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Update: 2018/2/9
The most common fuel that is used for power generation currently is a
chemical compound that contains carbon, hydrogen, and oxygen only,
and is called the hydrocarbon fuel.
Fuel is burned with sufficient amount of air such that all the carbon in the
fuel oxides to carbon dioxide, and all the hydrogen in the fuel oxides to
water. Besides, neither fuel nor oxygen remains.
Composition of air:
N2: 78.08%
O2: 20.95%
Argon: 0.93%
CO2: 0.03%
Others: 0.01%
Water vapor: variable
Average molecular weight: 28.97 kg/kmole
It is noted that the average molecular weight of the simplified air is 28.84
kg/kmole. However, the actual value of 28.97 kg/kmole is still used in
the calculation of combustion for accuracy.
The combustion formulas of several fuels with air for industry usage are
as following.
Methane(甲烷):
CH4 + 2(O2 + 3.76N2) → CO2 + 2H2O + 7.52N2
Ethene(乙烯):
C2H4 + 3(O2 + 3.76N2) → 2CO2 + 2H2O + 11.28N2
Acetylene(乙炔 Ethyne):
C2H2 + 2.5(O2 + 3.76N2) → 2CO2 + H2O + 9.4N2
Propane(丙烷):
C3H8 + 5(O2 + 3.76N2) → 3CO2 + 4H2O + 18.8N2
Propene(丙烯):
C3H6 + 4.5(O2 + 3.76N2) → 3CO2 + 3H2O + 16.92N2
Butane(丁烷):
C4H10 + 6.5(O2 + 3.76N2) → 4CO2 + 5H2O + 24.44N2
Butene(丁烯):
C4H8 + 6(O2 + 3.76N2) → 4CO2 + 5H2O + 22.56N2
Benzene(苯):
C6H6 + 7.5(O2 + 3.76N2) → 6CO2 + 3H2O + 28.2N2
Coal:
C + O2 + 3.76N2 → CO2 + 3.76N2
Hydrogen:
H2 + 0.5(O2 + 3.76N2) →H2O + 1.88N2
In general, we have
If oxygen is contained in the fuel, the amount of air required to oxide the
fuel is reduced due to the presence of oxygen in the air fuel mixture.
Methanol(甲醇):
CH3OH + 1.5(O2 + 3.76N2) → CO2 + 2H2O + 5.64N2
Ethanol(乙醇):
C2H5OH + 3(O2 + 3.76N2) → 2CO2 + 3H2O + 11.28N2
Combustion Engineering ME Dept NCHU 頁 2
Propanol(丙醇):
C3H7OH + 4.5(O2 + 3.76N2) → 3CO2 + 4H2O + 16.92N2
Butanol(丁醇):
C4H9OH + 6(O2 + 3.76N2) → 4CO2 + 5H2O + 22.56N2
Ethyl Ether(二乙醚):
C2H5OC2H5+ 6(O2 + 3.76N2) → 4CO2 + 5H2O + 22.56N2
In general, we have
m y m m y
Cn H m O y ( n )(O2 3.76 N 2 ) CO2 H 2O 3.76(n ) N 2
4 2 2 4 2
Gasoline and diesel fuels are mixtures of hydrocarbons rather than pure
substance. They don’t have chemical formula and fixed values of
molecular weight. In general, gasoline and diesel fuels are represented as
CH1.85
Stoichiometric combustion:
The air fuel ratio for complete combustion is called stoichiometric air fuel
ratio.
Lean combustion:
If the amount of air is more than that required for complete combustion,
there will be excess air after combustion. This is call lean combustion.
In a lean combustion, the air fuel ratio is greater than the stoichiometric
air fuel ratio.
Rich combustion:
If the amount of air is less than that required for complete combustion,
part of the fuel would not be fully oxidized such that either there will be
excess fuel left after combustion or there will be incomplete combustion
products, such as carbon monoxide or unburned hydrocarbon.
In a rich combustion, the air fuel ratio is less than the stoichiometric air
fuel ratio.
Fuel air ratio:the reciprocal of air fuel ratio, usually used by Diesel
engine and gas turbine engine people.
100%
% of theoretical air =
1 100%
% of excess air =
In an open system,
m f ma m p
Q m f h f ma ha mp hp W
e.g.: gas turbine engine, steam boiler.
m f ma mp
C + O2→ CO2
Since the process does not produce any output work, the energy equation
of an open system gives the relationship between the enthalpy of products
and that of reactants.
Q mr hr m p hp
Q hC hO2 hCO2
T
h h h h c p dT
o
f
o
f
T0
Q h f ,C h f ,O2 h f ,CO2
393520 h f ,C h f ,O2 h f ,CO2
hof ,C 0
hof ,O2 0
25℃Methane
1200K products
600K air
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Example:A mixture of liquid methanol and air is fed to the inlet of an
adiabatic fuel reformer to produce hydrogen. The inlet mixture is at 25℃,
and the outlet gas is at 600K. Determine the air fuel ratio.
(partial oxidation reforming process)
CH3OH + x(O2 + 3.76N2) → CO2 + 2H2 + (x-0.5)O2 + 3.76xN2
(Ans: x=3.017, A/F = 13.0)
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Example:In an electrolysis reaction, water is decomposed into hydrogen
and oxygen. Calculate the required power if 100 L/min of hydrogen is
produced. (19.23 kW)
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Continuous flows of air and fuel are feeding into an adiabatic burner
and the hot exhaust gas is cooled by water coiled around the exhaust pipe.
