API T D B CHAPTERS14 ** O732290 0537447 263

CHAPTER 14
COMBUSTION

Revised Chapter 14 to First Edition (1966),

Second Edition (1970), Third Edition (1976), and
Fourth Edition (1983)

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Copyright O 1985 American Petroleum Institute

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 The previous edition of Chapter 14, “Combustion,” was prepared in 1964. The
Technical Data Committee decided that material containing accurate heats of com-
bustion for pure hydrocarbons and associated compounds should be included, to-
gether with improved methods for estimating heats of combustion of petroleum
fractions, refiiery gases, and liquid fuels that would also be applicable to synthetic
fuels. Methods for estimating coal heats of combustion were also desirable.
Work on this revised chapter was carried out in 1981 and 1982. Evaluations are
documented in detail in Documentation Report 14-83, available from University
Microfilms, Ann Arbor, Michigan.
Miriam Maslanik and John Lobo, Research Assistants in Chemical Engineering,
carried out the work under the direction of Drs. T.E. Dauberî and R. P. Danner.
Dr. C. C. Williams III, Shell Oil Company, was the chapter coordinator for the
committee.

Thomas E. Daubert
Ronald P. Danner
Department of Chemical Engineering
The Pennsylvania State University
University Park, PA 16802

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CHAPTER 14
COMBUSTION
PAGE
14-0 Introduction.. . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14-1
Table 14-0.1 Liquid and Gaseous Fuels.. . . . . . . . . . . . . . . . 14-2
Table 14-0.2 Classification of Coal by Rank . . . . . . . . . . . . 14-3

14A Heats of Combustion

Table 14Al.l Heats of Combustion of Pure Compounds
(British Thermal Units per Pound). . . . . . . . . 14-5
Table 14A1.2 Heats of Combustion of Pure Compounds
(British Thermal Units per Cubic Foot). . , . . 14-9
Procedure 14A1.3 Heats of Combustion of Petroleum Fractions
and Synthetic Fuels . . . . . . . . . . . . . . . . . . . . . . 14-11

14B Heat Available from Combustion of Refinery Gases and

Liquid Fuels
Figure 14B1.1 Heat Available from Combustion of Refinery
Gas, 1000 Btu per Cu Ft (60 F) . . . . . . . . . . . 14-13
Figure 14B1.2 Heat Available from Combustion of Refinery
Gas, 1600 Btu per Cu Ft (60 F) . . . . . . . . . . . 14-14
Figure 14B1.3 Heat Available from Combustion of OOAPI
Fuel Oil . . , . . . . . . . , . . . . . . . . . . . . . . . . . , . . . 14-15
Figure 14B1.4 Heat Available from Combustion of SOAP1
Fuel Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14-16
Figure 14B1.5 Heat Available from Combustion of 10"API
Fuel Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14-17
Figure 14B1.6 Heat Available from Combustion of 15"API
Fuel Oil ................................ 14-18
Figure 14B1.7 Heat Available from Combustion of 20"API
Fuel Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14-19

14C Enthalpy of Flue Gas Components

Figure 14Cl.l Enthalpy of Flue Gas Components at Low
Pressures: H 2 0 , CO, COz, SOz.. . . . . , , , . . . 14-21
Figure 14C1.2 Enthalpy of Flue Gas Components at Low
Pressures: Air, Oz, N 2 . .. . . . . . . . . . . . . . . . . . 14-23

14D Grossmet Calorific Value of Solid Fuels

Procedure 14D1.1 Grossmet Calorific Value of Coals. . . . . . . . . 14-27

Bibliography . .. . .. . . .. . ... . .. . .. . . .. . .. . . . . . .. .. . . .. .... . .. . .... .. 14-29

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CHAPTER 14

COMBUSTION

144 INTRODUCTION of combustion for mixed liquid fuels, including- syn--

thetic fuels and petroleum fractions.
The heat of combustion of a substance is the heat Inasmuch as combustion reactions proceed with a
evolved when that substance is converted to its final decrease in enthalpy, the enthalpy change is negative in
oxidation products by means of molecular oxygen. The sign. However, the heat of combustion is defined as the
reaction represents the complete heat evolved; therefore, the values for heat of com-
of a hydrocarbon: bustion in this chapter and Chapter 1are positive. In all
cases, complete combustion (to carbon dioxide) is as-
C,H, + (a +$)Oz + 2b H z 0+ a(COz) sumed.
The standard heat of combustion is defined as the
change in enthalpy resulting from the combustion of a Refinery Gases and Fuel Oils
substance, in the state that is normal at 77 F and atmo- In most applications, the molecular oxygen necessary
spheric pressure, beginning and ending at a tempera- for combustion is supplied as air. To ensure complete
ture of 77 F. The gross heat of combustion is the same
combustion, excess air is commonly added. The follow-
as the standard heat of combustion except that the com- ing equation relates the heat available from combustion
bustion begins and ends at 60 F rather than 77 F. The
of a given fuel gas, when the flue gases exit at any
normal state for the water formed by the reaction is temperature, t, to the gross heat of combustion and the
liquid in both cases. composition of the flue gas. Excess air increases the
The difference between the standard and the gross negative term on the right-hand side of the equation,
heats of combustion is the difference between the sensi-
thereby decreasing the available heat, (H, - Hm):
ble heat changes of the products and the reactants from
60 F to 77 F. This sensible heat difference is usually n
negligible in comparison with the heats of combustion, (Ht- H a ) = Q - C d i ( H , - Ha)j (140.2)
so the gross and standard heats of combustion are ap- i= 1

proximately equal. Where:

The net heat of combustion is the heat evolved in a (H, - HW)= heat available from combustion when
combustion beginning and ending at 60 F with products the fuel is charged at 60 F and the flue
of gaseous water and carbon dioxide. Therefore, gases exit at t F, in British thermal units
per pound of fuel.
AH = Q - cAH@ (14-0.1) (H, - Ha)i = total enthalpy change of flue gas com-
Where: ponent i from 60 F to t F, in British
AH = net heat of combustion, in British thermal thermal units per pound of fuel.
units per pound of fuel. n = total number of components in flue gas.
(2 = gross heat of combustion, in British thermal di=pounds of flue gas component i per
units per pound of fuel. pound of fuel consumed.
c = pounds of water formed per pound of fuel con-
sumed. For water, (Hi - HW)H*O contains both the sensible heat
hHp= heat of vaporization of water at 60 F and at its from 60 F to t F and the heat of vaporization. Equation
vapor pressure, in British thermal units per (140.2) was used to develop Figures 14Bl.l through
pound of fuel. 14B1.7 for various refinery gases and fuel oils.
Equation (14-0.2) is a statement of the law of Hess:
Enthalpy is a function of the state and not of the path
Pure Compounds
used to reach the state. Therefore, the heat available
Net and gross heats of combustion are tabulated for from the combustion of a given fuel that is initially at 60
many pure hydrocarbons in Tables 14Al.l and 14A1.2. F with a given amount of air is a function only of the flue
Procedure 14A1.3 may be used in determining the heats gas temperature (i.e., the final state).
1983 14-1

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API TECHNICAL DATA BOOK

TABLE 144.1

LIQUID AND GASEOUS FUELS

Liquid Fuels
Sulfur Inerts Carbon-to-
Gravity (Percent by (Percent by Hydrogen
(Degrees API) Weight) Weight) Weight Ratio
O 2.95 1.15 8.80
5 2.35 1.OO 8.55
10 1.80 0.95 8.06
15 1.35 0.85 7.69
20 1.OO 0.75 7.65
25 0.70 0.70 7.17
30 0.40 0.65 6.79
35' 0.30 0.60 6.50

Gaseous Fuels
Nominal
Highb Actual Heat of Combustion
Heating
Value Gross
(British (British Gross Net
Thermal Thermal (British (British Molecular
Ilnits per Units per Thermal Thermal Sulfur Inert Gases Weight of
Cubic Foot Cubic Foot Units per Units per (Percent by (Percent by Hydrocarbon
at 6OF) at 60F) Pound) Pound) Weight)' Weight)d Portion
1,000 1,037 21,800 19,700 4.72 5.38 16.5
1,200 1,248 21,600 - 3.88 4.42 20.4
1,400 1,458 21,500 - 3.32 3.78 24.3
1,600 1,669 21,300 19,400 2.90 3.30 28.2
1,800 1,879 21,o00 - 2.52 2.88 32.1
2,000 2.090 20,800 - 2.29 2.61 36.1
' A b e 3S0API, the correction for impurities in Procedure 14A1.3 is negligible and the equations
represent pure paraffins (carbon-to-hydrogen weight ratio is 12.0n/2n + 2, where n is the number of
carbon atoms in the hydrocarbon).
bThe nominal high heating value is an approximate gross heat of combustion.
'Equivalent to 2.5 mole percent hydrogen sulfide.
dEquivalent to 1.25 mole percent carbon dioxide and 1.25 mole percent air.

Flue Gases Figures 14Bl.l through 14B1.7 (see Table 14-0.1)

The enthalpies of common flue gas components are were prepared for various liquid and gaseous fuels con-
taining arbitrary amounts of impurities.
plotted in Figures 14Cl.l and 14C1.2. The enthalpy
Most procedures include corrections to be used when
basis (enthalpy is zero for the ideal gas at 60 F) is more
the composition of the fuel differs appreciably from
convenient for combustion calculations than the basis
those previously tabulated.
used in the rest of this book. These enthalpies may be
used in equation (14-0.2) with Table 14A1.1 heats of The weight ratio of flue gas to fuel, for refinery gases
and fuel oil, can be determined as a function of percent
combustion to calculate the heat available from com-
excess air by making a simple material balance. Equa-
bustion as a function of temperature for pure hydro-
ting the weight of the fuel minus the inerts plus air to the
carbons.
weight of the flue gas gives the following relation for
fuel oil:

Ib flue gas- 64.1x*.~ 44.O(C/H)(1 -u -xW,)+ 18.00 -&s --GI)

1 Ib fuel 32.1 + 12.0 (c/H + 1) 2 (C/H + 1)
+ i%+ 12.O(C/H + 1)
+

4(C/H + 1) 21 I[
(UH)(l- xWs- xW,) 1- xws- xwt (79)(28.0) + (29.0)(% Ex Air)
21 1 (14-0.3)

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Where: C/H = carbon-to-hydrogen weight ratio,

% Ex Air = mole percent of excess air.
x,,.~= weight fraction of sulfur.
n, = weight fraction of inerts. The mole percent of carbon dioxide in the flue gas
may be obtained by a similar material balance. The
percent carbon dioxide on a water-free basis is given as

'i
(CM)(l - L s -xu./)
% CO*=
xWs ((XI)( 1 - xvs - xwl) 79 + % Ex Air
+(u
+

(12.0)(UH + 32.1 12.O(CM+ 1)

m ) ( 1 -xyQ-xw,) + (14(c/H+
-xyQ-xx,/
1) (14-0.4)

For refinery gases, calculations should account for

the fact that inert gases (in this case, carbon dioxide and
air) appear in the flue gas. Equations (14-0.3) and
(14-0.4) are based on data given by Maxwell (4), and the various grades of coal, as reproduced in Table
assumes average impurities as given in Table 14-0.1. 14-0.2.
Procedure 14Dl.l is used to compute the gross and
Coal net calorific values of coal. These heating values are a
function of the ultimate analysis and moisture per-
ASTM D 388 (1) gives the heating value ranges for centage of the coal.

TABLE 144.2

CLASSIFICATIONOF COAL BY RANK

Gross
Fixed Carbon Calorific Value
Agglomer- Limits. %b Limits, Btdb'
ating
Class Group Character' 2 <
Anthracitic Meta-anthracite N
Anthracite N
Semianhacited N
Bituminous Low-volatile bituminous CA' - -
Medium-volatile bituminous CA' - -
High-volatile A bituminous CA' 14,000' -
High-volatile B bituminous CA' 13,ood 14,000
High-volatile C bituminous CA' 11,500 13,000
A 10.500 11,500
Subbituminous SubbituminousA N 10.500 11,500
Subbituminous B N 9,500 10,500
Subbituminous C N 8,300 9,500
Lignitic Lignite A N 6,300 8,300
Lignite B N - 6,300

NOTE:This table is adapted and republished by permission of ASTM Dry, mineral-matter-free basis.
fromASTM D 388, "Standard Classification of Coals by Rank," 1983 Moist, mineral-matter-free basis, moist referring to coal containing
Annual Book of ASTM Standards, Volume 05.05. This classification its natural inherent moisture but not including visible water on the
does not include a few coals, principally nonbanded varieties, that surface of the coal.
have unusual physical and chemical properties and come within the dIf aggomerating, classify in low-volatile group of the bituminous
limits of fixed carbon or calorific value of the high-volatile bituminous class.
and subbiîuminous ranks. All of these coals either contain less than 'It is recognized that there may be nonagglomerating varieties in
48 percent dry, mineral-matter-free fured carbon or have more than these groups of the bituminous class, and there are notable exceptions
15,500 British thermal units per pound on the moist, mineral-matter- in high-volatile C bituminous group.
free basis. 'Coals having 69 percent or more fixed carbon on the dry, mineral-
'A = agglomerating; CA = commonly agglomerating; N = nonag- matter-free basis should be classified amrding to fixed carbon, re-
glomerating. gardless of calorific value.

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 TABLE 14Al.l
14A1.1
HEATS OF COMBUSTION OF PURE COMPOUNDS
(BRITISHTHERMAL UNITS PER POUND)

Gross Heat Net Heat of Standard Heat

of Combustion Combustion of Combustion
at 60 F at 60 F at 77 F
(Btdb) (Btu/lb) (Btdb)
Compound -w, -w.w -mcm

Nonhydrocarbons

Hydrogen (gas) 60,847 5 1,427 60.782

Carbon monoxide (gas) 4,347 4,347 4.344
Ammonia (gas) 8,831 7,155 8.818
Hydrogen sulfide (gas) 7,w1 6.533 7,087
Carbonyl sulfide (gas) 3,923 3,923 3.924
Carbon disulfide 6,075 6,075 6,077
Sulfur dioxide (gas) 954 954 954

Methane (gas) 23.884 21.511 23.860

Ethane (gas) 22,323 20,425 22,304
Propane (gas) 21,643 19,917 2 1,625
n-Butane (gas) 2 1,293 19,655 2 1,276
2-Methylpropane (gas) 21.231 19.594 21,214

n-Pentane 20.9 1 6 19,333 20,902

2-Methylbutane 20,883 19,301 20,870
2.2-Dimeth yipropane (gas) 20,949 19,367 20,933
n-Hexane 20,774 19.229 20,761
2-Methylpentane 20.744 19,198 20,730

