, the character of

curves illustrating the change of the specific heat capacity as a function
of temperature proposed by Merrick and Kirov is similar. The value of Fig. 11. The specific heat capacity change as a function of
specific heat capacity is increased and reaches the maximum of all the temperature of the same coal in the various cases, calculated by
examined coals in the temperature range of 700–800 K. Above this Kirov’s function and the graphite
temperature, the specific heat capacity of coals begins to decrease. In the
case of Postrzednik’s function, the character of curves is different. The
specific heat capacity increases across the whole range, however above
the temperature range of 600–700 K the increase is insignificant.
The following Figures 10÷12 show the same results for the
“Krupinski” coal but with three various assumptions:
• the decomposition of coal that takes place under the influence
of temperature is included (coal composition is changing with
temperature)
• the decomposition of coal that takes place under the influence of
temperature is not included (coal composition isn’t changing with
temperature)
• coke obtained from the coal.
For comparison, the specific heat capacity of graphite as a function
of temperature according to two [11,12] of several known correlations
is also presented on the diagram:
(26)

(27)
Fig. 12. The specific heat capacity change as a function
of temperature of the same coal in the various cases, calculated
where: by Postrzednik’s function and the graphite
cpgrafit1,cpgrafit2 – specific heat of graphite according to [11], J/kg/K*
and [12], kJ/kg/K*
T – temperature, K.

Fig. 10. The specific heat capacity change as a function of

temperature of the same coal in the various cases, calculated Fig. 13. The specific heat capacity change as a function of temperatu-
by Merrick’s function and the graphite re of the same coal calculated by different functions

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 In both case of the functions proposed by Kirov and Merrick 3. Hoffherr K., Simonis W.: Der Zusammenhang zwischen der zeitlichen Ande-

science • technique
considering or not carbonaceous substance changes in elevated rung der Temperaturfelder bei der Hochtemperaturaturverkokung von Stein-
temperature, leads to significantly different results. Disregarding of kohle im Laboratorium, im Technikum und im Betrieb. Glückauf Forschung-
carbonaceous material changes with temperature, and consequently shefte 1971, 32.
changing its composition during application of these functions, makes 4. Eisermann W., Johanson P., Conger W.L.: Estimating thermodynamic proper-
that the calculated specific heat capacity increases in the whole ties of coal, char, tar and ash. Fuel Processing Technology 1980, 3, 39–53.
investigated temperature range (Figs. 10, 11). There is a different 5. Coimbra C.F.M., Queiroz M.: Evaluation of a Dimensionless Group Number
in the case of function proposed by Potrzednik. In that case both to Determine Second-Einstein Temperatures in a Heat Capacity Model for All
considering or not the changes, there is almost no influence on obtained Coal Ranks. Combustion and Flame 1995, 101, 209–220.
result (Fig. 12). In the case of determining the specific heat capacity 6. Tomeczek J., Palugniok H.: Specific heat capacity and entalphy of coal pyroly-
of coke, both in case of application the Merrick’s as well as Kirov’s sis at elevated temperatures. Fuel Vol. 75, No. 9, 1996.
function, obtained values ​​are substantially similar to those obtained 7. Tang H., Guo Z., Guo X.: Numerical model of coal carbonization analysis of
for graphite. If the changes of carbonaceous material are taken into a coke oven charge using PHOENICS. Proceedings of PHOENICS 10th Inter-
account obtained values ​​of the specific heat capacity at temperatures national User Conference, Melbourne, Australia, 2004.
above 500 K are beginning to fall and strive to values ​​obtained for 8. Merrick D.: Mathematical models of the thermal decomposition of coal 2.
coke (Figs. 10,11). For function proposed by Postrzednik calculated Fuel Vol 62, May 1983.
values ​​for coke differ significantly from the values ​​for graphite 9. Postrzednik S.: Analiza termodynamiczna procesu odgazowania paliw stałych.
(Fig. 12). In the Figure 13 for comparison, the results obtained from Zeszyty naukowe nr 691, Politechnika Śląska, Gliwice, 1981.
the three function, both with considering the changes and without 10. Ściążko M.: Modele klasyfikacji węgla w ujęciu termodynamicznym i kinetycz-
its considering are presented. As can be observed the character nym. Rozprawy i monografie, 210, Wydawnictwa AGH, Kraków, 2010.
of curves for function proposed by Kirov and Merrick are similar 11. http://aries.ucsd.edu/LIB/PROPS/PANOS/c.html, grudzień 2012.
to each other, but for the Kirov’s function obtained values are of 12. Szarawara J.: Termodynamika chemiczna. WNT, Warszawa, 1969.
about 10% lower than according to Merrick’s. The values ​​of specific
heat capacity determined from the function proposed by Postrzednik Work realized within a framework of key project No. POIG.01.01.02-24-
017/08 „Smart coke plant fulfilling requirements of best available techniques”
are close to the values ​​calculated by using the Kirov and Merrick,
financed by European Regional Development Fund – ERDF
taking into account the changes.

