First and Second Law Thermodynamic Analysis of Air and Oxy-Steam Biomass Gasification
First and Second Law Thermodynamic Analysis of Air and Oxy-Steam Biomass Gasification
First and Second Law Thermodynamic Analysis of Air and Oxy-Steam Biomass Gasification
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abstract
Article history:
chemical conversion to produce gaseous fuel, and the two most important criteria involved
in such process to evaluate the performance, economics and sustainability of the tech-
12 September 2014
nology are: the total available energy (exergy) and the energy conserved (energy efficiency).
Current study focuses on the energy and exergy analysis of the oxy-steam gasification and
comparing with air gasification to optimize the H2 yield, efficiency and syngas energy
density.
Keywords:
Casuarina wood is used as a fuel, and mixture of oxygen and steam in different pro-
Exergy analysis
portion and amount is used as a gasifying media. The results are analysed with respect to
Thermodynamic analysis
varying equivalence ratio and steam to biomass ratio (SBR). Elemental mass balance
Hydrogen
technique is employed to ensure the validity of results. First and second law thermody-
Syngas
namic analysis is used towards time evaluation of energy and exergy analysis. Different
Oxy-steam gasification
component of energy input and output has been studied carefully to understand the in-
fluence of varying SBR on the availability of energy and irreversibility in the system to
minimize the losses with change in input parameters for optimum performance. The energy and exergy losses (irreversibility) for oxy-steam gasification system are compared
with the results of air gasification, and losses are found to be lower in oxy-steam thermal
conversion; which has been argued and reasoned due to the presence of N2 in the airgasification. The maximum exergy efficiency of 85% with energy efficiency of 82% is achieved at SBR of 0.75 on the molar basis. It has been observed that increase in SBR results in
lower exergy and energy efficiency, and it is argued to be due to the high energy input in
steam generation and subsequent losses in the form of physical exergy of steam in the
product gas, which alone accounts for over 18% in exergy input and 8.5% in exergy of
product gas at SBR of 2.7. Carbon boundary point (CBP), is identified at the SBR of 1.5, and
water gas shift (WGS) reaction plays a crucial role in H2 enrichment after carbon boundary
point (CBP) is reached. Effects of SBR and CBP on the H2/CO ratio is analysed and discussed
from the perspective of energy as well as the reaction chemistry. Energy density of syngas
and energy efficiency is favoured at lower SBR but higher SBR favours H2 rich gas at the
expense of efficiency.
Copyright 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
* Corresponding author.
E-mail addresses: [email protected], [email protected] (S. Dasappa).
http://dx.doi.org/10.1016/j.ijhydene.2014.09.134
0360-3199/Copyright 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 9 4 7 4 e1 9 4 8 4
Nomenclature
EO2 _SEPARATION energy spent for O2 separation from air,
kJ/kg
total exergy input during gasification, kJ/kmole
Exin
EAUXILLARY_UNIT energy spent on the auxillary units of
gasifier. eg. water pump, water chiller, kJ/
kg
Exsteam exergy spent on steam generation and
superheating, kJ/kmole
QSTEAM energy spent on steam generation and
superheating, kJ/kg
exergy of char, kJ/kmole
Exchar
energy efficiency of gasifier, %
hen
chemical exergy of dry biomass, kJ/kg
eCH
DB
Ex
exergy, kJ/mole
mole fraction of ith specie
xi
physical exergy, kJ/kmole
Exph
s
entropy, kJ/(kmole K)
chemical exergy, kJ/kmole
Exch
entropy at SRS, kJ/(kmole K)
s0
enthalpy of ith specie, kJ/mole
hi
entropy of the ith specie at SRS, kJ/(kmole K)
si;0
enthalpy of ith specie at SRS, kJ/kmole
hi,0
I
irreversibility
R
universal gas constant, 8.314 kJ/(kmole K)
Abbreviation
temperature at SRS, K
T0
CBP
carbon boundary point
3 i.o
standard chemical exergy of ith specie at SRS,
kJ/kmole
LHV
lower heating value
exergy of hot syngas, kJ/kmole
Exgas
ER
equivalence ratio
ExH2 O_gas exergy of H2O in hot syngas, kJ/kmole
SBR
steam to biomass ratio (on mole basis)
exergy spent in O2 separation from air, kJ/
ExO2
kmole
SRS
standard reference state
Exch_mix component of exergy lost in, kJ/kmole gas due
to mixture
SMFR
superficial mass flux rate, kg/(m2 s)
Introduction
With the growing demand for renewable fuel to substitute the
fossil fuel, biomass gasification is emerging as an important
technology to fill the gap [1]. Conversion of solid fuel to
gaseous fuel helps in providing alternate fuel for many like IC
engines, gas turbines, fuel cells etc. Apart from energy plantation; agro residue, municipal waste and organic industrial
waste provides sustainable ways to extract energy from
waste. Sadhan and Dasappa [2] have researched on one of the
challenging issues of electrification in rural areas away from
the power grid network. Based on the life cycle cost analysis,
their study examined the economic feasibility of
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(1)
Boudouard reaction
Carbon
Nitrogen
Sulphur
Hydrogen
Oxygen
Chemical Composition
Molecular weight
(2)
(3)
Methane reaction
C 2H2 CH4 75 kJ=mole
(4)
Element
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(5)
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LHVSYNGAS LHVCHAR
LHVBIOMASS EO2 _SEPARATION EAUXILLARY_UNIT QSTEAM
Ein
Eout I
where, Ein and Eout represent the input exergy and output
exergy, and I represent the irreversibility induced during the
conversion process.