The flow rate and the temperature difference of water are measured to
calculate the thermal energy released by the combustion products.
fuel
air exhaust
Q HR HP
Lower heating value (LHV): the heating value of a fuel in which that the
water vapor in the product remains in the form of vapor at 25℃.
h f , H 2O = -241818 kJ/kmole
Higher heating value (HHV): the heating value of a fuel in which that the
water vapor in the product is condensed to liquid water at 25℃.
h f , H 2O = -285830 kJ/kmole
HHV is greater than LHV. The difference between LHV and HHV is the
latent heat of water at 25℃.
The enthalpy of formation of any fuel can be obtained if the heating value
is already known.
m
h f , F h f ,CO2 h f , H 2O Q
2
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Example:Determine the lower heating value and the higher heating
value of ethylene.
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Example:Determine the lower heating value and the higher heating
value of hydrogen.
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Example:If the higher heating value of gasoline is 42000 kJ/kg, and the
H/C ratio is 1.85, determine the equivalent enthalpy of formation of
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Example:Dmethyl ether (DME, CH 3OCH 3 ) is considered to be an
alternative fuel to replace fossil diesel. The lower heating value of DME
is 28900 kJ/kg. Determine the enthalpy of formation of DME.
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It is noted that heating values of hydrocarbon fuels are about the same in
terms of weight.
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Assignment 2.9
Another way to produce is to synthesize DME directly from hydrogen
and carbon monoxide with the following reaction.
3CO 3H 2 CH 3OCH 3 CO2
Is this an endothermic reaction or exothermic reaction? Find the heat that
should be added or removed from the reaction if both the reactants and
products are at 25℃ and 100 kPa.
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Assignment 2.10
The averaged molecular weight of a jet fuel is 126 kg/kmole. The
hydrogen to carbon ratio is 1.85:1. If the lower heating value of the fuel
is 10280 kcal/kg, calculate the equivalent enthalpy of formation of the jet
fuel.
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Assignment 2.11
A synthesized gas is composed of 30% CO, 50% H2, 10% C3H8, and 10%
CH4 in molar basis.
(1). Determine the stoichiometric air fuel ratio of the synthesized gas.
(2). Determine the lower heating value of the synthesized gas in kJ/m3 at
25℃ and 100 kPa.
(3). The synthesized gas is mixed with excess air to burn in a heater, and
the flame temperature is 1500K. Determine the molar fraction of CO2 in
the products on a dry basis.
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Assignment 2.12
A turbojet engine runs on the fuel mentioned above. The temperature
and the pressure of the inlet air are 0℃ and 90 kPa. Jet fuel is injected
into the combustion chamber at 25℃. The pressure ratio of the
compressor is 10. The efficiency of compressor is 0.85. Find the air fuel
Combustion Engineering ME Dept NCHU 頁 17
ratio of the mixture if the temperature at the outlet of combustor is
confined to 1200K. Assume that air is an ideal gas.
m l m m l
Cn H mOl (n )(O2 3.76 N 2 ) nCO2 H 2O 3.76(n ) N 2
4 2 2 4 2
m l
(n ) 4.76 28.97
( A / F ) st 4 2
12n m 16l
The amount of heat that can be released expressed in terms of much fuel
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Example:Fuel is burned with stoichiometric air in an internal
combustion engine. The engine displacement volume is 1 L. The
temperature of mixture is 300K and the pressure is 100 kPa. Find the
energy that can be released in the combustion process.
(1). Hydrogen. (2). Methane. (3). Liquid gasoline. (4). Liquid methanol.
PV nRuT
PV
n = 4.009×10-5 kmole
RuT
H 2 0.5(O2 3.76 N 2 ) H 2O 1.88N 2
Heating value of hydrogen is 241942 kJ/kmole
n
nH2 nxH2 = 1.186×10-5 kmole
1 0.5 4.76
E nH 2 QH 2 =1.186×10-5 kmole×241942 kJ/kmole= 2.87 kJ
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Combustion efficiency:
QR
c
QHV
-----------------------------------------------------------------------------------------
Example:Methane is burned with dry air. The molar analysis of the
products on a dry basis is CO2 9.7%,CO 0.5%,O2 2.95%,and N2
86.85%。Determine the combustion efficiency.
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M a 28.97kg/kmole
As a result, Wobbe Index (WI) may be defined as
Ma
IW Q
MF
Pressure gauge
Fuel supply
Control valve
2P
V cd A
where V (Nm3/sec) is the fuel flow rate, A (m2) is the valve open area,
P (kPa) is the pressure difference, (kg/m3) is the fuel density, and cd
The total energy supply is the product of fuel flow rate and fuel
heating value.
For the same pressure difference and valve open area, the total energy
supply is proportional to the Wobbe index of the fuel. That is, if two fuels
have the same value of Wobbe index, they can be interchanged without
any adjustment of control valve to maintain the same level of total energy
supply.
The Wobbe Index of common fuel gases are as the following table.
(2.3.1). Wood
Type C H O HHV(kJ/kg)
Cedar(杉) 48.8 6.37 44.46 19540
Cypress(柏) 54.98 6.54 38.08 22960
Fir(樅) 52.3 6.3 40.5 21050
Hemlock(松) 50.4 5.8 41.4 20050
Pine(松) 59.0 7.19 32.68 26330
Redwood(紅木) 53.5 5.9 40.3 21030
Ash(梣) 49.73 6.93 43.04 20750
Beech(山毛櫸) 51.64 6.26 41.45 20380
Birch(樺) 49.77 6.49 43.45 20120
Elm(榆) 50.35 6.57 42.34 20490
Hickory(山胡桃) 49.67 6.49 43.11 20170
Maple(楓) 50.64 6.02 41.74 19960
Oak(橡) 48.78 6.09 44.98 19030
Poplar(白楊) 51.64 6.26 41.45 20750
Source:E.L. Keating, "Applied Combustion", Marcel Dekker, 1992.
