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CHEMICAL ENERGIES AND EXERGIES OF FUELS

V. S. STEPANOV
Siberian Energy Institute, Russian Academy of Sciences, I30 Lermontov Street, Irkutsk 664033. Russia

(Received 9 September 1993: receiveci,fiw puhlicution 7 October 1994)

Abstract-Available methods for estimating chemical energies and exergies of fuels are described
and the results compared. One of the procedures is recommended for practical application in
improved form.

INTRODUCTION

The correct estimation of the energy value supplied to a process by fuels is important. The lower heating
value Q: has generally been chosen in this country. Calculations using Q: mean that we artificially
decrease the energy expenditure for energy and production processes and overestimate their energy
efficiency.
As the result of introduction of contact economizers in gas-fired boilers, efficiencies calculated by
using existing methods may exceed loo%. Therefore, a question arises about using the higher heating
value Q,. In addition to steam, the waste gases contain other components which may be incompletely
devalued with respect to energy contents. Therefore, Q, is not the total potential energy for a fuel. Its
chemical energy and exergy show this potential.

METHODS

Estimations of chemical energies and exergies of fuels with complex but known compositions are
performed as for other chemicals. Gaseous fuels include natural gas, shale-derived gas, coke-oven gas,
blast furnace gas, etc. These are mixtures of components containing hydrogen, methane, butane. etc.
The energies and exergies are calculated, respectively, from the relations

i,.,, = C u, i:$, e,.,, = x u, e:!,, (1)

I,
I I

where vi = mass fraction of chemical element or compound j and i:;,,, e:;, = specific chemical energy
and exergy of the element or compound j, respectively. Since many solid and liquid fuels (e.g., hard
and brown coals, coke, peat, wood, oil, fuel oil, etc.) have unknown structures with known chemical
compositions, we cannot estimate energies and exergies because of the lack of standard enthalpies of
formation and absolute entropies.
Several methods for estimations have been proposed.3m7 The bases for these methods are similar.
Relations between different characteristics of homogeneous organic substances are determined and then
transferred to fuels with unknown structures. Since different authors often used data for fuels from
different countries with statistical samples of homogeneous organic substances, the suggested
expressions and resulting values differ substantially. It is therefore difficult to choose a best procedure.
We have compared different methods and some of the results will now be presented. Rant was one
of the early workers to suggest use of analogies for homogeneous organic fuels. After estimating chemi-
cal exergies of many homogeneous organic fuels, he calculated the ratios of exergies to heating values
and then estimated average values of these ratios for both liquid and gaseous fuels. Assuming that these
ratios are also valid for fuels with unknown structures, he proposed to estimate the chemical exergy
of a liquid fuel if its molecule contains more than one atom of carbon from the relation

e,,, = 0.975 Q>, (2)

and the chemical exergy of a gaseous fuel if its molecule contains more than one atom of carbon from
235
236 V. S. Stepanov

e,.,,= 0.95 Qs. (3)

In Rants view, a solid fuel may be considered to be a mixture of C, S and free H. The quantity of
free H is the remainder after reacting all 0 with H to form Hz0 in the liquid phase, (H,O)ri,. Assuming
that the exergies of C, H and S differ negligibly from their heats of combustion and equating the exergy
of water contained in the fuel to zero, Rant obtained the following relation for hard and brown coals:

e<.,,= Qt. (4)

