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Article history:
Received 4 November 2011
Received in revised form 25 January 2012
Accepted 31 January 2012
Available online 15 February 2012
Keywords:
Coal gasication
Ternary diagram
Ash rich coal
Cold gas efciency
a b s t r a c t
The present paper addresses the development of a comprehensive thermodynamic approach for the evaluation of gasication processes. A ternary diagram is introduced for a South African coal with an elevated
ash content of 25.3 wt.%(wf). The ternary diagram allows the evaluation of most of the commercially
applied gasication technologies depending on the three variables O2, H2O and coal mass ow. Cold
gas efciency, dry CH4 yield, specic syngas production, H2/CO ratio, CO/C and CH4/C selectivity as well
as temperature and carbon conversion were selected as performance measures. Based on literature data,
generic models of the commercial Shell, Siemens, ConocoPhillips, HTW and GE coal gasications systems
were developed enabling an integration into the ternary diagram at standardized boundary conditions.
The graphical approach indicates the existence of optimum congurations for the specic gasier types
and leads to an individual potential assessment. At a typical gasication pressure of 30 bar, a theoretical
maximum cold gas efciency of 87.4% was identied at a temperature of 980 C for the above mentioned
coal, whereas the maximum syngas yield of 2.09 m3(H2 + CO STP)/kg(waf) was located at 1135 C. It is
shown that only uid-bed or two-stage processes have the potential to achieve these global maxima.
The sensitivity of these maxima to varying ash contents from 5 to 45 wt.% and to coal rank is investigated
as well. The study is concluded by the introduction of a simplied user diagram which was derived in
order to drive a process towards the identied maxima.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Due to midterm depletion of oil and gas, coal gains importance
not only as energy carrier but as feedstock for various chemical
syntheses [1]. The available commercial gasication processes
which have been presented earlier [2] must be evaluated if they
are capable for such conversion strategies. The main challenge is
the increasing ash content of the coal as reported from South Africa
[3], India [4], Japan [5], and China [6].
The comprehensive assessment of gasication processes is difcult due to lots of independent variables such as coal composition
and reactivity, temperature, pressure, H2O supply and other varying boundary conditions. A well-known approach, which was suggested rst by Grout [7], is to split coal in its molar CHO
composition plotting a ternary diagram. While Ghosh [8] used
the diagram for coal rank indication, Stephens [9] and Battaerd
and Evans [10] incorporated reacting gases and hydrocarbons as
well. Recently, Li et al. [11] used the same diagram to illustrate carbon deposition isotherms for a gasication system. However,
Corresponding author.
E-mail address: Martin.Graebner@iec.tu-freiberg.de (M. Grbner).
0016-2361/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2012.01.069
Please cite this article in press as: Grbner M, Meyer B. Introduction of a ternary diagram for comprehensive evaluation of gasication processes for ashrich coal. Fuel (2012), doi:10.1016/j.fuel.2012.01.069
1. Temperature and carbon conversion in equilibrium are combined offering a general overview and an easy location of gasier domains.
2. Cold gas efciency on lower heating value (LHV) basis and dry
methane gas yield are tted together because the high LHV of
methane contributes signicantly to the cold gas efciency
but limits gas quality in terms of synthesis applications or
pre-combustion CO2 separation.
3. Syngas yield and H2/CO ratio are combined since the expected
carbon utilization as well as the CO shift conversion efforts for
a desired downstream process can be derived directly.
4. The selectivity of carbon gasied to CO, CH4 and CO2 permits
carbon management, illustrating to which species the carbon
is converted. In order to normalize the sum to 100%, the isolines refer only to the converted part of the carbon. Higher
hydrocarbons (tars) are neglected.
A pressure of 30 bar is selected due to the suitability for various
chemical syntheses [13] and integrated gasication combined cycle (IGCC) power generation including CO2 capture as well [14].
Coal
O2
H2O
O2
Gasifier
- Siemens
- Shell
- HTW
- GE
- ConocoPhillips
Ternary
gasifcation
diagram
(on wt% basis)
H2O
Results of
generic models
Table 2
Unied boundary conditions for gasication modeling (LHV lower heating value, IP
intermediate pressure).
