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Fuel xxx (2012) xxxxxx

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Introduction of a ternary diagram for comprehensive evaluation


of gasication processes for ash-rich coal
Martin Grbner , Bernd Meyer
Department of Energy Process Engineering and Chemical Engineering, Technische Universitt Bergakademie Freiberg, Fuchsmhlenweg 9, Reiche Zeche, 09599 Freiberg, Germany

a r t i c l e

i n f o

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).

regarding performance parameters, technology comparison and


optimum identication, the CHO plot has not been used,
although it has a signicant potential to illustrate basic relations.
It should be noted that in a CHO molar plot, the region of gasier
operation in the range of the triangle O2H2OCxHyOz would be
very small. However, if the same O2H2OCxHyOz-system is used
as corner points for a new molar based ternary diagram, recalculations of the coal ow eliminating sulfur, nitrogen, moisture and ash
as well as recalculations of the technical oxygen ow eliminating
nitrogen and argon will be necessary.
In the present paper, we introduce a novel approach of plotting
O2H2Ocoal mass ow in wt.% in a ternary plot. It allows the
assessment of temperature, carbon conversion, cold gas efciency,
dry methane yield, specic synthesis gas production, H2/CO ratio as
well as CO/C and CH4/C selectivity of the converted carbon in an
easy way without recalculations of the input ows.
With the disengagement from molar fractions, a distinct atomic
ratio is not longer necessary for each stream. Hence, CxHxOz can be
replaced by coal containing all impurities (e.g. mineral matter) and
oxygen may include nitrogen as well. Consequently, the diagram is
easy to use because the mass ows into a technical gasier from
practice can be applied directly.

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

M. Grbner, B. Meyer / Fuel xxx (2012) xxxxxx

An ash-rich South African coal was selected for the investigation


since elevated ash contents pose a challenge to most of the commercial gasication processes. Table 1 presents the coal composition and LHV showing an ash content of 25.3 wt.%.
Since all diagrams are based on isobar, adiabatic equilibrium
calculations, all gures represent the maximum achievable values
of the distinct parameters. In the next step, technical gasiers are
incorporated in the diagram according to their O2H2Ocoal
consumptions.

2. Theoretical and technological background


2.1. Ternary diagram setup
The O2H2Ocoal ternary diagram is developed by means of
equilibrium modeling applying minimization of Gibbs free enthalpy, e.g. in the software Aspen Plus [12]. Fig. 1 indicates the principal scheme of the ternary gasication diagram setup. It can be seen
that the mass ow rates into the gasication systems are normalized to unity and treated as mass fractions in wt.% which serve as
input parameters for the diagram. In order to concentrate information and maintain applicability, reasonable combinations of output
parameters are identied leading to four types of ternary diagrams
as presented in Fig. 1.

2.2. Location of technical gasiers


Higman and van der Burgt [13] provide detailed descriptions for
the ConocoPhillips (E-Gas), General Electric (GE), Shell, Siemens,
HTW (high-temperature Winkler) and Lurgi xed-bed dry bottom
(Lurgi FBDB) gasication technologies, which are selected to be
integrated in the diagram. In a rst step, for each entrained-ow
and uid-bed process a generic thermodynamic Aspen Plus model
is developed. Deviations from equilibrium are included using user
dened functions. Verication data for the models are given by
Woods et al. [15] for ConcoPhillips, by McDaniel [16] for GE, by
Rich et al. [17] for Shell, by Deutsche Babcock [18] for Siemens,
and by Bellin et al. [19] for HTW. In a second step, unied boundary
conditions were applied to the models to maintain comparability.
From the two types of Lurgi xed-bed gasiers, the low-temperature Lurgi xed-bed dry bottom (Lurgi FBDB) system was integrated in the study, because Modde and Krzack [20] provide data
which was gained from operating experiences for a similar coal
(German bituminous coal from Dorsten with 22.0 wt.%(wf) ash).
For the high-temperature slagging British Gas/Lurgi (BGL) xedbed gasier, no data for ash-rich coal was available. Table 2 shows
all the operating conditions and the physical states of all entering
streams serving as boundary conditions for the models.
In order to simplify the location of gasiers and the analysis of
the diagrams, four different domains A, B, C and D are introduced.
These four domains apply for single stage processes and their
boundaries are given mostly by technical limitations. For entrained-ow gasiers, an upper temperature limit of 2000 C and
a lower temperature limit of 1440 C (ash uid temperature) must
be maintained to ensure material lifetime and slag discharging
conditions. In case of dry feeding systems, moderator steam can
vary between 0 and 6 wt.%. Hence, the domain A for dry feed

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

Temperature & Cold gas efficiency


carbon conversion & dry CH4 content

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

CO/C & CH4/C


selectivity

Location of gasifiers, operating range and potential assessment


Fig. 1. Schematic overview of the ternary gasication diagram setup.