Szargut and Styrylska4 made an attempt to correct Rants formulas by taking into consideration the
chemical composition of fuels. They obtained the correlation formulas expressing dependence between
the ratio of the standard chemical exergy to the heat of combustion and the numbers describing the
chemical composition of the fuel. The mass ratios H/C, O/C, N/C and S/C were taken as such numbers.
The formula for calculating the chemical exergy of a solid fuel (on the basis of as received mass)
obtained by the authors has the following form:

ech = (Q; + r,,. W) (1.0437 + 0.1896 IF/C + 0.0617 Or/c + 0.0428 M/c) + 9710 $:, (5)

where r,, = heat of moisture evaporation; W, S: = total mass content, respectively, of moisture and
sulphur in the fuel; F/C, O/C, M/C? = ratios of mass fractions of hydrogen, oxygen and nitrogen
with respect to carbon. The authors of Ref. 4 suggested the following formula for estimating exergies
of liquid fuels:

e& = (Qf + I-,,,W) [1.0401 + 0.1728 B/C? + 0.0432 OlC + 0.2196 x/C? (1 - 2.0628 IF/C)]. (6)

The expression for calculating chemical energies suggested by them has the form

&h = Q: + mso,iS02, (7)

where mso2 = mass of SO* obtained as the result of combustion of the sulphur contained in the fuel,
so* = enthalpy of devaluation (the chemical energy) of SO,.
Zakharovs tried to correct the relations obtained by Szargut and Styrylska for another reference level.
Taking account of the different reference levels used by many researchers, he proposed to call the
exergy estimated by Szargut a higher and that estimated by Rant a lower value. Zakharov considered
it expedient to carry out all calculations using the lower exergy and an analogy with the heat of combus-
tion. In this case, the relations for estimating the lower chemical exergy were obtained by Zakharov
by eliminating the residual exergy components from the formulas proposed by Szargut and Styrylska.
Zakharov recommended the following formulas:
for hard coals and anthracites,

0.131 0+0.116 W
Q: ; (8)
100 - (A+ W) I

for brown coals and peat,

0.267 0 + 0.103 W
Q; ; (9)
100 - (A+ W) I

for low-sulphur residual oils,

cc./,,= 1.O1 Qr ; (10)

for sulphurous residual oils,

 Chemical energies and exergies of fuels 237

ed,, = I .02 p: (11)

Here, A, W = ash and moisture content of a fuel, respectively; 0 = content of oxygen in the as
received fuel mass.
Based on the idea of using structural formulas for the heat of combustion, Fratzscher and Schmidt
proposed to describe the exergies of fuels by using non-dimensional coefficients. Approximate equations
for the heat of combustion can be derived relatively easily because the calculated values may be com-
pared with values obtained experimentally. It is, however, necessary to know the entropy change for
the combustion reaction to estimate the exergy of a fuel, which is the case if the entropy of the fuel
is determined beforehand.
Fratzscher and Schmidt expressed the entropy of coal as a weighted sum of entropies of its elements.
Instead of the entropy of carbon, they substituted a quantity which accounted for the entropy of chemical
bonding. They allowed only for entropy of formation of carbon compounds with hydrogen contained
in the volatile components of coal. They did not consider entropy changes in the formation of other
chemical bonds. As a result, the following expression was obtained for estimating exergies of all sorts
of coals:

e.,,,,,,,= K (809.1 + 67.4 w + 187.5 v + 3784 o - 177.8 5) , (12)

where K=7.817kJ/kg C; v=(3/7) N/C, o= 1 +3 [H-(0-S)B]lC; 0=6 H/C; {=(3/g) S/C. It

follows from the atomic composition that C + H + 0 + S + N = 1. Exergies of raw and refined oils were
calculated from the relation

e, .,,,,,,= K (1066 + 67.4 w + 1875 v + 3784 (T - 177.8 5) , (13)

which differs from the equation for coals in the constant term.
An interesting study of energies and exergies of materials with complex structures was carried out
by Shieh and Fan.7 They assumed that 1 kg of combustible mass of the fuel with the formula C,,, H,,
N,, 0, X,. S, undergoes the following combustion reaction:

2 (m + t) - q + (n - r)/2
CmH,,N,,0, X,.S,+ 2
02 -
1
+ m CO? + [(n - r)/2] (H,O),i, + (p/2) Nz + r H X + t SO?,

where the subscripts m, n, p, q, r, and t = number of atoms of the elements C, H, N, 0. halogens X.