Coal
Results of adiabatic
equilibrium calculation
Syngas yield
& H2/CO ratio
Parameter
Value
Comment/reference
Pressure
Temperature
30 bar
1550 C
Thermal capacity
Coal/N2
Coal/transport gas
Solids in slurry
Slurry temperature
O2 purity
O2 temperature
Moderator steam
Quench water
500 MW
25 C
350 kg/m3(eff.)
65 wt.%
120 C
95 vol.%
240 C
37 bar/246 C
37 bar/175 C
[13,14]
>100 K above ash uid temperature
for slagging systems
LHV basis, equivalent to 2066 t/d
+3 bar above reactor pressure
[13]
[21]
[25]
Residual: 3 vol.% Ar and 2 vol.% N2
+3 bar above reactor pressure
Saturated from IP level
Preheated for high gas moisture
Table 1
Ultimate analysis of South African high-volatile bituminous coal (waf water and ash free, wf water free, ar as received, LHV lower heating value).
C
wt.%(waf)
Ash
wt.%(wf)
Moisture
wt.%(ar)
LHV
MJ/kg(wf)
79.6
4.1
13.3
2.1
0.9
25.3
6.0
22.39
Please cite this article in press as: Grbner M, Meyer B. Introduction of a ternary diagram for comprehensive evaluation of gasication processes for ashrich coal. Fuel (2012), doi:10.1016/j.fuel.2012.01.069
(w
t%
)
75
50
75
em
.t
ax
e
ur
at
er
r
fo
O
H2
n
co
2000
1500
2500 C
25
C
1000
100
50
3000 C
st.
Lurgi FBDB
GE
Siemens
Shell
ConocoPhillips
HTW
t%
100
A Entrained flow (dry feed)
B Entrained flow (slurry feed)
C Fluidized bed
D Fixed bed (dry ash) 25
(w
O2
10
0%
500 C
Carbo
n
%
8 0 70 % 0 %
6
0%
40
conve
rsion
30
20
0
0
25
50
75
100
Please cite this article in press as: Grbner M, Meyer B. Introduction of a ternary diagram for comprehensive evaluation of gasication processes for ashrich coal. Fuel (2012), doi:10.1016/j.fuel.2012.01.069
0
Lurgi FBDB
GE
Siemens
Shell
ConocoPhillips
HTW
100
Entrained flow (dry feed)
Entrained flow (slurry feed)
Fluidized bed
25
Fixed bed (dry ash)
Cold
30
0%
70
A
0.1
1.0
2.5
25
5
7
50
10
30
20
100
50
75
100
FBDB gasier. Besides cold gas efciency, the dry methane content
of the product gas in vol.% is exhibited. Fig. 3 shows that in the carbon-rich region (carbon conversion <100%) the dry methane yield
is mostly between 1 and 20 vol.%. In contarst, high cold gas efciencies (>80%) accompanied by methane contents of <0.1 vol.%
can be reached left of the 100% carbon conversion line, which is
typical for entrained-ow technologies.
Regarding technology potential, the HTW gasier or other uidbed processes (e.g. U-Gas [24]) show the highest exibility and potential for further optimization towards maximum cold gas efciency. But also the ConocoPhillips system shows a certain
potential since the mixing point inside the uid-bed domain may
be shifted towards increased cold gas efciency as well.