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

M. Grbner, B. Meyer / Fuel xxx (2012) xxxxxx

(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.

In Fig. 2, the temperature and carbon conversion is given while


the regions for single-stage processes are marked. The Shell and
Siemens systems group above the sticky ash temperature range
on the O2coal-axis indicating that no moderator steam is necessary due to the high ash content. In case of the Siemens system, little H2O is participating in the reaction because of the slight CO shift
conversion in the full water quench. In the slurry feeding entrained
ow domain B, the GE technology and the rst stage of the ConocoPhillips gasier appear. The point of ConocoPhillips is moved towards the O2coal-axis since the slurry feed stream is upgraded by
recycled char which is left over from the chemical quench [13,15].
If two stage processes occur (e.g. ConocoPhillips, Mitsubishi [2]) or
independent gasifying agent inlets exist (e.g. Tsinghua two-stage
oxygen gasier), mixing lines can be drawn in the diagram. The
law of reverse levers can be applied to identify the mixing points
which is described in detail by Stephens [9]. Hence, for the ConocoPhillips gasier three points appear which are located on one
line. The central (mixing) point represents the second stage (gasier outlet) and the point on the H2Ocoal-axis represents the slurry point which is contacted with the product gas from the rst
stage. Consequently, the mixing point occurs outside the slurryfed domain and can theoretically move along the mixing line at
varying slurry mass ows.
If the coal had a higher ash uid temperature, which might apply to other high ash coals, all slagging gasier points would be
shifted towards the 100 wt.% O2 point resulting in higher
temperatures.

Lurgi FBDB
GE
Siemens
Shell
ConocoPhillips
HTW

t%

3.1. Ternary diagram for temperature and carbon conversion

100
A Entrained flow (dry feed)
B Entrained flow (slurry feed)
C Fluidized bed
D Fixed bed (dry ash) 25

(w

3. Results and discussion

O2

entrained-ow systems is dened. The slurry feed entrained-ow


domain B refers to the concentration of solids in the coalwater
slurry ranging from 50 to 70 wt.% [21]. For the uid-bed gasier
domain C a maximum temperature of 1200 C ( 80 K below softening temperature) is suggested to avoid undesired bed agglomeration. Although carbon conversions in most uid-beds were very
low because of lower gasication temperature, Adlhoch et al.
[22] and Keller et al. [23] report from test runs, that carbon conversions >80% are feasible, which was selected as boundary. Accordingly, Bellin et al. [19] suggested a minimum exit gas
temperature of 850 C. The left boundary represents a maximum
gasifying agents to coal mass ratio of 3 as, e.g. tested in the UGas system [24]. For completeness, the xed-bed domain for dry
ash conditions D was also integrated between 600 and 800 C
being aware that thermodynamic equilibrium is not reached at this
temperature level.
Since all iso-lines (e.g. temperature) are gained by idealized adiabatic equilibrium calculations at 30 bar, only the gasier input
mass ows are necessary to locate the individual systems in the
ternary diagram. Consequently, the gasier points in the diagram
represent a hot, well-mixed reaction zone where equilibrium
might be approached. Except for xed-bed gasiers, this zone is
equivalent to the hot raw gas outlet before any heat recovery
(e.g. GE, HTW) or quenching (e.g. Shell, Siemens). For two-stage
processes like ConocoPhillips, more points can occur. If the ash
or slag mass ows leave the hot reaction zone apart from the
raw gas (e.g. HTW, Shell, ConocoPhillips), the gasier points will
refer to the raw gas ow. The integration of the ash in the calculations is explained in detail in Section 3.6.
Since the generic gasier models incorporate deviations from
equilibrium, differences between the model results and the ternary
diagram emerge regarding performance measures. Their magnitude is an indicator for the potential of process optimization and
is therefore addressed in Section 3.5.

10

0%

500 C

Carbo
n

%
8 0 70 % 0 %
6

0%

40

conve
rsion

30

20

0
0

25

50

75

100

South African Coal (wt%)


Fig. 2. Ternary diagram for temperature and carbon conversion (30 bar).