and S, respectively, in 1 mole of combustible mass of the fuel.
In accord with material and energy balances for the combustion process and the chosen values of
specific chemical energies of substances participating in the reaction, Shieh and Fan obtained the for-
mulas for calculating energies of fuels for following two cases: when the heat of combustion AH, is
determined experimentally and when it is unknown. For the second case, the authors assumed that all
combustible constituents of a fuel (carbon, nitrogen, hydrogen, sulphur, halogens) are represented in
their elementary states and that their properties are additive.
Shieh and Fan also obtained analogous formulas for the exergies of fuels. They used the well
known expression

AC;) = AM. - r,, A,!$ (14)

and also the assumption that the entropy of a fuel equals the sum of the entropies of the elements
forming it and ash. In this expression, AS, is the entropy change for the combustion reaction under
standard conditions (T,, = 298.15 K, p,, = 101.325 kPa).
In our comparative analysis, we corrected the equations obtained by Shieh and Fan. It was first
necessary to reduce all methods to the same reference data. Our corrections consist of using our own
238 V. S. Stepanov

values for the specific chemical energies and exergies of substances contained in a fuel and formed
during its combustion.
For the case when the value of AH, is experimentally determined, the calculations are carried out
by using the expressions

ic.,,,.=10218.75 [S] + 3058.217 [F] + 2132.1 [Cl]

+ 2560.06 [Br] + 2020.17 [I] - AH:,

qhr = 70.746 [Cl - 24 150.743 [H]+ 4327.948 [ 0] + 7060.306 [S]
+ 1547.588 [F] + 1774.422 [CI] + 1750.363 [Br] + 1463.267 [I]

- 298.15 Vashs;~,,- AH; . ( 16)

When the calorimetric characteristics of the fuels were not known, the values of the chemical energy
and exergy were estimated by using the following expressions

i+.= (1 + 0.15 [O]) i32833.333 [C] + 141865.08 ([H]- [0]/8

1
+ 19500 [S] + 9789.474 [F] + 705.06 [Cl] + 1226.288 [Br]

+ 685.471 [I] I , (17)

Q,,. = 32904.076 [C] + 2040.24 [N] + 117714.337 [H]

+ 16341.556 [S] - 13405.192 [0] + 8278.838 [F]
+ 348.382 [C!] + 416.593 [Br] + 128.567 [I]

- 298.15 Vash
s:,,,
+ 0.15 [0] i32833.33 [C] + 141865.08 [H]

- [0]/8+ 19500 [S] + 9789.47 [F]+ 705.06 [Cl]

+ 1226.29 [Br] + 685.47 [I] (18)

In these expressions, the letters in the square brackets are mass fractions of the elements; Va,,,= mass
of ash in 1 kg of the fuel; SO,,,,= specific entropy of ash.
We observe that the last method is the most useful although the calculations of entropies are not
performed entirely correctly. Therefore, we proposed to use it in combination with a better method for
estimating the entropy of a fuel, as described in Ref. 8, where empirical expressions are obtained on
the basis of statistical studies of corresponding characteristics of uniform organic substances. For solid
fuels, the proposed expression may be applied only to the organic part; the influence of the mineral
part and moisture must, however, also be taken into account. The following expressions for calculating
entropies were obtained:
for liquid fuels,

S,.= 4.69 +18.41 (HJC,)+ 44.61 (0,/C,) + 86.01 (NJC,) + 86.61 (SJC,) ; ( 19)

for solid fuels,

Sr= 5.69 + 13.12 (HJC,,)

+ 14.19 (OJC,) + 21.45 (NJC,) . (20)

Here, (HJC,), (0,/C,), (NJC,), (SJC,) = ratios of the number of moles of hydrogen, oxygen, nitrogen,
and sulphur, respectively, to the number of moles of carbon in the organic mass of the fuel.
 Chemical energies and exergies of fuels 233

Table 1. Energies and exergies NC from different producing tields.