3.3. Ternary diagram for syngas yield and H2/CO ratio
As a further measure to assess gasication, the synthesis gas
yield in m3(H2 + CO STP)/kg(waf) was selected. The water and
0
100
Lurgi FBDB
GE
Siemens
Shell
ConocoPhillips
HTW
CO
75
1.25
H2/CO= 2.0
0.75
1.0
1.5
1.75
%
90
75
1 .5
3
STP)/kg(wa
0.5 m (H 2+CO
25
0.1%
25
10%
20%
40% conversion to CH
100
100
1%
2.5%
5%
f)
1.0
70
50
Re
sid
ua
l to
1.5
5
1.7
2. 0
50
%
0. 5
O
2
0.25 1.0
0.5
50
75
)
t%
(w
50
)
t%
(w
50
Lurgi FBDB
GE
Siemens
Shell
ConocoPhillips
HTW
O2
O2
(w
t%
)
75
100
(w
t%
)
25
25
%c
on v
ers
ion
to C
30
%
O
10
is m
ain
ly
85
0%
10
0%
(w
t%)
O
2
50
5
75
t%)
(w
50
O2
Ga
sE
fficie
10
ncy
%
75
A
B
C
D
ash free basis was suggested by Bellin et al. [19] for comparison
of varying ash contents. The molar H2/CO ratio is decisive determining the gas treatment steps. Fig. 4 presents the according plot
for syngas yield and H2/CO ratio. The highest syngas yield of
2.09 m3(H2 + CO STP)/kg(waf) was identied at 1135 C marked
by a hexagon in the diagram. Accordingly, the zone where syngas
yield is higher than 2.0 m3(H2 + CO STP)/kg(waf) is small resulting
in the exclusion of nearly all entrained-ow gasiers from that
area. According to the considered technologies, only the ConocoPhillips mixing points are located in the syngas yield area
>2.0 m3(H2 + CO STP)/kg(waf) if equilibrium is assumed. Unexpectedly, most of the uid-bed domain C overlaps with syngas yields
above 2.0 m3(H2 + CO STP)/kg(waf) indicating that not only dryfed entrained ow-processes can deliver a high syngas yield as
broadly concluded. Additionally, the elevated amount of syngas
can be supplied by uid-bed processes accompanied by much
higher H2/CO ratios up to 1.5 at 2.0 m3(H2 + CO STP)/kg(waf). The
observed extension of the high syngas yield area towards the
H2O corner reects basically the proceeding of the non-catalytic
water gas shift reaction at H2O excess conditions. In conclusion,
the CO shift conversion effort to meet the requirements of syntheses can be signicantly reduced for an optimized uid-bed system
in comparison to dry-fed entrained-ow processes with H2/CO ratios of 0.250.5 for the same gas production.
0
25
50
75
100
25
50
75
100
Fig. 4. Ternary diagram for syngas yield and H2/CO ratio (30 bar).
Fig. 5. Ternary diagram for for CO/C and CH4/C selectivity (30 bar).
Please cite this article in press as: Grbner M, Meyer B. Introduction of a ternary diagram for comprehensive evaluation of gasication processes for ashrich coal. Fuel (2012), doi:10.1016/j.fuel.2012.01.069
+4.6
Shell
Maximum for
slurry feed
slagging systems (B)
Siemens
+3.7
Maximum for
dry feed
slagging
systems (A)
Global
maximum (C)
+14.1 %-pts.
GE
possible percentage of increase relating the domain specic maximum to the generic model results. The same overall tendencies are
observed like in the case of cold gas efciency. The only difference
is that the HTW gasier shows the highest potential due to its comparatively low carbon conversion and high CH4 yield [19]. Due to
the high potential of the HTW gasier, enhanced concepts like
Power-HTW [26] or the internal circulation gasier (INCI) [27]
have been suggested earlier.
+13.7 %-pts.
CoP
60
65
70
75
80
85
90
t%
)
(w
O
50
Global
maximum (C)
50
25
+18.7 %
CoP
Maximum
cold gas efficiency
)
t%
+18.4 %
GE
ConocoPhillips
Shell
Siemens
HTW
75
(w
GE
+4.7 %
25
Maximum for
dry feed
slagging
systems (A)
O2
Siemens
Maximum for
slurry feed
slagging systems (B)
+5.8 %
Shell
HTW
+27.4 %
HTW
75
25
1.5
1.6
1.7
1.9
2.0
2.1
2.2
0
50
75
100
Please cite this article in press as: Grbner M, Meyer B. Introduction of a ternary diagram for comprehensive evaluation of gasication processes for ashrich coal. Fuel (2012), doi:10.1016/j.fuel.2012.01.069
70
Reference case
60
Shell
Siemens
GE-R
ConocoPhillips
HTW
50
10
40
2.0
Thermodynamic maximum
1.8
1.6
Shell
Siemens
GE-R
ConocoPhillips
HTW
1.4
1.2
0
10
Reference case
20
30
40
50
Coal type
/
South African
/
Pittsburgh #8
GE
GE
ConocoPhillips
ConocoPhillips
Shell
Shell
Siemens
Siemens
HTW
HTW
75
80 % Cold
gas efficiency
50
(w
O2
t%
)
(w
(w
)
t%
)
t%
50
50
50
2.2
25
30
Fig. 10. Cold gas efciency at varying ash content derived from gasier modeling.