3-methyl pentme 20,750 19.205 20.737

2.2-Dimethylbutane 20,705 19.159 20.69 1
n-Heptane 20.673 19,153 20,660
2-Mcthylhexane 20,647 19.128 20.634
3-Methylhcxane 20,662 19.142 20,649

2,4-Dimethylpentane 20,626 19,107 20.6 13

n-Octane 20,593 19,094 20.580
2-Meth ylheptane 20.577 19.078 20.564
2,2-Dimethylhexane 20,547 19,047 20.534
2,2.4-Tnmethylpentane 20,558 19.059 20.545

n-Nonane 20,536 19,052 20,524

n-Decane 20,487 19.016 20.475
n-Undecane 20,447 18,986 20.435
n-Dodecane 20,4 15 18.962 20,403

n-Tridecane 20.387 18.942 20,375

n-Tetradecane 20,365 18,926 20,353
n-Pcntadeane 20.344 18,911 20,333
n-Hexadtcane 20.326 18.897 20.314

n-Heptadecane 20.3 14 18,889 20,300

n-Octadecane 20.194 18,773 20.181
n-Nonadecane 20.2 1 2 18.795 20.200
n-Eicosane 20, i 69 18,755 20,157

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TABLE 14A1.1
14Al .1 HEATS OF COMBUSTION OF PURE COMPOUNDS
(BRITISH THERMAL UNITS PER POUND)

Gross Heat Net Heat of Standard Heat

of Combustion Combustion of Combustion
flt60F at60F at 77 F
(Btdb) (Btdb) @tullb)
Compound - A b -AH,60 -AHc.71

Napbtbenes

Cyclopentane 20,182 i 8.825 20.1 69

Methylcycloptane 20.121 18.764 20,lO8
Ethylcyclopentane 20.609 19,253 20,597
1.I-Dimethylcyclopentane 20,077 18.721 20,065
cis- 1.2-Dimcthylcyclopentane 20,102 18.745 20,090

trans-1.2-Dimthylcyclope 20,074 18,717 20,062

cis-1,3-Dimethylcyclopentane 20.08 1 18,724 20,069
trans-l,3-Dimethylcyclopentane 20.086 18,729 20,074
n-Propylcyclopentane 20,lO0 18.743 20,088
n-Butylcyciopentane 20,039 18.682 20,027

n-Pentylcyclopentane 20,097 18,740 20,085

n-Hexylcyclopentane 20,094 18,737 20,082
n-Heptylcyclopentane 20,092 18,736 20.08 I
n-ûctylcyclopentane 20,090 I 8.734 20,079
n-Nonylcyclopentane 20,089 18.733 20,078
n-lkcylcyclopentane 20,089 18.733 20,078
n-Undecylcyclopentane 20,088 18.731 20.076
n-Dodecylcyclopentane 20,087 18,731 20,076
n-Tridecylcyclopentane 20,087 18,730 20,076
n-Tetradecylcyclopentane 20,086 18.730 20,075

n-Pentadecylcyclopentane 20,086 18.729 20,074

Cyclohexane 20,028 18,672 20,016
Meth ylcyclohexane 19,989 18,632 19,977
Ethylcyclohexane 20.012 18,656 20,000
1,l -Dimethylcyclohexane 19,987 18,630 19,975
cis-1.2-Dimethylcyclohexane 20.013 18,657 20,001
trans- 1,2-Dimethylcyclohexane 19,988 18,632 19,976
cis-1,3-Dimcthylcyclohexane 19,970 18,614 19.958
trans- 1,3-Dimethylcyclohexane 19.998 18.641 19,986
cis-1.4-Dimethylcyclohexane 19.998 18.642 19,986

crans-1,dDimethylcyclohexane 19.973 18.616 19,961

n-Propylcyclohexane 20.0 I4 18.658 20,002
n-Butylcyclohexane 20,020 18,663 20,008
n-Pentylcyclohexane 20,027 18,670 20,015
n-Hexylcyclohexane 20.03 1 18,675 20,019
n-Heptylcyclohcxane 20,034 18,678 20,022
n-ûctylcyclohexane 20.037 18,680 20.025
n-Nonylcyclohexane 20,040 18,683 20.028
n-Decylcyclohexane 20.025 18.668 20.0 I 3
n-Undecylcyclohexane 20.036 18,679 20,024

n-Dodecylcyclohexanc 20,047 18,690 20,036

n-Tridecylcyclohexane 20,049 i 8,692 20.037
n-Tetradecylcyclohexane 20,050 18,694 20.039

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 TABLE 14Al.l
14A1.1
HEATS OF COMBUSTION OF PURE COMPOUNDS
(BRITISHTHERMAL UNITS PER POUND)
Gross Heat Net Heat of Standard Heat
of Combustion Combustion of Combustion
at 60 F at 60 F at 77 F
(Btdb) (Btuilb) (Btdb)
Compound -AH,, -AH,., -AHc,77
Olefins