Composition of dry gas (vol. r/r)

Q: Cl> r,t,
Field CH, C,H,, C& C,H,,, C,H,, NZ tMJ/m) (MJ/m) tMJ/m)

Orenburg 82.1 3.69 I so I .40 2.2 9.2 3X.26 42.44 39.23

North-Stavropol 9X.6-99.1 0.3-0.4 0.12-0.23 0.05%O.lS 0.0-0.05 0.93-0.07 35.6X-36.21 39.63-40.22 36.40-36.95
Berezovo 8X.X-94.8 0.1-0.8 0.05-0.20 0.0-0.05 - I I .05-4.15 3 I .92-34.7 I 35.46-38.55 32.56-35.41
Medvezhic 99.0 0. I _ _ 0.9 35.05 39.47 36.24
Urengoi 98.0 0. I _ _ _ I .9 35.53 39.07 35.87
Ust-Viljui 92.1-93.8 0.7-2.9 0.0-1.0 0.0-0.6 0.0-O. I 7.2-1.6 33.44-37.22 37.14-41.27 34.1 I-38.00
Shebelinka 91.1-92.2 4.3-4.8 0.9 0.3-I .2 _ 3.4-0.9 36.55-38.33 40.53-42.47 37.32-39. IS
Carli 95.0 3.0 0.3 0.2 0. I I .4 36.60 40.6 I 37.35
South-Mubarek 85.X-90.9 I .3-3.x 0.4-0.9 0.1-1.5 0.2-1.8 12.2-1.1 32.34-40.21 35.x9-44.53 33.0&41.15
Kyzylkum 91.8-92.X 0.4-1.5 I .4-2.3 2.2-2.7 0.2-0.7 4.0-0.0 37.32-40.52 41.34-44.83 38.12-41.42

CALCULATIONS

Estimations of the chemical energies and exergies were performed for a large group of gaseous,
liquid and solid fuels found in the former U.S.S.R.~ The results obtained for the gaseous fuels are
presented in Table 1 for natural gas from different fields and in Table 2 for coke-oven gases from
different metallurgical mills. This analysis has shown that the chemical energies of natural gases are,
as a rule, significantly higher (by 11%) than Q\ while the exergies exceed Q; by approximately 2%.
Differences in chemical energies for the coke-oven gases are 13% and for the exergies approximately
equal to Q;. In practice, this means that using the lower calorific value for calculations, we overestimate
the efficiencies of gas-burning units in direct proportion to ich > Q:.
The results of calculations of chemical energies and exergies of solid and liquid fuels are presented
in Tables 3 and 4, respectively. Analysis of the results allows one to draw the following conclusions:
values of the fuel energies obtained by the Szargut-Styrylska method are always lower than Q, by 0.8-
3.6% for solid and 4.0-5.8% for liquid fuels. The values calculated by using the Shieh-Fan method
are higher than Q, by 0.1-I 1% for both solid and liquid fuels, depending on their chemical composition.
The Rant method gives i,.,,= Q,.
The values of chemical energies of liquid fuels obtained by using the Shieh-Fan formulas when Q:
and Q, are unknown are. as a rule, OS-3.5% higher than the values obtained experimentally. The values
ich for solid fuels can be both higher and lower than the values obtained by using Q: and (2, (from -3.0
to +5.0%).
As can be seen from Table 4, values of the exergies of solid fuels calculated by the use of all of
the methods are always higher than the ech from the Rant method. The exergies of liquid fuels obtained
by using the Szargut-Styrylska and Fratzscher-Schmidt methods are l-4% higher than those from the
Rant method. On the other hand, the chemical exergies obtained by using the Zakharov, Shieh-Fan
and combined methods are l-4% lower.
The exergies of solid fuels calculated from the Shieh-Fan method when calorimetric data are unavail-
able differ from those obtained using Q: and Q, by -3.0 to +3.5%. The exergies for liquid fuels when

Table 2. Energies and exergies of coke-oven gases of different metallurgical mills.