Exergy or the available energy in any gaseous species is the
sum of chemical and physical exergy (equation (7)). Physical
exergy depicts the change in enthalpy of particular gaseous
specie from standard state to the given pressure and temperature and also accounts for the loss in entropy in the
process (equation (8)). Chemical exergy of the mixture is the
standard chemical exergy mixing of all the constituents (1st
term in equation (9)) and the loss in entropy due to mixing of
different species of gases (2nd term in equation (9)).
Exergy efficiency
(6)
(10)
eCH
DB
where,
is the chemical exergy of dry biomass, and C, H, O,
N and S are respective elemental constituents in biomass and
A is the ash content, all in wt%.
Using the equation (10), standard exergy of wood is calculated
as 20.8 MJ/kg for the dry casuarina wood used in the present work.
Exergy efficiency is evaluated using equations 7e11.
ExSYNGAS ExCHAR
ExBIOMASS ExO _SEPARATION ExSTEAM
2
(11)
O2 ;H2 O
Ex Exch Exph
Exph
Exch
(7)
X
hi hi;0 T0 si si;0
X
xi i;0 RT0
X
xi ln xi
(8)
(9)
Product gas composition, mass flow rates of the fuel and reactants along with the gas temperature was used to arrive at
energy input and efficiency for varying SBR and ER. With the
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Exergy analysis
All the components in the equation (11) are evaluated separately to provide an insight on the system losses. Fig. 2 gives
the schematic representation of the exergy flow.
From Table 3, the highest exergy efficiency recorded was
at 86% with the SBR of 0.96 and then the value reduced to
69% at the SBR of 2.7. The component of sensible heat in the
gas is identified as physical exergy, which is lost during the
gas cooling process and is one of the major factors in the
deviation of energy efficiency from exergy efficiency. Physical exergy in the syngas was found to be increased from
about 6% to 12% with increase in SBR from 0.75 to 2.7, while
the physical exergy is found to be quite low with a value of
3.2% in the case of air gasification (Table 3). The data clearly
suggests the reduction in energy efficiency at higher SBR
due to the extra loss in sensible heat or physical exergy in
syngas. Presence of unreacted steam in the hot syngas is
found to be contributing significantly to the physical exergy,
which increases from 13% to 76% of physical exergy in
product gas. The exergy of mixture also contribute to the
losses and were found to be roughly 2% of total exergy of
syngas and no significant variations were observed with the
change in SBR. Mixture exergy in the case of air gasification
was found to be higher at 3.2%, and is argued due to the
presence of large fraction of N2 in product gas, where N2
accounts for 35% of the total mixture exergy in the product
gas.
Fig. 3 presents the exergy input fraction in O2 and steam
generation with change in SBR. Exergy input for O2 separation
and steam generation were roughly same for low SBR, but
with the increase in SBR, the steam exergy increased significantly from 6% to over 18%. Marginal increase in oxygen level
to maintain the bed temperature had shown no significant
impact on the exergy input.