Reference:
K. W. Ragland, D. J. Aerts, & A. J. Baker, “Properties of Wood for
Combustion Analysis”, Bioresource Technology 37 (1991) 161-168
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Example:Determine the equivalent enthalpy of formation of cedar.
4.067×(-390509) +3.185×(-285830)-hf=(-19540)×99.63
hf= -3941.5 kJ/kg
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Example:Dry cedar log is burned in a fireplace. Determine the amount
of excess air if the burned temperature is 700 K.
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Q=20000(1-x)-2400x=(20000-22400x) kJ/kg
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Example:Cedar log is burned in a fireplace, determine the amount of
excess air if the burned temperature is 700 K and the moisture content is
30%.
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(2.3.2). Coal
Ash content of coal is the non-combustible residue left after coal is burnt.
It represents the bulk mineral matter after carbon, oxygen, sulfur and
water (including from clays) has been driven off during combustion.
The fixed carbon content of the coal is the carbon found in the material
which is left after volatile materials are driven off. This differs from the
ultimate carbon content of the coal because some carbon is lost in
hydrocarbons with the volatiles. Fixed carbon is used as an estimate of
the amount of coke that will be yielded from a sample of coal.
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Example:An Illinois coal that has the following ultimate analysis:
81.3% C; 5.3% H; 9.8% O; 1.7% N; 1.9% S. Find the stoiciometric air
fuel ratio of the Illinois coal.
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Heating value
(2.3.3)、Hydrocarbon fuels
Alkane(烷類)
An alkane is a saturated hydrocarbon. Alkanes consist only of hydrogen
and carbon atoms, all bonds are single bonds, and the carbon atoms are
not joined in cyclic structures but instead form an open chain. They have
the general chemical formula CnH2n+2.
Alkene(烯類)
An alkene is an unsaturated hydrocarbon containing at least one carbon–
carbon double bond. They have the general chemical formula CnH2n.
HHV= 0.3491C+1.1783H+0.1005S–0.1034O–0.0151N–0.0211A
Reference:
Channiwala S.A. and P.P. Parikh, “A unified correlation for estimating
HHV of solid, liquid, and gaseous fuels”, Fuel 81 (2002) 1051-1063.
The members of the series (in terms of number of carbon atoms) are
named as follows:
Alkane Formula Boiling Melting Density [g·cm−3]
point [°C] point [°C] (at 20 °C)
Methane CH4 -162 -182 gas
Ethane C2H6 -89 -183 gas
Propane C3H8 -42 -188 gas
Butane C4H10 0 -138 gas
Pentane C5H12 36 -130 0.626 (liquid)
Hexane C6H14 69 -95 0.659 (liquid)
Heptane C7H16 98 -91 0.684 (liquid)
Octane C8H18 126 -57 0.703 (liquid)
Nonane C9H20 151 -54 0.718 (liquid)
Decane C10H22 174 -30 0.730 (liquid)
Undecane C11H24 196 -26 0.740 (liquid)
Dodecane C12H26 216 -10 0.749 (liquid)
Hexadecane C16H34 287 18 0.773
Icosane C20H42 343 37 solid
Triacontane C30H62 450 66 solid
Tetracontane C40H82 525 82 solid
Pentacontane C50H102 575 91 solid
Hexacontane C60H122 625 100 solid
(%) T (℃)
0 36.5 IBP
10 51.5 T10
33.7 70 V70
50 92.6 T50
54.1 100 V100
85.2 150 V150
90 161.2 T90
100 199.4 FBP
Temperature os saturation
200
150
T (C)
100 T
50
0
0 20 40 60 80 100
Ratio (%)
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天然氣和煤氣的優劣
近年來國內天然氣產業大力發展,城鎮氣化率快速提高,不過大中城市
天然氣已經普及,經濟較為發達的縣城、鄉鎮也已經鋪設了大量的天然氣管
道。
我們江西省新餘市也開始了煤氣改造成天然氣的步伐。可是很多用戶不
知道煤氣和天然氣的差別,不知道為什麼要將煤氣改造成天然氣,再加上用
天然氣比用煤氣的收費要高,使家裡的每月支出多了一些,很多用戶都有意
見。在此,我向大家介紹一下煤氣和天然氣的優缺點,幫大家更好地認識用
天然氣的必要性。
一、什麼是煤氣
煤氣是以煤為原料加工制得的含有可燃成分的氣體。我們一般用的煤氣
是水煤氣,它是由水蒸氣通過熾熱的焦炭而生成的氣體,主要成分是一氧化
碳、氫氣,燃燒後排放水和二氧化碳,有微量 CO、HC 和 NOX。
將水蒸氣通過熾熱的煤層可制得較潔淨的水煤氣(主要成分是 CO 和
H2),現象為火焰騰起更高,而且變為淡藍色(氫氣和 CO 燃燒的顏色)。
煤氣中有一氧化碳,家庭中煤氣中毒主要指一氧化碳中毒。由於人們用煤氣
不當或煤氣洩漏,也常造成人員傷亡,所以人們要更加小心煤氣的使用情
況。煤氣廠常在家用水煤氣中特意摻入少量難聞氣味的氣體,因為 CO 和 H2
為無色無味氣體,目的是為了當煤氣洩漏時能聞到並及時發現。
二、什麼是天然氣
從廣義的定義來說,天然氣是指自然界中天然存在的一切氣體,包括大
氣圈、水圈、生物圈和岩石圈中各種自然過程形成的氣體。它主要存在於油
田和天然氣田,也有少量出於煤層。天然氣燃燒後無廢渣、廢水產生,相較
煤炭、石油等能源有使用安全、熱值高、潔淨等優勢。
三、煤氣和天然氣的優缺點對比
1.煤氣和天然氣在燃燒後的成分差別對比
煤氣主要是一氧化碳和氫氣的成分,天然氣主要是甲烷等烴類和非烴類
氣體。煤氣和天然氣如果都完全燃燒,生成的都是二氧化碳和水,它們對空
氣污染極少,差別不大。但是水煤氣要是燃燒不完全,就會有大量的一氧化
碳、碳、氫氣進入到大氣當中。
從環境污染上講天然氣優於水煤氣,現在全球都在節能減排,所以用天
然氣是大勢所趨。
2.煤氣和天然氣的每月用量和收費
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Example:The composition of coke oven gas is as the following.