The uidized bed region C indicates an operation in carbon-rich


bed inventory mode (carbon conversion <100 %) or ash-rich bed
inventory mode where the HTW gasier operates at carbon-rich
conditions. The broad extension of the domain indicates the high
exibility in gasifying agent supply for the uidized-bed region.
It must be noted that the plotted carbon conversion refers to equilibrium carbon (e.g. HTW) and is not identical to non-converted
carbon of low reactivity leaving a gasier (e.g. GE). These minor
quantities of inert carbon can be subtracted from the feed coal
mass ow since it is not taking part in the reaction.
In the xed-bed domain D, the Lurgi FBDB gasier is integrated
according to its consumption parameters showing the highest H2O
consumption amongst all evaluated systems. As a result of combining slagging and xed-bed conditions, a potential BGL gasier
point would be located outside domain D shifted towards higher
O2 and lower H2O conditions.
A great advantage of the diagram is to asses directly the effect of
additional O2, H2O or coal injection with the help of mixing lines.
For example, if it is considered to upgrade the Lurgi FBDB product
gas by oxygen injection, the mixing line between the gasier point
and the top corner (O2) of the diagram applies following the law of
reverse levers for the intercepts as in every ternary diagram.
3.2. Ternary diagram for cold gas efciency and dry methane yield
Fig. 3 shows the cold gas efciency which is dened on lower
heating value basis [13]. A tongue-shaped region of elevated cold
gas efciency (>85%) can be observed surrounding the 100% carbon
conversion iso-line. Along this line, a maximum cold gas efciency
of 87.4% was identied at 980 C being inside the uid-bed gasier
domain C indicated by the hexagon. Since any moderator steam
injection to a dry feed single stage entrained-ow process would
cause losses in cold gas efciency, no exibility or signicant potential can be derived from domain A. If very optimistic stable slurry concentrations of 70 wt.% solids were assumed, still cold gas
efciencies >80% would not be possible for single stage slurry feed
entrained ow processes in domain B. At lower temperatures again
an increase in cold gas efciency can be determined. However, kinetic limitations and tar formation might offset the theoretical
equilibrium values below 800 C. Hence, the indicated equilibrium
cold gas efciency of 85% is in practice not achieved by the Lurgi

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

M. Grbner, B. Meyer / Fuel xxx (2012) xxxxxx

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

40 vol% (dry gas) CH

50

75

100

South African Coal (wt%)


Fig. 3. Ternary diagram for cold gas efciency and dry methane yield (30 bar).

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

A Entrained flow (dry feed)


B Entrained flow (slurry feed)
C Fluidized bed
D Fixed bed (dry ash)

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

A Entrained flow (dry feed)


B Entrained flow (slurry feed)
C Fluidized bed
D Fixed bed (dry ash) 25

(w
t%
)

25

Fig. 5 reveals that only the dry feed entrained-ow processes


(Shell and Siemens) can yield product gases where more than
90% of the coals carbon is converted to CO. For all other examined
processes, less than 80% CO/C selectivity was observed. In case of
the slurry fed GE system mainly CO2 emerges whereas in terms
of the ConocoPhillips and HTW technologies also considerable
amounts of methane accompanied by CO2 can be expected. Comparing the discussed syngas yield maximum from Fig. 4 to the
equivalent area in Fig. 5, the decreasing CO/C selectivity towards
the H2O corner illustrates the conversion of CO to CO2 producing
H2. Again the uid-bed domain provides the highest exibility
and potential for further optimization especially in the area close
to the O2coal-axis.

3.4. Ternary diagram for CO/C and CH4/C selectivity

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

South African Coal (wt%)

South African Coal (wt%)

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

M. Grbner, B. Meyer / Fuel xxx (2012) xxxxxx

+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

3.6. The inuence of ash content


+10.0 %-pts.

60

65

70

75

80

85

90

Cold gas efficiency (%)


Fig. 6. Cold gas efciency potential analysis (30 bar).