Ethene (gas) 21,636 20.279 2 i ,622

Propene (gas) 21,030 19,673 21,016
1-Butene (gas) 20.823 19,467 20,809
2-Butene (gas) 20.77 I 19,414 20.757
ms-2-Butene (gas) 20,743 19,386 20,729

2-Methylpropenc (gas) 20.696 19,340 20,683

I-Pentcne 20.538 19,182 20.527
1-Hexene 20,454 19,097 20,443
2,3-Dimethyl-2-Butene 20.308 18,951 20.297
1-Heptene 20,394 19,037 20,383

1-0cttne 20,349 18,992 20,338

1-Nonene 20.3 17 i 8,960 20,306
1-Decene 20,282 18.925 20.27 1
1-Undecene 20,264 18,908 20.253

1-Dodecene 20,249 18,892 20.238

1-Tridecene 20,234 18,878 20,223
1-Tetradecene 20.22 1 18,864 20.2 1o
1-Pentadecene 20.2 12 18.855 20.201
1-Hexadecene 20.200 18,843 20.1 89

1 -Heptadecene 20.197 18,841 20.1 86

1-Octadecene 20,188 18,832 20,177
I -Nonadecene 20, i 76 18.820 20.165
I-Eicosene 20.115 18,759 20.104

Diolefins and Acetylenes

Propadiene (gas) 20.853 19.902 20,844

1.2-Butadiene (gas) 20,62 1 19,566 20,611
1.3-Butadiene (gas) 20,199 19,144 20, i 89
Ethync (acetylene) (gas) 2 1,482 20.75 1 2 1.477
Propyne (gas) 20,792 19.842 20.784
1-Butyne (gas) 20.644 19.589 20,634

Aromatics

Benzene 17,985 17,254 17,980

Methylbcntene 18,245 17,419 18,239
Ethylbenzene 18,487 17.59 1 18,480
1,2-Dimthylbcnzcnt 18,438 17,542 18,431
1.3-Dimethylbenzcne 18,434 17,538 18.427

1 .CDimethylbenzene 18.439 17.543 18,432

n-Propylbenzene 18,666 17,716 18,659
Isopropylbenzene 18,659 17.709 18,651
1-Methy1-2-Ethylbenzene 18,641 17.691 18.633
1-Methyl-3-Ethylbcnzene 18,635 17.685 18.627

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TABLE 14Al.l

HEATS OF COMBUSTION OF PURE COMPOUNDS

(BRITISHTHERMAL UNITS PER POUND)
14A1.1
Gross Heat Net Heat of Standard Heat
of Combustion Combustion of Combustion
at 60 F at 60 F at 77 F
(Btdb) (Btdb) (Btflb)
Compound -w.w -Akw -AH,.,

1-Methyl4Ethylbemne 18,628 17,678 18.620

1.2,3-Trimethylbenzene 18,600 17,650 18.593
1W-Trimethylbcnzcnc 18.588 17,638 18,581
1.3.5-Trimethylb~~~ 18.578 17.628 18.570
n-Butylbenzene 18.813 17.821 18,805

n-Pentylbenzenc 18.936 17,909 18.928

n-Hex ylbenzene 19,028 17,972 19,019
n-Hcptylbenzene 19,106 18,027 19,097
n-ûctylbemne 19,177 18.077 19.167
n-Nonylbenzene 19,234 18,116 19.225

n-Decylbenztne 19,288 18,155 19.279

n-Undecylbenzene 19,333 18.186 19.323
n-Dodecylbenzene 19.378 i 8,220 19.368
n-Tridecylbenzene 19417 18.248 19.407
n-Tctradecylbenzene 19,453 18,275 19.443

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TABLE 14A13
HEATS OF COMBUSTION OF PURE COMPOUNDS 14A1.2
(BRITISH THERMAL UNITS PER CUBIC FOOT)

Gross Heat of Net Heat of

Combustion at 60 Combustion at 60 F
(Btu/fi,) (BWfi,)
Compound - A b -AH,
Hydrogen 323.9 273.7
Carbon monoxide 320.8 320.8
Ammonia 396.3 321.1
Hydrogen sulfide 636.8 586.7
Carbonyl sulfide 621.1 621.1
Carbon disulfide 1218.8 1218.8

Sulfur dioxide 161.O 161.0

Methane 1009.5 909.2
Ethane 1768.8 1618.4
Ropane 2s15.0 2314.4
n-Butane 3260.9 3010.2
2-Methylpropane 325 1.4 3000.7

n-Pentane 3976.5 3675.6

2-Methylbutane 3970.3 3669.5
2.2-Dimethylpropane 3982.8 3682.0
n-Hexane 4717.6 4366.6
n-Heptane 5458.2 5057.1
n-Octane 6198.5 5747.2

Cyclopentane 3729.5 3478.8

Methylcyclopentane 4462.1 4161.2
Eth ylcyclopentane 5332.3 498 I .3
n-Propyicyclopentane 5943.6 5542.5
Cyclohexane 4441.6 4 140.7
Methylcyclohexane 5171.8 4820.8