H2 54.0%,CH4 30.6%,CO 7.4%,N2 5.6%,CO2 2.0%,O2 0.4%.
Find the heating value of coke oven gas in kJ/m3.
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Q 0 ,W 0
mF hF ma ha m p hp , H R H p
T
hF h 0
f ,F hF h 0
f ,F c pF dT
T0
T
hO2 h0f ,O2 hO2 c pO2 dT
T0
T
hN2 h 0
f , N2 hN2 c pN2 dT
T0
mF u F maua m pu p , U R U p
T
u h RT h c p dT RT
0
f
T0
nb RTb
Pb
V
Pb nb Tb
P0 n0 T0
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Example:Hydrogen is mixed with air at an equivalence ratio of 1.0 in a
constant volume chamber at 25℃and 100 kPa. Determine the adiabatic
flame temperature and the final pressure.
H 2 0.5(O2 3.76 N 2 ) H 2O 1.88N 2
u H 2 0.5uO2 1.88u N 2 u H 2O 1.88u N 2
hH 2 0.5hO2 3.76hN 2 3.38RT1 h f , H 2O hH 2O 1.88hN 2 2.88RTb
Pb 2.88 Tb
100 3.38 298
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Example:Hythane is a mixture of hydrogen and methane at the ratio of
1:1 in volume. Hythane is mixed with stoichiometric amount of air at
25℃ and 100 kPa in a constant volume chamber. Determine the flame
temperature and the final pressure if the combustion process is adiabatic
and the volume remains the same.
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Assignment 2.15
An internal combustion engine runs on the fuel of propane with an
equivalence ratio of 0.9. The temperature and the pressure at the
end of compression stroke are 500℃ and 2.6 MPa. If a constant
volume combustion process occurs in the cylinder, find the
temperature and the pressure after combustion.
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Assignment 2.16
A synthesized gas is composed of 30% CO, 50% H2, 10% C3H8, and 10%
(1). Determine the stoichiometric air fuel ratio of the synthesized gas.
(2). Determine the lower heating value of the synthesized gas in kJ/m3 at
25℃ and 100 kPa.
(3). The synthesized gas is mixed with excess air to burn in a heater, and
the flame temperature is 1500K. Determine the molar fraction of CO2 in
the products on a dry basis.
(4). The synthesized gas is mixed with 20% excess air to burn in a
constant pressure adiabatic combustor. Both the synthesized gas and air
are at 100 kPa and 25℃. Determine the adiabatic lame temperaure.
(5). The synthesized gas is mixed with 20% of excess air in a constant
volume adiabatic combustor. Both the synthesized gas and air are at 100
kPa and 25℃. Determine the final temperature and pressure of the
products.
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Example:Methane is burned with stoichiometric air at 25℃and 100 kPa
in a constant pressure process.
CH 4 2(O2 3.76 N2 ) CO2 2 H 2O 7.52 N2
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Example:Methane is burned with 25% excess air at 25℃and 100 kPa in
a constant volume process.
CH 4 2.5(O2 3.76 N2 ) CO2 2H 2O 0.5O2 9.4 N 2
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Example:Methane is burned in a gas turbine engine with an
equivalence ratio of 0.4. The pressure ratio of the engine is 10.0. Find
the specific work of the engine and the thermal efficiency.
wc h2 h1 = kJ/kg, wt h3 h4 = kJ/kg,
wnet wt wc = kJ/kg, work output per kg of mixture.
A / F = 43.09
mf 1
=0.0227, mass of fuel per kg of mixture.
m 1 A/ F
Q f = 50009 kJ/kg, heating value of methane.
qH m f Q f = 1135.2 kJ/kg, heat of combustion per kg of mixture.
wnet
= , thermal efficiency.
qH
P
2 = 10, pressure ratio.
P1
1
Brayton 1 k 1 = 0.6019, theoretical efficiency of Brayton cycle.
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wc u2 u1 , we u3 u4 , wnet we wc
w V
W wnet V Tq 2 , Tq net , engine torque
2
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Example:A jet engine runs on the fuel of propane with an
equivalence ratio of 0.3. The pressure ratio is 9.0. The compressor
efficiency is 85%, and the turbine efficiency is 90%. Find the
thrust of the engine.