Summary
In the article an analysis of four different functions used for
determining the specific heat capacity of coal as a function of Bartosz LEŚNIAK – M.Sc., is a graduate of the Faculty of Power and
temperature is presented. For the analysis six coals were used. Environmental Engineering, Silesian University of Technology (2010).
The simulation calculations were carried out, using the pyrolysis He has been working for the Institute for Chemical Processing of Coal
model developed by Ściążko to obtain the composition of chars in Zabrze since graduation. Competence area includes a system of coke
in the investigated temperature range. For the received chars the oven battery monitoring and operation control as well as development
calculations of the specific heat capacity using a presented function of simulation models. He is co-authored of three articles in the technical
were made. As is apparent from the analysis, for the functions – scientific press.
proposed by Kirov as well as Postrzednik, specific heat capacity of e-mail: [email protected]; phone: +48 32 271 00 41
coal increases with content of volatiles and decreases with carbon
content, which is consistent with presented Speight’s publication. In
the case of function proposed by Richardson, the impact of these
parameters on the specific heat capacity is quite the opposite. Łukasz SŁUPIK received M.Sc degree in Power Engineering from the
Furthermore the values of the specific heat capacity, calculated from Silesian University of Technology. He is currently working at the Institute
the function proposed by Richardson at the temperature range from for Chemical Processing of Coal in Zabrze. His research interests
300 to 600 K are much higher than those prescribed on the basis include mathematical modelling of thermal and flow processes in coking
of the other functions. Due to the limitation of the temperature chambers.
range of applicability, the function proposed by Richardson was not e-mail: [email protected]; phone: + 48 32 271 00 41
analyzed at temperatures higher than 600 K. As was shown by further
analysis, the character of change the specific heat capacity, calculated
using functions proposed by the Kirov and Merrick is similar to each
other. In the case of using these functions significant influence on the Grzegorz JAKUBINA – M.Sc., is a graduate of the Silesian University
obtained values of the specific heat capacity is fact of considering of the Faculty of Power and Environmental Engineering, specialization
carbonaceous substance changes with temperature. In the case of Environmental Engineering. In 2009, he completed postgraduate studies
Postrzednik’s function this influence is negligible. at the University of Science and Technology in Cracow at the Department
of Fuels and Energy on „Modern Methods of Management and Technology
Translation into English by the Author in coke-making.” He has been working for to the Institute for Chemical
Processing of Coal as a senior engineering technical specialist and project
Editors’ annotation: manager for seven years.
* Symbols of units by the Author
He co-authored 5 articles and a monograph. He is also the author or
co-author of 5 papers and 3 posters at national and international
Literature
conferences. Competence areas include :construction, operation and
1. Szargut J.: Termodynamika techniczna. Wydawnictwo Politechniki Śląskiej,
modernization of coke oven batteries.
Gliwice, 2010.
e-mail: [email protected]; phone: + 48 601 057 284
2. Speight J.G.: Handbook of Coal Analysis. Published by John Wiley&Sons,
New Jersey, 2005.

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