Ethylcyclohexane 5917.7 55 16.6

Ethene 1599.2 1498.9
Propene 233 1.8 2181.4
1-Butene 3078.8 2878.2
cis-2-Butene 307 1.O 2870.5
trans-2-Butene 3066.9 2866.3

2-Methylpropene 3060.0 2859.4

1-Pentene 3795.4 3544.7
1-Hexene 4535.9 4235.1
1-Heptene 5276.6 4925.6
1-&iene 601 7.3 5616.1
Ropadi ene 220 1.2 2100.9

i .2-Butadiene 2939.1 2788.7

1.3-Butadiene 2879.0 2728.6
Ethyne 1474.0 1423.9
Propyne 2194.8 2094.5
1-Butyne 2942.4 279 1.9
Benzene 3701.8 355 1.4

Methylbenzene 4429.7 4229.1

i ,2-Dimethylbenzene 5158.3 4907.6
1,3-Dirnethylbenzcne 5157.2 4906.5
i ,CDimethylbenzene 5158.6 4907.9

1999 14-9

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 API T D B CHAPTERxL4 t* 0732270 0537459 T85

14A1.3

PROCEDURE 14A1.3

HEATS OF COMBUSTION OF PETROLEUM FRACTIONS

AND SYNTHETIC FUELS

Dlscusslon
The following equation is used to predict the gross heat of combustion of petroleum
fractions and synthetic fuels:
-AH:* = 17,672 + 66.66 - 0.316G2 - 0.00146’ (14A1.3-1)
Where:
-AH:no = gross heat of combustion at 60 F, in British thermal units per pound.
6 = API gravity.
If water is present in the fuel or if impurities are significantly different from those given
in the Introduction, the following equation should be used to correct for it:
-AH,.ao = (-AH&,) -O.Ol(-AH:m)(% H 2 0 + % S, + % Inerts,) + 40.5(% S.)
(14A1.3-2)
Where:
= corrected gross heat of combustion, in British thermal units per pound.
% H20= weight percent of water in the fuel.
% S. = weight percent of sulfur in the fuel minus the average weight percent (given
in the Introduction).
% Inerts. = weight percent of inerts in the fuel minus the average weight percent (given in
the Introduction).
The net heat of combustion is obtained from equation (14A1.3-3).
-AH:,ao (net) = 16,796 + 54.56 - 0.217G2- 0.0019G3 (14141.3-3)
Where:
-AH:ao (net) = heat of combustion at 60 F, in British thermal units per pound.
-AH,., (net) = [-AH:w (net)] - O.Ol[-AH: 6o (net)](% €120 + % S, + % Inerts,)
+ 40.5 (% Se) - 10.53 (% &O) (14A1.3-4)
Where:
-AHc.* (net) = corrected net heat of combustion at 60 F, in British thermal units per pound.

Procedure
Srep I : Obtain the API gravity and the impurity and moisture weight percents of the
petroleum fraction or synthetic fuel.
Step 2: Use equations (14Al.3-1) and (14Al 3-2) to calculate the gross heat of combustion.
Step 3: Calculate the net heat of combustion from equations (14A1.3-3) and (14A1.3-4).

1983 14-11

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 A P I TDB C H A P T E R X I 4 X t = 0 7 3 2 2 9 0 05374b0 7 T 7 M

14A1.3

COMMENTS ON PROCEDURE 14A1.3

Purpom
Procedure 14A1.3 is a method to estimate heats of combustion of petroleum liquids and
synthetic fuels.

Reliability
Gross heats of combustion estimated by this procedure have an average error of 180 British
thermal units per pound of fuel. An average deviation of 205 British thermal units per pound
of fuel was obtained for predicted net heat of combustion values.
Lîteratum Sources
Equations (14A1.3-1) and (14A1.3-3) were developed using the figure given by J. B.
Maxwell, Data Book on Hydrocarborn, D. Van Nostrand Company, Inc., Princeton, N.J.
(1950). Equations (14A1.3-2) and (14A1.34) were given in Standard Design Daru, Foster
Wheeler Corporation, New York (1960).

Example
Determine the gross and net heats of combustion of an 11.3"APIfuel oil that contains 1.49
weight percent sulfur, 1.67 weight percent inerts and 0.30 weight percent water.
The average percent of sulfur in an 11.3"API fuel on which equations (14A1.3-1) and
(14A1.3-3) are based is 1.68 by interpolation from the table in the Introduction, so
% Se = 1.49 - 1.68 = - 0.19, Similarly, the average inerts content for the basis fuel is 0.92,
so % Inerts, = 1.67 - 0.92 = 0.75.
The gross heat of combustion can now be raiculated from equations (14A1.3-1) and
(14A1.3-2).
17,672+66.6(11.3) -ü.316(11.3)2-0.0014(11.3)3
= 18,382
- AHc,, = 18,382 - (0.01) (18,382) (0.3 - 0.19 + 0.75) + 40.5 ( - 0.19)
= 18,216 British thermal u .its per pound of fuel
An experimental value is 18,088 British thermii units per pound of fuel.
From equations (14A1.3-3) and (14A1.3-4), the net heat of combustion is
- AHc:w(net) = 16,7% + 54.5 (11.3) - 0.217 (11.3)'- 0.0019(11.3)3
= 17,381
- AHc., (net) = 17,381 - 0.01(17,381) (0.30 - 0.19 + 0.75) + 40.5 ( - 0.19) - 10.53 (0.30)
= 17,221 British thermal units per pound of fuel
An experimental value is 17,128 British thermal units per pound of fuel.