Water has been distilled out with a filter ahead of the inlet of
analyzer to avoid the problem of clogging and corrosion.
1 1 1 n n
1 3O2 (2 ) CO (3 ) CO2 HC
1.76(1 n ) CO CO2 HC 2 2
4
( A / F )st
A/ F
( A / F ) st
A/ F
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Example:Find the air fuel ratio of the following measured data.
(141200+57472)/581700=0.0.3415
34.15% of energy has not been released during the combustion process.
The combustion efficiency is 65.85%.
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Example:Find the combustion efficiency of a gasoline engine with the
following measured data.
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Example:Find the combustion efficiency of a gasoline engine with the
following measured data.
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Work
2.41kW
Pumping
Mechanical 0.22kW
3.32kW Friction
0.69kW
Burned Heat loss
9.7kW 4.54kW
Unburned
1.26kW
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The oxygen concentration in normal air is about 21%. The oxygen rich
combustion is to increase the concentration of oxygen artificially to
enhance combustion. The flame temperature could be raised due to the
less content of dilute gas.
1 n n 1 n X n
CH n (1 )(O2 XN 2 ) CO2 H 2O ( 1)(1 )O2 (1 ) N 2
4 2 4 4
1
y : the molar fraction of oxygen
1 X
1
X 1
y
The amount of oxygen required for oxygen rich combustion:
For one mole of methane, if oxygen rich air is used as the oxidizer, the
amount of pure oxygen that has to be mixed with normal air is
y
n 2 z 7.52 2
1 y
For example, 40% oxygen rich air is used, 3.013 kmole of pure oxygen is
required for 1 kmole of methane.
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Example:Find the products of methane mixed with oxygen rich air and
the associated adiabatic flame temperature.
(1). y 30%
(2). y 40%
(3). y 80%
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1 n n 1 n X n
CH n (1 )(O2 XN 2 ) CO2 H 2O ( 1)(1 )O2 (1 ) N 2
4 2 4 4
n
h f , F QHV h f ,CO2 h f , H 2O
2
n
h f , F h f ,CO2 h f , H 2O QHV
2
n n 1 n X n
h f , F h f ,CO2 hCO2 h f ,H 2O hH 2O ( 1)(1 )hO2 (1 )hN2
2 2 4 4
n 1 n X n
QHV hCO2 hH 2O ( 1)(1 )hO2 (1 )hN2
2 4 4
If the products are cooled to the room temperature, then the heat of
combustion would be the same no matter how much excess air is.
Since both TL and QL are fixed values, the higher the value of Tb is, the
lower the waste heat would be. The advantage of rich oxygen
combustion is that the burned gas temperature could be higher than that
of normal air.
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Example:In a steam boiler, coal is fired with 150% excess air. The flue
gas temperature is 200℃. Find the saving of fuel if 50% oxygen rich air
is used instead of normal air.
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Assignment 2.19
In a foundry, molten iron is kept warm with stoichiometric propane flame.
Find the saving of fuel if 40% oxygen rich air is used instead of normal
air. The melting point of iron is 1536℃.
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Assignment 2.20
An internal combustion engine runs on the fuel of propane with an
equivalence ratio of 0.9. The compression process is assumed to be
isentropic and the compression ratio is 9.0. The temperature and
the pressure before the compression stroke are 40℃ and 90 kPa. If
40% oxygen rich air is used instead of normal air, find the IMEP of the
engine.
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Example:In an insulated rigid chamber, propane is mixed with
Combustion Engineering ME Dept NCHU 頁 49
stoichiometric amount of nitrous oxide. The temperature and pressure
in the chamber are 250℃ and 100 kPa. Find the adiabatic flame
temperature of the system.
C3H8+14N2O→3CO2+4H2O+14N2
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Assignment 2.21
In an internal combustion engine, liquid gasoline is mixed with
stoichiometric amount of nitrous oxide instead of air. For the same
displacement of cylinder, find the increase in energy content at 100 kPa
and 300K.
CH1.85+2.925N2O→CO2+0.925H2O+2.925N2
CH1.85+1.4625(O2 + 3.76N2)→CO2+0.925H2O+5.499N2
(dS )isolated 0
In a closed system, the system exchanges energy with its environment via
heat transfer and work. If an amount of heat Q is transferred from
system to its environment, the entropy change associated with the transfer
of heat is
Q
dS , or TdS Q
T
Q dU PdV
Combing the inequality of entropy and the first law results the following
equation.
The inequality implies that (dS )U ,V 0 , which means that entropy would
increase for all processes in a system in which U and V are kept constant.
As the system reaches the equilibrium state, in which no more changes
would occur, the entropy would be at a maximum value.
The inequality implies that (dS ) H , P 0 , which means that the entropy
would reach the maximum value at the equilibrium state for a system in
which H and P are kept constant.
Combustion Engineering ME Dept NCHU 頁 51
There is another way to interpret the inequality, i.e., (dH ) S , P 0 . It
means that the enthalpy reaches a minimum value as the system is at the
equilibrium state if S and P are kept constant in the system.
dA PdV SdT 0
The inequality implies that (dA)T ,V 0 , which means that the Helmholtz
function would reach the minimum value at the equilibrium state for a
system in which T and V are kept constant.
dG VdP SdT 0
The inequality implies that (dG )T , P 0 , which means that the Gibbs
function would reach the minimum value at the equilibrium state for a
system in which T and P are kept constant.