Composition of gas (vol. C/r)

Q: ,I, e,r1
Mill CO? co H2 CH, C& N, + Oz (MJ/m) (MJ/m) tMJ/m)

Magnnogorsk 2.4 7.5 57.5 23.2 2.1 7.3 16.81 19.00 16.81
Karaganda 2.5 7.0 60. I 24.2 2.5 3.7 17.64 19.95 17.66
West-Siberian 2.x 6.X 57. I 24.4 2.9 6.0 17.61 IO.90 17.65
Cherepoveta 2.6 6.9 59.4 24.X 2.4 3.9 17.70 20.02 17.73
Lipetsk 2.3 7.X 49.6 30.7 I .7 7.9 I x.42 20.74 I x.49
Krivoi Rog 2.5 6.4 60.8 25. I 2.2 3.0 17.77 20. I I 17.x0
Chelyabinah 3.2 7.0 57.0 25.3 2.5 5.0 17.70 19.99 17.73

EGY 20-3-F
240 V. S. Stepanov

Table 3. Comparison of energy values of solid and liquid fuels obtained by different methods

i,, from the method of

Basin, deposit. sort of fuel Q: Rant Szargut & Styrylska Shieh & Fan

I 2 3 4 5

Solid fuel
Donetsk basin. coal:
- long-flame 17.25 18.28 17.94 18.77
I8.59t
- gas 18.92 19.90 19.56 20.40
20.52.t

Moscow basin (average)

- brown coal 8.67 9.88 9.80 10.58
10.12t

Pechora basin. coal:

- long-flame 16.87 17.78 17.48 18.20
17.9ot
- fat 20.77 21.66 21.11 21.85
21.55t

Kuznetsk basin. coal:

Subterranean mining
- long-flame 21.90 23.50 22.23 23.10
22.95t
- weak-caking 25.33 26.29 25.59 26.34
26.20t

Open-pit mining
- long-flame 21.39 22.52 21.75 22.58
22.36)
- gas 23.1 I 24.22 23.39 24.28
24.311

Liquid fuel
Gas shale tar 38.49 40.75 38.68 40.82
41 .OSt

Chamber shale tar 37.14 38.92 37.33 38.99

39.07t

Residual oil:
- F5 41.93 44.56 41.98 44.59
45.56:
- F12 41.57 44.13 41.64 44.18
45.29t
- Saratov M40 40.15 42.59 40.52 42.85
44.23t
- Orsk M40 40.80 43.24 41.09 43.44
44.32t
- Omsk Ml00 39.74 42.07 40.12 42.34
43.28:
- Krasnodar Ml00 40.23 42.67 40.37 42.72
43.93:

tValues not based on experimental measurements of a.

Q: and Q, are unknown are, as a rule, OS-3.5% higher than those based on the experimentally obtained
calorimetric values.

CONCLUSIONS

Chemical energies and exergies reflect more correctly and completely the energy potentials of fuels
than the calorimetric values QI and Q., that are generally used in practical calculations. Using chemical
 Chemical energies and exergies of fuels 241

Table 4. Comparison of exergy values of solid and liquid fuels obtained by different methods.