14-12
1983

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 A P I TDB C H A P T E R f L 4 f f W 0732270 0 5 3 7 4 b L b33

1461.1

FLUE GAS TEMPERATURE ,F

1983 14-13

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 API TDB CHAPTER814 88 0732290 0537462 57T

1491.2

FLUE GAS TE

14-14 1983

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 A P I TDB CHAPTER*Lq ** O732290 05374b3 406 W

1983

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 A P I TDB C H A P T E R S 1 4 t S W O732290 0537464 342 m

1461.4

14-16 1983

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 1481.5

G
Y

f
8
i
Y
4s
<
3

FLUE GAS TEMPERATURE,f

1983 14-17

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 A P I TDB C H A P T E R X I 4 X f m 0732290 05374bb IL5 m

1481.6

FLUE GAS TEMPERATURE, F

14-18 1983

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 A P I TDB C H A P T E R t L i 1 t t = O732290 O537467 O51 =

1481.7

moo I
FIGURE 1481.7
HEAT AVAILABLE
FROM COMBUSTION
2 0 API FUEL Oll

18000 - TECHNICAL DATA BOOK

Jun. 19.93 '
..
Aooroved TED 6 RPD

,. I
.
':
>
I
" :a
. . . ,'
1 :i?...

.]iNOTE:h e Cunrnsntr on

14000 i;:
I

1800 30 2600
FLUE GAS TEMPERATURE .F

1983 14-19

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 A P I TDB C H A P T E R X I V X X m 0732290 0537Vb8 T98 m

1481.l-1481.7

COMMENTS ON FIGURES 1481.1 THROUGH 1481.7

Purpose
The heat available from the combustion of refinery gases and fuel oils to gaseous products
is given in Figures 14Bl.l through 14B1.7 as a function of temperature and percent excess
air.

Llmitations
An allowance was made for an average sulfur and inerts content in the fuel, but not for the
presence of water.

Rellablllty
The estimated average deviation of these figures is 1 percent for the fuels defined in the
Introduction.

Speclal Comments
Figures 14Bl.l and 14B1.2 were derived using only mixtures of paraffin gases. The figure
more nearly corresponding to the gross heat of combustion of the fuel gas can be used without
interpolation with very little error. In correcting for the variation in impurities, however, the
available heat must be adjusted in proportion to the weight percentage of the hydrocarbon
present in the fuel gas. Consider half of the hydrogen sulfide u hydrocarbon (¡.e., a source
of heat) and half as an inert gas (see Example).
Figures 14B1.3 through 14B1.7 represent the heat available from fuel oils having API
gravities of O, 5, 10, 15, and 20 degrees. If the impurities are known to be appreciably
different from the average values, the available heat may be corrected in direct proportion
to the weight percentage of the hydrocarbon present in the fuel, with sulfur considered an
inert material. The average impurities used to develop the figures are tabulated in the
Introduction.
Interpolation between the figures is unnecessary; the available heat at any temperature and
percent of excess air can be read from the chart which most nearly corresponds to the gravity
of the fuel oil.

Literature Source
These charts were patterned after those of Maxwell, Daru Book on Hydrocarbons, D. Van
Nostrand Company, Inc., Princeton, N.J. (1950). The figures were replotted to be consistent
with the more recent enthalpy data in Chapter 7.

Example
Estimate the heat available from the combustion of a refinery gas having a gross heat of
combustion of 1200 British thermal units per cubic foot (60 F) with 100 percent excess air.
The fuel contains the following impurities: 8.0 percent by weight hydrogen sulfide and 12.0
percent by weight inert gases. The flue gases exit at 2000 F.
Inasmuch as 1200 British thermal units per cubic foot (60 F) is closer to lo00 than 1600,
Figure 14Bl.l should be used. Because the amount of impurities is significantly larger than
the average values, the heat available must be corrected. From Figure 14Bl.1, the uncor-
rected heat available is 1950 British thermal units per pound of fuel for the average fuel
containing 8.3 percent inert gases from the table in the introduction. Half the hydrogen
sulfide, or 4 percent by weight, must be considered inert gases. Therefore, the total amount
of impurities is 4 + 12 = 16 percent by weight.
Total heat available = (1950)(100 - 16)/(100 - 8.3) = 1786 British thermal units per pound
of fuel.

