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Calculation of exergy values in sample points

of cogeneration system

Point No 10 (see transp. No 1 part 8):


parameters of methane supplied to combustion chamber:

m = 1.6419 [kg/s]
T = 298.15 [K]

p = 12 [bar]

chemical exergy of methane for state 10:


_____
• • e CH  kg kJ  kg  −1 
ECH
10 = m10 ⋅ CH 4
 ⋅ ⋅  =
M  s kmol  kmol  
 kJ 
=   = [kW ]
 s 
where:
M – molecular weight [kg/kmol]
_____
• • CH
= (1.6419 ) ⋅
e 824348
E CH
10 = m10 ⋅ CH 4
= 84.3668[ MW ]
M 16.043

physical exergy of methane for state 10:

• •
E PH
10 = m10 [(i10 − i0 ) − T0 (s10 − s0 )]

but: T10 = T0 so the physical exergy is the work of expansion of


ideal gas (maximum work i.e. irreversible i.e. ideal gas) at T0 , i.e.
___
• • •
p10 R p
E PH
10 = m10 ⋅ R ⋅ T0 ⋅ ln = m10 ⋅ ⋅ T0 ⋅ ln 10
p0 M p0

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Calculation of exergy values in sample points
of cogeneration system

Point No 10:
check of dimensions:
___
• • p  kg   kJ 
⋅ K  =   = [MW ]
R kJ kmol
E PH
= m10 ⋅ ⋅ T0 ⋅ ln 10 
p0  s K ⋅ kmol kg
10
M   s 
physical exergy of methane for state 10:
___
• •
⋅ ln⋅ T0 ⋅ 10 = (1.6419) ⋅ ⋅ (298.15) ⋅ ln
R p 8.314 12
E PH
10 = m10 ⋅ =
M p0 16.034 1.013
= 627[kW ] = 0.627[MW ]

where p0 = 1 [atm] = 1.013 [bar]

total exergy of methane for state 10:


• • •
E10 = E CH
10 +EPH
10 = 84.3668 + 0.627 = 84.9938[MW ]

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Calculation of exergy values in sample points
of cogeneration system

Point No 9 (see transp. No 1 part 8):


parameters of saturated steam:

m9 = 14 [kg/s]

T9 = 485.57 [K]

p9 = 20 [bar]

Notice: there is no chemical reaction and since the heat of phase


transition is included in physical exergy, then the standard chemical
exergy for water will be applied, i.e.
_____
• •
CH
eH 2 O
= (14) ⋅
45
ECH
9 = m9 ⋅ = 35[kW ] = 0.035[ MW ]
M 18.015
Question: do we have to take into account the fact, that the pressure
of saturated steam is 20 [bar] and not 1 [atm] as in tables ?

Answer: NO, it is exergy per kmole, so there is no need to account


for pressure in calculating chemical exergy of non – reacting steam

physical exergy of saturated steam for state 9:


• •
E PH
9 = m9 [(i9 − i0 ) − T0 (s9 − s0 )]
where enthalpies and entropies must be evaluated from steam table
data or calculated using the recipe from Table C.1, i.e.

E PH
9 = (14) ⋅ [2799.5 − 104.88 − 298.15 ⋅ (6.3409 − 0.3674 )] =
= 12.79[MW ]
total exergy of saturated steam for state 9:
• • •
E9 = E CH
9 +E PH
9 = 0.63 + 12.79 = 13.42[MW ]

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Calculation of exergy values in sample points
of cogeneration system

Point No 4 (see transp. No 1 part 8):

Assumptions:
- combustion is complete
- N2 is inert
- ideal – gas mixture principles apply for the air and combustion
products
- kinetic and potential energies of both products and reactants are
neglected
- heat transfer from combustion chamber is 2 % of LHV of fuel

Problem: the chemical composition of flue gases at p. 4 is unknown

Solution: assuming idealized combustion i.e. complete combustion at


stoichiometric conditions (i.e. supplying minimum air needed for
complete combustion) the chemical composition of flue gases may be
evaluated from balances of species involved in the reaction

molar flow rates of fuel and combustion products are related by:
• •
___ ___
nF nP