Energy analysis
Similar to exergy efficiency, energy efficiency was also found
to be decreased with the increase in SBR. Efficiency reduced
from 80% to about 66% with the increase in SBR from 0.75 to
2.7. Efficiency in the case of air gasification is 80%, slightly
lower compared to oxy-steam gasification. The fraction of
energy input in oxygen separation accounts for over 5%e8%
for the range of SBR used in the experiment, even though in
absolute terms the input energy spent almost double to little
0 (Air)
0.75
0.86
0.96
1.39
1.5
1.66
1.8
2.43
2.52
2.7
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0 (Air)
80
83.1
3.2
0.8
0
0
24.1
3.2
0.1
0.1
0.03
0.01
0.01
0.01
0.75
0.86
0.96
1.39
1.5
1.66
1.8
2.43
2.52
2.7
80.3 0.2
85 0.2
5.9 0.04
0.8 0.02
6.1
5.1
13.7 0.01
1.7 0.01
75.2 0.1
83.1 0.1
6.5 0.03
1.6 0.01
6.9
4.9
25.4 0.02
1.9 0.01
73.5 0.1
85.7 0.1
6.6 0.05
1.7 0.02
7.7
4.5
25.9 0.03
1.9 0.01
76.3 0.3
80.3 0.3
6.9 0.03
2.3 0.01
10.6
5.1
33.2 0.02
2 0.01
73.5 0.2
76.6 0.2
7.3 0.02
3 0.01
11.3
5.5
41.1 0.01
2.1 0.01
68.1 0.1
84.3 0.1
8.1 0.05
3.2 0.02
12.4
5.1
39.4 0.02
2.2 0.01
77 0.1
83.9 0.1
8.6 0.06
4.1 0.02
13.2
5.8
47.4 0.03
2.4 0.01
64.7 0.2
79.6 0.2
10.6 0.07
6.7 0.05
16.1
6.1
68.2 0.03
2.5 0.01
65.8 0.2
77.8 0.2
11.1 0.05
8.5 0.04
17.4
6.3
76.2 0.02
2.7 0.01
65.6 0.3
69.2 0.3
11.3 0.06
8.6 0.06
18.4
6.3
76 0.03
2.8 0.01
0 (Air)
0.25
NA
NA
NA
NA
13.72 0.3
4.96 0.2
42.5 0.2
80 0.1
0.75
0.21
1.5
2.2
6.9
10.3
17
8.91
46.5
80.3
0.2
0.1
0.2
0.2
0.86
0.17
1.2
2.6
5.6
12.2
14.6
8.45
53.6
75.2
0.3
0.2
0.3
0.1
0.96
0.18
1.3
2.8
5.8
13
15.8
8.63
52
73.5
0.3
0.1
0.4
0.1
1.39
0.21
1.5
4
6.4
17.4
17.5
8.82
48.4
76.3
0.2
0.1
0.2
0.3
1.5
0.23
1.5
4
6.3
17.5
17.5
8.68
48.5
73.5
1.66
0.4
0.2
0.2
0.2
0.22
1.6
4.8
6.5
20
16.2 0.2
7.8 0.1
65.3 0.2
68.1 0.1
1.8
0.25
1.8
5.2
7.2
21.3
18.9
7.75
62.5
77
0.2
0.1
0.1
0.1
2.43
0.28
2
7
7.4
26.5
17.1
7.42
69
64.7
0.3
0.1
0.2
0.2
2.52
0.29
2.1
7.3
7.8
27.1
17.7
7.53
68.1
65.8
0.2
0.1
0.1
0.2
2.7
0.3
2.1
7.8
7.5
28.5
18
7.43
67.4
65.6
0.4
0.2
0.3
0.3
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Fig. 4 presents the exergy and energy efficiency for air gasification and oxy-steam gasification with the varying SBR. Data
for air gasification is plotted at SBR 0. Decrease in energy and
exergy efficiency with SBR is evident from Fig. 4. As expected,
the 2nd law exergy efficiency is evaluated to be higher than
First law energy efficiency. The differences are attributed to
the loss in sensible heat of the hot gas.
a. The exergy loss due to the mixing of gases in the case of air
gasification is about 3.2% of total hot gas exergy value
compared to 1.7% in case of oxy-steam gasification at lower
SBR of 0.75.
b. Total exergy (chemical and physical) in the hot gas due to
N2 itself accounts for 3.3% which directly translates to loss
in energy efficiency.
c. Loss in efficiency due to H2O accounts for 0.8%, which is
comparable to that in the case of oxy-steam gasification at
lower SBR of 0.75.
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The analysis suggests that the presence of N2 in the product gas contributes significantly towards the losses, while in
the case of oxy-steam gasification, the H2O fraction in the hot
gas leads to the similar losses at lower SBR, which makes air
gasification a less efficient process. It also justifies and reasons
the results presented by Silva and Rouboa [6] on the numerical
studies for the oxygen enriched air gasification with pine
wood suggesting the higher exergy efficiency at lower N2.
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Conclusion
The paper presents an in-depth study of the energy transformation during the gasification of biomass using exergy
analysis based on the experimental results of air and oxysteam gasification in a 50 kWTh downdraft reactor configuration. Sub-components contributing to the exergy flow are
studied and causes of irreversibility and inefficiencies have
been identified. Presence of N2 in the reaction system is
attributed towards slightly lower efficiency level in air gasification compared to oxy-steam gasification at lower SBR. The
current study provides scientific basis towards the increase in
efficiency in the oxygen enriched air gasification as reported
by Silva and Rouboa [7].
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references
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