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Example: Calculate the Gibbs function of saturated water and that of
saturated vapor at 100℃.
g f h f Ts s f = 419.04-373.14×1.3069 = -68.617
g g hg Ts s g = 2676.1-373.14×7.3549 = -68.307
The error is caused by the uncertainty of the measured data.
g g g f (hg Ts sg ) (h f Ts s f ) h fg Ts s fg 0
Note: When two phases are in equilibrium, their Gibbs functions are the
same.
-----------------------------------------------------------------------------------------
dG VdP SdT
G G(T , P)
G G
dG dT dP
T P P T
G G
S , V
T P P T
G
Since S 0 , we may conclude that 0 . That is, G
T P
decreases when T is raised at constant pressure.
G
Since V 0 , we may conclude that 0 . That is, G
P T
increases when P is raised at constant temperature.
GH G GH
S ,
T T P T
G G H
T P T T
Gibbs-Helmholtz Equation
G H
T T
P T2
G g
V , v
P T P T
RT
For ideal gas, v
P
g RT
P T P
P
RT P
g dP RT ln
P0
P P0
P
g g 0 RT ln
P0
g g 0 v( P P0 )
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Example: Steam is compressed from a state of 200℃ and 1.5 bars to
another state of 10 bars adiabatically, calculate the change of the Gibbs
function.
G G G
dG dT dP dni
T P ,n P T ,n
i T , P ,n j
n
G
Define i ,chemical potential of component i
i T ,P ,n j
n
dG SdT VdP i dni
i k
,the effect of the mole number of component j
nk T , P ,n j ni T ,P ,n j
on the Gibbs function of the component i.
Why does the mole number of component j affect the Gibbs function of
the component i ?
For a system in which T and P are kept constant, the variations of Gibbs
function in terms of the variations in the mole fractions of each
component is
dG i dni , dg i dxi
Euler’s Theorem:
f f ( z1 , z2 , , zr )
f is homogeneous of degree m if
f ( z1 , z2 , , zr ) m f ( z1 , z2 , , zr )
H H (T , P, n1, n2 , , nr )
H TS i ni
G H TS i ni
When ni 1 , G g
The Gibbs function of each component at the reference state will not
be the same.
g h Ts
C O2 CO2
gC hC TsC
It is noted that the Gibbs function of formation does not equal to the
enthalpy of formation minus the product of temperature and entropy.
g f ,C h f ,C T0 sC
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Example: Calculate the Gibbs function of formation H2O at 298K and 1
bar.
g H 2O g H 2 0.5 gO2 (hH 2O TsH 2O ) (hH 2 TsH 2 ) 0.5(hO2 TsO2 )
g 0f g 0f ,0 (h h0 ) (Ts T0 s0 )
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Example: Calculate the Gibbs function of formation H2O at 1000K and
1 bar.
0
gCO2
-395939 kJ/kmole
PCO2
gCO2 gCO
0
RT ln = -395939 + 8.314×1000 ln(0.095) = -415509
2
P0
g H0 2O -192652 kJ/kmole
PH 2O
g H 2O g H0 2O RT ln = -192652 + 8.314×1000 ln(0.19) = -206459
P0
g N0 2 0 kJ/kmole
PN2
g N2 g N0 2 RT ln = 0 + 8.314×1000 ln(0.715) = -2789
P0
1
g i xi ( gCO2 2 g H2O 7.52 g N2 ) -80741 kJ/kmole
10.52
-----------------------------------------------------------------------------------------
A A B B C C D D
AdA B dB C dC D dD 0
dA Ad , dB B d , dC C d , dD D d
g A A g B B gC C g D D 0
P
g A g A0 (T ) RuT ln A
P0
P P
g A0 RuT ln A A g B0 RuT ln B B
P0 P0
P P
gC0 RuT ln C C g D0 RuT ln D D 0
P0 P0
C D
PC PD
C gC D g D A g A B g B RuT ln 0 A 0 B
0 0 0 0 P P
PA PB
P0 P0
G
K p1 exp 1.303×10
-3
RuT
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Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
1
H 2 O2 H 2O
2
1
G2 g H0 2O gO0 2 g H0 2 -135643 – (0) = -135643 kJ/kmole
2
G
K p 2 exp 3489.47
RuT
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Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
H 2 CO2 H 2O CO
1 1
G g H0 2O gCO0
gCO
0
g H0 2 ( gO0 2 gCO
0
gCO
0
) ( g H0 2O gO0 2 g H0 2 )
2
2 2
2
G G1 G1
G1 G2 G1 G2
G
K p exp e
RuT
e RuT
e RuT
K p1 K p 2
RuT
K p 4.547
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Assignment 2.21
Calculate the equilibrium constant of the reaction at temperature of 2000
K and pressure of 10 bars.
N2 O2 2 NO
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Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
H 2 CO2 H 2O CO
-----------------------------------------------------------------------------------------
-----------------------------------------------------------------------------------------
Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
2CO2 2CO+O2
-----------------------------------------------------------------------------------------
T B
log K p A ln( ) C DT ET 2
1000 T
1
1: H 2 H
2
1
2: O2 O
2
1 1
3: H 2 O2 OH
2 2
Combustion Engineering ME Dept NCHU 頁 62
1 1
4: N 2 O2 NO
2 2
1
5: H 2 O2 H 2O
2
1
6: CO O2 CO2
2
A B C D E
1 0.432168e+00 -0.112464e+05 0.267269e+01 -0.745744e-04 0.242484e-08
-----------------------------------------------------------------------------------------
Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
H 2 CO2 H 2O CO
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Assignment 2.22
Calculate the equilibrium constant of the following reaction at
temperature in the range of 1000~3000K.