=λ •
= 1+ λ (S.1)
na na
where:

nF - molar flow rate of fuel

na - molar flow rate of air

nP - molar flow rate of combustion products
___
λ - fuel – air ratio

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Calculation of exergy values in sample points
of cogeneration system

Point No 4 ( part 2):


___
λ ⋅ CH 4 +
(one mole of air)

(S.2)
+ [0.7748 ⋅ N 2 + 0.2059 ⋅ O2 + 0.0003 ⋅ CO2 + 0.019 H 2O ] =
___
= [1 + λ ] ⋅ [ xN 2 ⋅ N 2 + xO2 ⋅ O2 + xCO2 ⋅ CO2 + xH 2 O ⋅ H 2O]

Notice: Eq.(S.2) results from Eq.(S.1), i.e.



• • ___
nF ___
na = 1 =λ nF = λ
1


• nP ___ • ___
na = 1 = 1+ λ nP = 1 + λ
1

balance of nitrogen (comparing both sides of Eq. S.2):

 ___ 
0.7748 ⋅ ( N 2 ) = 1 + λ  ⋅ x N 2 ⋅ ( N 2 )
 

0.7748
xN 2 = ___ (S.3.a)
1+ λ

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Calculation of exergy values in sample points
of cogeneration system

Point No 4 ( part 3):

balance of oxygen ( see l.h.s. of Eq. S.2):

___
 __ __
  __ __

λ ⋅ CH 4 →  λ ⋅ C + λ ⋅ O2  +  λ ⋅ H 4 + λ ⋅ O2 
   

___ ___
 ___ 
− λ ⋅ O2 − λ ⋅ O2 + 0.2059 ⋅ O2 = 1 + λ  ⋅ xO2 ⋅ O2
 

___
0.2059 − 2 ⋅ λ (S.3.b)
xO2 = ___
1+ λ

balance of carbon ( see l.h.s. of Eq. S.2):


___
 __ __
  __ __

λ ⋅ CH 4 →  λ ⋅ C + λ ⋅ O2  +  λ ⋅ H 4 + λ ⋅ O2 
   

___
 ___ 
λ ⋅ CO2 + 0.0003 ⋅ CO2 = 1 + λ  ⋅ xCO2 ⋅ CO2
 

___
0.0003 + λ
xCO2 = ___
(S.3.c)
1+ λ

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Calculation of exergy values in sample points
of cogeneration system

Point No 4 ( part 4):

balance of hydrogen ( see l.h.s. of Eq. S.2):


___
 __ __
  __ __

λ ⋅ CH 4 →  λ ⋅ C + λ ⋅ O2  +  λ ⋅ H 4 + λ ⋅ O2 
   

___
 ___ 
2 ⋅ λ ⋅ H 2O + 0.019 ⋅ H 2O = 1 + λ  ⋅ xHO ⋅ H 2O
 

___
0.019 + 2 ⋅ λ (S.3.d)
xH 2O = ___
1+ λ
energy balance (see Eq. 6.5 from p.4 of the lecture):
• • 1 •
0 = QCV − WCV + ∑ mi (ii + Vi 2 + g ⋅ zi ) +
i 2
• 1 (6.5)
− ∑ me (ie + Ve2 + g ⋅ z )
e 2
neglecting kinetic and potential energies (see assumptions):
• • • • • • • •
0 = QCV − WCV + nF ⋅ iF + na ⋅ ia − nP ⋅ iP (S.4)

from the assumption concerning the energy loss from combustion


chamber (and introducing Eq. S.1):
• • •

_______ _______

QCV = −0.02 ⋅ nF ⋅ LHV = na ⋅  − 0.02 ⋅ λ ⋅ LHV  (S.5.a)
 

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Calculation of exergy values in sample points
of cogeneration system

Point No 4 ( part 5):

since control volume is constant:



WCV = 0 (S.5.b)

introducing Eqs. (S.5.a) and (S.5.b) into Eq. (S.4) and making use of
Eq. (S.1):