14-20 1983

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 A P I TDB C H A P T E R r L 4 t* 0732290 0537469 924

í4cí.í

1963 14-21

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 A P I TDB C H A P T E R * 1 4 ** m O732290 0537470 b4b m

14C1.1

ENTHALPY ABOVE 60 F, Biujlb

14-22 1983

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 A P I TDB CHAPTERx34 x x m 0 7 3 2 2 7 0 0537473 582 m

14C1 .2

ENTHALPY ABOVE 60 F, h / l b
1983 14-23

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 A P I TDB C H A P T E R x 2 4 ** m 0732270 0537472 429 m

14C1.2

f
a s 8
* ss 8 O
a i c

ENTHALPY ABOVE 60 F, Biu/lb

14-24 1983

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 A P I TDB C H A P T E R * 1 4 ** m 0732290 0537473 355 m

14C1.1-14C 1.2

COMMENTS ON FIGURES 14C1.1 and 14C1.2

Purpose
The enthalpy above 60 F for various flue gas components is plotted as a function of
temperature. The enthalpy values are for low-pressure gases only (less than 50 pounds per
square inch absolute).

Rellablllty
The estimated average deviation of these figures is 1 percent.

Special Comments
To prepare the figures, the ideal gas enthalpies given in Chapter 7 were converted to a basis
of zero for the ideal gas at 60 F. This basis is preferable for combustion calculations inasmuch
as standard heats of combustion are normally given at these conditions. The curve for air was
obtained by assuming a composition of 21 percent by volume oxygen and 79 percent by
volume nitrogen. No correction has been made for dissociation of the molecules at high
temperatures.

Literature Source
The figures were plotted using the ideal gas enthalpy data given in Chapter 7.

1983 14-25

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 A P I TDB C H A P T E R t 1 4 t t W 0732290 0537474 291 W

1401.1

PROCEDURE 14D1.1

GROSSINET CALORIFIC VALUE OF COALS

Discussion
The following equation is used to estimate the gross calorific value of coal:
Q, = 146.58C+568.78fI+29.4S-6.58A-51.53(0 + N) (14Dl.l-1)
Where:
Q,, = gross calorific value at constant volume. British thermal units per pound. on a
dry basis.
C = weiglit percent of carbon.
1-I = weight percent of hydrogen.
S = weight percent of total sulfur.
A = weight percent of ash.
(O + N ) = weight percent of oxygen plus nitrogen by difference.
The weight percents are on a dry basis.
The gross calorific value at constant pressure is obtained from the equatioii (14Dl.l-2).
Q, = Q , + 2.6H - 0.330 (14D1.1-2)
Where:
0,= gross calorific value at constant pressure.
Equation (14Dl.l-3) is used to calculate the net or low calorific value at constant pressure.
Q,(net) = Q, - 92.211 - (0.33)0 - 10.50M (14U I. 1-3)
Where:
Qp(net) = net calorific value at constant pressure.
M = percent moisture in the coiil.
Q , , 11, O are on a moist basis.

Procedure
S f e p I : Obtain the ultimate analysis and percent iiioisture of the coal.
Step 2: Use equation (14D1.1-1) or (14Dl.l-2) to calculate the gross calorific vuliie.
Step 3: Calculate the net calorific value from equations (14Dl.l-1) and (14Dl.l-3).

1983 14-27

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 A P I TDB CHAPTERt14 t t D 0732290 0537475 128 =

14Dl.l

COMMENTS ON PROCEDURE 14D1.1

Purpose
This procedure may be used to predict the gross and net calorific value of a coal given the
ultimate analysis and percent moisture of the coal.

Reliability
Gross calorific values estimated by this procedure have an average error of 115 British
thermal units per pound.

wature source
Equations (14Dl.l-1) through (14Dl.l-3) were given in Coal Conversion System Tech-
nical Datu Book, U.S. Department of Energy (1978).

Example
Calculate the gross calorific value of an Illinois No. 6 coal with the following composition
given on a dry basis:
Carbon = 68.92%
Hydrogen = 5.01%
Nitrogen = 1.01%
Sulfur = 6.66%
Ash = 10.84%
Oxygen = 7.57% (by difference)
From equation (14D1.1-1)
Qv =146.58(68.92) + 568.78(5.01) + 29.4(6.66) - 6.58(10.84) - 51.53(7.57 + 1.01)
= 12,634 British thermal units per pound
Qp=12,634 + 2.6(5.01) - 0.33(7.57)
=12,645 British thermal units per pound
The experimental value is 12,773 British thermal units per pound.

14-28 1983

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 A P I TDB CHAPTERJ14 ** W 0732290 0 5 3 7 9 7 6 Ob4

API TECHNICAL DATA BOOK

BIBLIOGRAPHY

1. ASTM D 388, "Standard Classificationof Coals by Rank," 1983 4. Maxwell, J. B., Data Book on Hydrocarbons, D. Van Nostrand
Annual Book of ASTM Standards, Volume 05.05. Co., Inc., Princeton, N.J.(1950).
2. Foster Wheeler Corporation, Standard Design Data (1960).
3. Institute of Gas Technology, Cool Conversion Syslems Technical
Data Book, U.S. Department of Energy (extant 1978).

1983 14-29

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