H 2 CO2 H 2O CO
-----------------------------------------------------------------------------------------
PV nRuT
ni P P P P
[Ci ] i i xi
V RuT P RuT RuT
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Example: Carbon monoxide reacts with excess oxygen at temperature of
2000 K and pressure of 10 bars. Calculate the CO remaining in the
exhaust.
CO+O2 aCO2 bCO cO2
Balance in C atoms: a b 1 , b 1 a
a
Balance in O atoms: 2a b 2c 3 , c 1
2
a a
a b c 11 2
2 2
1
CO2 CO + O2
2
a a 2a
xCO2
abc 2 a 4a
2
b 1 a 2 2a
xCO
abc 2 a 4a
2
H 2O CO H 2 CO2
1 1 0 0
1-y 1-y y y
1111
xCO2 xH 2 P y y
K p =0.22
xCO xH 2O P0 (1 y )(1 y )
y=0.319
xH 2 16%
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Assignment 2.23
Hydrogen is reacting with 140% of theoretical air in an insulated constant
volume chamber. The initial temperature and pressure are 298K and
100kPa.
O2 2O
N2 2 N
O2 N2 2 NO
1
H 2O O2 2OH
2
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1 m
Cn H m (n )(O2 3.76 N 2 )
4
CO2 , CO, H 2O, H 2 , O2 , N2 , OH , O, H , N , NO,.........
For a lean combustion, CO2, H2O, and O2 are abundant in the products of
reaction, dissociation reactions do not affect the concentrations of these
components. As a result, it is reasonable to obtain the concentrations of
CO2, H2O, and O2 directly from atom balance.
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Example: A gas turbine engine runs on natural gas with an equivalence
ratio of 0.3. The inlet air is at 25℃ and 101.3 kPa. Fuel is injected into
the combustion chamber at 25℃. The pressure ratio of the compressor
is 10. The efficiency of compressor is 0.85. Assume that NO is in
equilibrium. Find the molar fraction of NO and CO at the exit of
combustor. Assume that air is an ideal gas.
1 1
N 2 O2 NO
2 2
1
CO2 CO + O2
2
-----------------------------------------------------------------------------------------
However, for rich and stoichiometric mixtures, O2 and H2 are rare in the
products of reaction, dissociation reactions play an important role to
determine the concentrations of these components.
Carbon balance: a + b = 1
Hydrogen balance: 2c + 2d = 4
Oxygen balance: 2a + b + c + 2e =4
Nitrogen balance: f = 7.52
There are six unknowns in the reaction equation. However, there are
only four balance equations. We need two more equations. These two
equations should be derived from the equilibrium between components.
We propose the following equations.
1
CO2 CO O2
2
1
H 2O H 2 O2
2
0.5 0.5
xCO xO2 P
0.5
b e P
K p1
xCO2 P0 a P0
0.5 0.5
xH 2 xO0.52 P d eP
K p2
xH 2O P0 c P0
0.5
P
(1 a) (2 c) (1 a) (2 c) 0 24.04 (a c) K p1a K p 2c
P
2
P0 0.5 3
(1 a) (2 c) 24.04 (a c) K p1a K p 2c
P
1
P 0.5
P0
0.5
P
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Assignment 2.23
Propane is burned with insufficient air with an equivalence ratio of
1.1. If the temperature is 2000 K and the pressure is 10 bar, calculate
the equilibrium constants and find the equilibrium concentrations of
the products. Assume the combustion products contain CO, H2,
H2O, CO2, and N2 only.
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Example: Methane is burned with stiochiometric amount of air.
CH 4 2(O2 3.76 N 2 )
aCO2 bCO cH 2O dH 2 eO2 fN 2 gOH hO iH jN kNO
Carbon balance: a + b = 1
Hydrogen balance: 2c + 2d +g + I = 4
Oxygen balance: 2a + b + c + 2e + g + h + k =4
Nitrogen balance: 2f + j + k = 15.04
There are eleven unknowns in the reaction equation. However, there are
only four balance equations. We need seven more equations. These
seven equations should be derived from the equilibrium between
components.
We propose the following equations.
1
CO2 CO O2
2
1
H 2O H 2 O2
2
O2 2O
H 2 2H
N2 2 N
H 2 O2 2OH
N2 O2 2 NO
0.5 0.5
xCO xO0.52 P b e P
K p1
xCO2 P0 a P0
0.5 0.5
xH 2 xO0.52 P d eP
K p2
xH 2O P0 c P0
xO2 P h 2 P
K p3
xO2 P0 e P0
xH2 P i2 P
K p4
xH 2 0
P d P0
CH 4 2(O2 3.76 N 2 )
aCO2 bCO cH 2O dH 2 eO2 fN 2 gOH hO iH jN kNO
There are twelve unknowns in the reaction equation. Besides the mole
fractions that are not known, the temperature is also unknown. We need
eight more equations. These seven equations should be derived from the
equilibrium between components. The last equation is derived from the
conservation of energy before and after combustion.
HR=HP
-----------------------------------------------------------------------------------------
CH 4 2(O2 3.76 N 2 )
aCO2 bCO cH 2O dH 2 eO2 fN 2 gOH hO iH jN kNO
There are thirteen unknowns in the reaction equation. Besides the mole
fractions that are not known, the temperature and the pressure are also
unknown. We need nine more equations. These seven equations
should be derived from the equilibrium between components. One
equation is derived from the conservation of energy before and after
combustion, and the other equation is derived form the state equation of
ideal gas.