 ___ _______
 • ___ ___ • ___ •  ___  ___
0 = na ⋅  − 0.02 ⋅ λ ⋅ LHV  + na ⋅ λ iF + na ⋅ ia − na ⋅ 1 + λ  ⋅ iP
   
and after some algebra:
___ _______
 ___  ___
___ ___ ___
0 = −0.02 ⋅ λ ⋅ LHV + λ iF + ia − 1 + λ  ⋅ iP (S.6)
 
from Table C.1 (since we assume perfect gas and data are given per
kmole, then the data are taken for p= 1 [bar] instead for p=12[bar]):
___
iF = - 74 872 [kJ/kmol] (S.7.a)

from thermodynamic tables:


________
LHVCH 4 = 802 361 [kJ/kmol] (S.7.b)

other quantities for Eq. (S.6):


___
 ___ ___ ___ ___

ia = 0.7748 ⋅ iN 2 + 0.2059 ⋅ iO2 + 0.0003 ⋅ iCO2 + 0.019 ⋅ iH 2O  ⋅ T3
 
(S.7.c)
___ ___ ___ ___ ___
(1 + λ ) ⋅ iP = [0.7748 ⋅ iN 2 + (0.2059 − 2 ⋅ λ ) ⋅ iO2 +
___ ___ ___ ___
+ (0.0003 + λ ) ⋅ iCO2 + (0.019 + 2 ⋅ λ ) ⋅ iH 2O ] ⋅ T4 (S.7.d)

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Calculation of exergy values in sample points
of cogeneration system

Point No 4 ( part 6):

introducing Eqs. S.7.a – S.7.d into Eq. S.6 and solving for fuel–air
ratio:
___ ___ ___ ___
___ 0.7748 ⋅ ∆ iN 2 + 0.2059 ⋅ ∆ iO2 + 0.0003 ⋅ ∆iCO2 + 0.019 ⋅ ∆ iH 2 O
λ = ___

________ ___ ___ ___

iF − 0.02 ⋅ LHV −  − 2 ⋅ iO2 + iCO2 + 2 ⋅ iH 2 O  ⋅ T4
  (S.8)

data for Eq. S.8 evaluated from Table C.1:

Table S.1
component i850K i1520K ∆i
[kJ/kmol] [kJ/kmol] [kJ/kmol]
N2 17 072 39 349 22 277
O2 17 540 41 138 23 598
CO2 - 367 121 - 330 159 36 962
H2O - 221 321 - 192 283 - 29 038

inserting data from Table S.1 into Eq. S.8 one obtains the fuel – air
ratio:

___
λ = 0.0321 (S.9)

that allows to solve Eqs. S.3.a – S.3.d and gives chemical composition
of flue gases at the outlet from combustion chamber, i.e.
x N 2 = 0.7507
x CO2 = 0.0314
(S.10)
x O2 = 0.1373

x H 2 O = 0.0806

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Calculation of exergy values in sample points
of cogeneration system

Point No 4 ( part 7):

Notice: when calculating exergy we assume T0=298.15 [K] (25oC),


i.e. below the dew point, then it is necessary to calculate mole
fractions for liquid water and water vapour, i.e.
x H 2O ( g ) x H 2O ( l )

saturation pressure pυ for xH2O=0.0806:

pυ = xH 2O ⋅ p = 0.0806 ⋅1.013 = 0.0817[bar ]


and for this pressure the dew point ≈ 420 [C], so certainly a part of
water will condensate, let us assume it is:

nυ - molar fraction of gaseous water (unknown)

i.e. for 1 kmole of combustion products there will be nυ of water


vapour and its fraction will be (approximately):


pυ H2O = ⋅ pa (S.11)
0.7507 N 2 + 0.1373O2 + 0.0314CO2 + nυ

1 − 0.0806 = 0.9194
inserting numerical values:


0.0317 = ⋅1.013
0.9194 + nυ
solving for nυ gives:

nυ = 0.0297[kmol ]

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Calculation of exergy values in sample points
of cogeneration system

Point No 4 ( part 8):

corrected values of mole fractions:

x N 2 = 0.7507 x N' 2 = 0.791

x CO2 = 0.0314 gas xO' 2 = 0.1446


phase
x O2 = 0.1373 = '
xCO2
= 0.0331
0.949
x H 2O ( g ) = 0.0297 xH' 2O = 0.0313

x H 2O ( l ) = 0.051
∑ = 1.000

finally:
x N' 2 = 0.791 xO' 2 = 0.1446 '
xCO2
= 0.0331
(S.12)
xH' 2 O ( g ) = 0.0313 x H 2O ( l ) = 0.051

chemical exergy of flue gas (i.e. gas mixture – Eq. 7.4):