O2
20
t%
)
80
50
(w
Thermodynamic maximum
GE
ConocoPhillips
Shell
Siemens
HTW
75
25
90
25
25
Ash fluid
temperatures
3
Maximum
syngas yield
Maximum
cold gas efficiency
75
75
25
0
50
75
100
25
50
75
100
Coal (wt %)
Fig. 9. Sensitivity of the 2.0 m3(H2 + CO STP)/kg(waf) and ash uid temperature isolines to coal ash content.
Fig. 12. Sensitivity of the 80% cold gas efciency and ash uid temperature iso-lines
to coal rank.
Please cite this article in press as: Grbner M, Meyer B. Introduction of a ternary diagram for comprehensive evaluation of gasication processes for ashrich coal. Fuel (2012), doi:10.1016/j.fuel.2012.01.069
Coal type
/
South African
/
Pittsburgh #8
25
t%
)
Maximum
syngas yield
50
)
t%
(w
(w
O2
GE
GE
ConocoPhillips
ConocoPhillips
Shell
Shell
Siemens
Siemens
HTW
HTW
75
50
25
50
100
75
Coal (wt %)
Fig. 13. Sensitivity of the 2.0 m3(H2 + CO STP)/kg(waf) and ash uid temperature
iso-lines to coal rank.
procedure as for the varied ash content was carried out. The 80%
cold gas efciency and the ash uid temperature iso-lines are presented in Fig. 12. Comparing the Pittsburgh #8 coal iso-lines to the
blue reference coal iso-lines, a shift is observed which can be partly
traced to the altered ash content. However, the change in the shape
of the curves refers to the change in coal rank.
Regarding the gasier points, it can be seen that for the dry feed
single stage entrained ow processes steam injection can help to
increase cold gas efciency in case of Pittsburgh #8 coal. Here,
the steam acts as temperature moderator. Otherwise the temperature would exceed 2000 C for 99.9% carbon conversion under dry
conditions. In case of the South African coal, the lower rank
1 bar
0
100 bar
6
Maximum
1
4
0.55
2.3
2.2
0.50
2.1
2.0
0.45
1.9
0.40
1.8
0.35
1.7
0.30
1.6
1400
Temperature (C)
30 bar
4
25
In order to exploit the identied potential, a simplied user diagram was developed for the specic syngas yield as exhibited in
Fig. 14. The user diagram allows identication of the maximum
possible syngas yield for pressures between 1 and 100 bar and
temperatures between 600 and 1500 C for the selected South African coal. The diagram is derived from the ternary diagram by setting the temperature and pressure to constant values and nding
the maximum syngas yield. For the identied point the steam/oxygen ratio in kg/m3(STP), the molar H2/CO ratio, the temperature in
C and the oxygen consumption O2/coal in m3(STP)/kg (ar) were
extracted from the diagram or calculated from the ow streams.
The relations are plotted in a quad diagram where monotonic correlations are used to link the individual curves in the diagrams. The
dashed curves represent the maximum syngas yield path at varying pressure. Hence, it is possible to draw connection lines
amongst the curves (see arrows in Fig. 14). All information to adjust the maximum syngas yield for a given pressure can be read
off easily from the plot. The arrows demonstrate the utilization
of the diagram for a 30 bar process. The maximum syngas yield
being 2.09 m3(H2 + CO STP)/kg(waf) is selected as starting point
which can be extended along the H2O/O2-line of 0.5 kg/m3(STP)
1400
1200
1200
1000
1000
800
800
Temperature (C)
75
600
600
0
Fig. 14. User diagram for optimum syngas yield for South African coal.
Please cite this article in press as: Grbner M, Meyer B. Introduction of a ternary diagram for comprehensive evaluation of gasication processes for ashrich coal. Fuel (2012), doi:10.1016/j.fuel.2012.01.069
Acknowledgements
We like to thank the Ministry of Science and the Arts of the Free
State of Saxony (R&D number 12272-1979) as well as the German
Federal Ministry of Economics and Technology for the nancial
support of the present work (R&D number 0327865). Special
thanks is regarded to P.A. Nikrityuk and A. Laugwitz for various
hints and productive discussions.
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Please cite this article in press as: Grbner M, Meyer B. Introduction of a ternary diagram for comprehensive evaluation of gasication processes for ashrich coal. Fuel (2012), doi:10.1016/j.fuel.2012.01.069