UR=UP
uCH 4 2(uO2 3.76u N2 ) a uCO2 b uCO c u H 2O d u H 2 e uO2
f u N2 g uOH h uO i u H j u N k u NO
ni RT
P
V
The mole fractions to be determined are functions of temperature and
pressure. However, temperature should be solvable only when all the
mole fractions are already known. As a result, temperature and pressure
should be guessed before calculations proceed. The energy equation is
used to check if the guessed temperature is correct or not, and the ideal
gas equation is used to check if the pressure is correct or not.
-----------------------------------------------------------------------------------------
-----------------------------------------------------------------------------------------
Example: Methane is burned with air at 2000K and 10 bar. If the
combustion products contain CO, CO2, O2, H2, H2O, HO, H, O, NO,
N, and N2, find the equilibrium concentrations of products at
equilibrium ratio of 1.0.
-----------------------------------------------------------------------------------------
Example: Mixtures of methane and air at 300K and 100 kPa are
A:No dissociation
2 2 2
CH 4 (O2 3.76 N 2 ) CO2 2 H 2O ( 2)O2 3.76 N 2 , 1
2 2
CH 4 (O2 3.76 N 2 ) aCO2 bCO 2 H 2O 3.76 N 2 , 1
B:Weak dissociation
2
CH 4 (O2 3.76 N 2 ) aCO2 bCO cH 2O dH 2 eO2 fN 2
C:Strong dissociation
2
CH 4 (O2 3.76 N 2 )
aCO2 bCO cH 2O dH 2 eO2 fN 2 gOH hO iH jN kNO
A B C
0.8
0.9
1.0
1.1
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Assignment 2.24
Propane is burned with air at 2000K and 10 bar. If the combustion
products contain CO, CO2, O2, H2, H2O, HO, H, O, NO, N, and N2,
find the equilibrium concentrations of products at equilibrium ratios
from 0.7 to 1.3 with an increment of 0.1. The calculations may be
conducted with STANJAN. Plot the results of calculations.
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Assignment 2.25
Mixtures of propane and air at 300K and 100 kPa are burned in a
constant pressure process. If the combustion products contain CO,
CO2, O2, H2, H2O, HO, H, O, NO, N, and N2, find the adiabatic
flame temperature and the equilibrium concentrations of products at
equilibrium ratios from 0.7 to 1.3 with an increment of 0.1. The
calculations may be conducted with STANJAN. Plot the results of
calculations.
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Assignment 2.26
Mixtures of propane and air at 300K and 100 kPa are burned in a
constant volume process. If the combustion products contain CO,
CO2, O2, H2, H2O, HO, H, O, NO, N, and N2, find the adiabatic
flame temperature, the final pressure, and the equilibrium
concentrations of products at equilibrium ratios from 0.7 to 1.3 with
an increment of 0.1. The calculations may be conducted with
STANJAN. Plot the results of calculations.
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Assignment 2.27
A gas turbine engine runs with mixtures of propane and air. The
equivalence ratio is 0.4. The inlet air is at 300 K and 1 bar. The pressure
ratio is 10.0. Fuel is injected into the combustion chamber at 300 K and
10 bars. Calculate the work output. Assume that the products contain CO,
CO2, H2O, H2, O2, H, O, OH, NO, N, and N2.
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Assignment 2.28
An Otto engine runs with stoichiometric mixtures of propane and air.
The inlet condition is 300K and 100 kPa. The compression ratio is
11. If the combustion products contain CO, CO2, O2, H2, H2O, HO,
Combustion Engineering ME Dept NCHU 頁 73
H, O, NO, N, and N2, find the equilibrium concentrations of
products during the expansion stroke. The calculations may be
conducted with STANJAN. Plot the results of calculations.
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a b
, [CO2 ] , [ HC ] 1 c
[CO ]
abc x y w
[ H 2 ][CO2 ] yb
K
[ H 2O][CO] za
a
y Kz
b
1 a
y (n cn) z Kz
2 b
a 1
( K 1) z (n cn)
b 2
1 n cn
z
2 a K 1
b
a
K
a n cn b
y Kz
b 2 a K 1
b
1 n 1 1 n 1 1 n cn
x (1 ) (a 2b z ) (1 ) (a 2b )
4 2 4 2 2 a K 1
b
3.76 n
w (1 )
4
a
K
1 n 1 1 n cn n cn b 3.76 n
a b c (1 ) (a 2b ) (1 )
4 2 2 a K 1 2 a K 1 4
b b
1 1 1
4.76(1 ) CO CO2 HC
n
4
n 1 n 3 kn CO CO CO2
1 ( ) CO CO2 HC
4 2 4 4 CO2 k CO
( A / F ) st
A/ F
[CO] [CO2 ]
n
1 n 1 [CO] 2[CO2 ] 1 [CO] [CO2 ] [ HC ]
x (1 ) ( )
4 2 [CO] [CO2 ] [ HC ] [CO] [CO2 ] [ HC ] 2 [CO]
K 1
[CO2 ]
1 n 1 1 n [CO] [CO2 ]
x (1 ) ([CO] 2[CO2 ] )
4 2 [CO] [CO2 ] [ HC ] 2 [CO] K 1
[CO2 ]
x
[O2 ]
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Example:The measured emission data of a motorcycle at idling are
shown as the following.
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Assignment 2.29
Find the air fuel ratio of the following measured data without the oxygen
concentration, and then compare the oxygen concentration obtained with
the measured one.