__ CH __ CH __
e = ∑ xk e k + R T0 ∑ xk ln xk (7.4)

and introducing notation for corrected mole fractions (Eq. S.12):

 __ CH  __ CH __
 e  = ∑ xk e k + R T0 ∑ xk' ln xk'
' (S.13)
 
 g

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Calculation of exergy values in sample points
of cogeneration system

Point No 4 ( part 9):

calculating chemical exergy with mole fractions (Eq. S.12) and


standard chemical exergies (Table C.2) gives:

 __ CH  __ CH __
 e  = ∑ xk e k + R T0 ∑ xk' ln xk' =
'
 
 g
= 0.791 ⋅ 639 + 0.791 ⋅ ln(0.791) + gas
+ 0.1446 ⋅ 3951 + 0.1446 ⋅ ln(0.1446) + phase
=
+ 0.0331 ⋅14176 + 0.0331 ⋅ ln(0.0331) + 0.949
+ 0.0313 ⋅ 8636 + 0.0313 ⋅ ln(0.0313) =
 kJ 
= 115
 kmol 

chemical exergy rate per mole at Point N0 4:

• CH
 kJ 
e 4 = 0.949 ⋅115 + 0.051 ⋅ 45 = 111.43  (S.14.a)
 kmol 

chemical exergy rate of combustion products at Point N0 4:


_____
• • CH
e4 111.43
E CH
4 = m4 ⋅ = 92.9176 ⋅ = 0.3665[ MW ] (S.14.b)
M 28.254

Question: is such a low value of chemical exergy at the outlet of


combustion chamber surprising ?

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Calculation of exergy values in sample points
of cogeneration system

Point No 4 ( part 9):

physical exergy at Point No 4 :

 ___ ___   ___ ___ 


• •
 i4 − i0  − T0 ⋅  s4 − s0 
E PH
4 = m4 ⋅    
(S.15)
M
___ ___
i4 for N2 , O2 , CO2 , H2O given in Table S.1(see transp.9), i4 for
the mixture:

 ___   kJ 
 i4  = 9304.5  (S.16.a)
 M  kmol 
Notice: subscript M for mixture

reference enthalpy and entropy evaluated from Table C.1, i.e.

 ___ 
 i0  = 0.7507 ⋅ (0) + 0.1372 ⋅ (0) + 0.0314 ⋅ (−393521) +
 M
+ 0.02971 ⋅ (−241856) + 0.051 ⋅ (−285829) =
 kJ 
= −34117 
 kmol 
(S.16.b)

 ___ 
 s0  = 0.7507 ⋅ (193.452) + 0.1372 ⋅ (221.115)
 M
+ 0.0314 ⋅ (242.022) + 0.02971⋅ (217.53)
 kJ 
+ 0.051 ⋅ (69.948) = 193.17  (S.16.c)
 kmol 
13
Calculation of exergy values in sample points
of cogeneration system

Point No 4 ( part 10):

Notice: contributions of particular gas components at s0 are


calculated for partial pressures, e.g.

xN' 2 ⋅ p0
( )
___ ___ ___
s N 2 T0 ; x N' 2 ; p0 = s 0
N2 (T0 ) − R ⋅ ln =
pref
0.791 ⋅1.013  kJ 
= 191.61 − 8.314 ⋅ ln = 193.452 
1  kmol 

introducing Eqs. S.16.a – S.16.c into Eq. S.15 we obtain the physical
exergy of combustion products at Point N04:
 ___ ___   ___ ___ 
• •
 i4 − i0  − T0 ⋅  s4 − s0 
E4PH = m4 ⋅    =
M
[9304.5 − (−34117)] − 298.15 ⋅ [235.7 − 193.17]
= 92.92 ⋅ =
28.254
= 101.1[MW ] (S.17)

summation of Eqs. S.14.b and S.17 gives the total exergy rate of
combustion products at Point N04:

• • •
E4 = E CH
4 +E PH
4 = 0.3665 + 101.1 = 101.4665[MW ]

14

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