L,~ from the method of

Combined
Szargut & Fratzscher & method
Basin. field, sort of fuel Rant Styrylska Zakharov Schmidt Shieh & Fan (S, by Ref. 8)

I 2 3 4 5 6 7

Solid ,firel
Domxsk hosirt. coal:
- long-flame 17.25 19.07 18.15 18.28 17.86 18.36
18.05: 18.35:
- gas 18.92 20.70 19.67 20.2 I 19.30 19.94
19.85t 20.24t

Moscow basin (average)

- brown coal 8.67 10.46 9.75 9.9 I IO.00 IO.10
9.90t 9.94t

Pechora basin. coal:

- long-flame 16.87 18.58 11.72 17.90 17.52 17.91
17sot 17.73t
- fat 20.11 22.36 21.45 21.60 20.82 21.51
20.90: 2 I .34f

Kummk basin, coal:

Subterranean mining
- long-flame 21.90 23.76 22.89 22.97 22.37 22.85
22.411 22.76;
- weak-caking 25.33 27.06 26.05 26.62 25.45 26.04
25.53.t 26.00:

Open-pit mining
- long-flame 2 I .39 23.24 22.42 22.47 2 I .96 22.34
21.9l.I 22.19t
- gas 23.1 I 24.92 22.98 24.32 23.42 24.00
23.681 24.1 Ot

Liyuirl,fuel
Gas shale tar 39.73 41.07 38.88 40.39 38.56 39.33
38.92t 39.66:
Chamber shale tar 37.95 39.43 37.5 I 39.65 37.27 37.73
37.421- 37.86t

Residual oil:
- F5 43.44 44.65 42.35 43.94 41.76 43.22
42.74: 44.20:
- F12 43.03 44.26 41.99 43.78 41.41 42.70
42.48t 43.76t
- Saratov M40 41.52 42.89 40.95 42.88 40.15 39.94
41.58.t 4 I .37t
- Orsk M40 42.16 43.52 41.62 43.06 40.16 40.96
41.691- 41.89t
- Omsk Ml00 41.02 42.44 40.54 42.15 39.79 39.43
40.77i 40.42 t
- Krasnodar M IO0 41.61 42.85 40.68 42.95 40. I7 41.37
41.42f 42.61 f

+Values not based on experimental measurements of Q:.

energies and exergies for analysis of energy efficiencies in energetic and technological processes may
greatly change the estimated levels of efficiencies for different technical systems.
For practical use, we recommend a method based on both the Shieh and Fan method and that of
Ikumi et alx for determining the entropies of fuels. Our calculations have shown that chemical energies
of fuels exceed their lower calorific values (for solid fuels, by 3.5% for lean coals to 20% for brown
coals; for liquid fuels, by 54%; for natural gases, by IO-12.5% for different fields; for coke-oven
gases by about 13%).
242 V. S. Stepanov

REFERENCES

I. T. Jannenmann, VDI-Ber., No. 59 I. 16 I ( 1986).

2. V. S. Stepanov, Chemical Energy and Exerp of Substances(in Russian), 2nd ed., Nauka. Novosibirsk ( 1990).
3. Z. Rant, A//g. WZirmetechn. 10, I72 ( 1961).
4. J. Szargut and T. Styrylska, BWK 16, 589 (1964).
5. N. D. Zakharov. Exergy of Organic Fuels. Izvestiya vuzov. Energetika (in Russian), No. 9. 63 ( 1970).
6. W. Fratzscher and D. Schmidt, Zur Bestimmung der Spezifishen Exergie von Brennstoffen, Wiss. Z. Dresden
Techn. Univ. 10, I83 ( 196 I ).
7. J. H. Shieh and L. T. Fan, Energy Sources 6, I (1982).
8. S. Ikumi, C. D. Luo. and C. Y. Wet-r, A Method of Estimating Entropies of Coals and Coal Liquids, The
Canadian J. Chem. Engng 60,551 ( 1982).
9. V. M. Baboshin. E. A. Krichentsov. V. M. Abzalov, and Ya. M. Shchelokov, Thermnphysicol Properties of
Fuels and Charge Materials of the Iron Metallurgy (in Russian), Metallurgy, Moscow ( 1982).
IO. V. S. Vdovchenko, M. 1. Martynova, N. V. Novitsky, and G. D. Yushina, Energy Fuel of the U.S.S.R. (in
Russian), Energoatomizdat, Moscow ( I99 I ).