3.5. Technology potential analysis


The comparison of the results of the generic gasier models to
the idealized indications of the ternary diagrams permits the evaluation of distinct potentials for each technology. Fig. 6 exhibits the
cold gas efciency results obtained from the generic models indicated by the symbols. The maximum possible cold gas efciency
values obtained from the ternary diagrams domain limits A, B, C
are inserted as well. Hence, the difference between the gasier
point and the domain limits represents the optimization potential
for each technology.
Although ash rich coal is processed, the Siemens (78.8%) and the
Shell (77.9%) systems show the highest cold gas efciency closely
followed by the HTW gasier (77.4%). The two-stage slurry fed
ConocoPhillips (CoP) system achieves a cold gas efciency of
73.7% while the single-stage GE system has only 60.9% due to poor
single pass carbon conversion [16]. Fig. 6 also indicates the possible increase in cold gas efciency in %-pts. if adiabatic equilibrium
is approached. The highest potential is obvious for the GE system
accompanied by a low maximum. The Siemens and Shell systems
show little potential on an already high level. The ConocoPhillips
and HTW systems can theoretically approach the global maximum
exceeding all other systems.
The same analysis is carried out for the syngas yield presented
in Fig. 7. Again the Siemens (1.91) and Shell (1.89) systems show
the best performance followed in a distance by ConocoPhillips
(1.76), HTW (1.64) and GE (1.52). The potential is shown by the

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)

Coal ash content


/
5.0 wt% (wf)
25.3 wt% (wf)
/
/
45.0 wt% (wf)

+5.8 %

Shell

In order to investigate the inuence of the ash content, a part of


the ternary diagram is enlarged where coal mass ow is between
25 and 100 wt.% including all modeled gasiers. The ash content
of the South African coal is varied from 5 to 45 wt.%(wf) by scaling
the reference case from Table 1. The ash is respected in the calculation of the ternary diagram and in the gasier models as a nonreacting stream. It has a constant specic heat capacity of
1.05 kJ/(kg K) and a melting enthalpy which increases between
the ash softening and uid temperature to a nal value of
678.6 kJ/kg. The value was obtained from the FactSage database
[28] applying the measured ash composition under reducing
conditions.
Corresponding to Figs. 2 and 3 only the 80% cold gas efciency
and ash uid temperature (1440 C) iso-lines are shown in Fig. 8
for three different ash contents. The gasier points are displayed
and consistent with the ash content in color. The maximum cold
gas efciency points are displayed as well.
It can be seen that the area of cold gas efciencies >80 % as well
as the ash uid temperature iso-lines are shifted towards the 100 %
coal corner due to the increased ash fraction of the coal mass ow.
Another effect is that the same area becomes smaller with increasing ash content due to the energy consumption by ash heating. The
location of the single stage slagging gasiers is determined by the
necessity to operate well above the ash uid temperature. Consequently, the Siemens and Shell systems are located within the high
cold gas efciency area at 5 wt.%(wf) ash. They cannot approach
the same area at 45 wt.% because the area is shifted towards lower
temperatures. The shift of the GE and ConocoPhillips systems with
increasing ash content is related to the constant slurry solids

HTW

Ash fluid temperature


80 % Cold gas efficiency

+27.4 %

HTW

75
25

1.5

1.6

1.7

1.9

2.0

2.1

Syngas Yield (m(H2+CO STP)/kg(waf))


Fig. 7. Syngas yield potential analysis (30 bar).

2.2

0
50

75

100

South African Coal with variable ash content (wt %)


Fig. 8. Sensitivity of the 80% cold gas efciency and ash uid temperature iso-lines
to coal ash content.

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

M. Grbner, B. Meyer / Fuel xxx (2012) xxxxxx

3.7. The inuence of coal rank


To assess the inuence of the coal rank, a Pittsburgh #8 bituminous coal was selected which has an ash content of 10.2 wt.%(wf)
and a LHV of 34.0 MJ/kg(waf) while the LHV of the reference coal
is 29.9 MJ/kg(waf). The composition and ash data were taken from
Miller and Tillman [29]. A lower ash uid temperature of 1340 C
permits slagging conditions at 1450 C. The same analysis
Coal ash content
/
5.0 wt% (wf)
/
25.3 wt% (wf)
/
45.0 wt% (wf)

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

Ash content (wt% (wf))


Fig. 11. Syngas yield at varying ash content derived from gasier modeling.

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

Ash content (wt% (wf))

t%
)

80

50

Ash fluid temperature

(w

Thermodynamic maximum

GE
ConocoPhillips
Shell
Siemens
HTW

75

25

90

Cold gas efficiency (%)

concentration of 65 wt.%. Hence, the decreasing energy density of


the slurry leads to an exclusion from the high cold gas efciency
area at high ash contents.
The analysis of the diagram shows that the HTW gasier is able
to follow the elevated cold gas efciency area due to its operation
at dry ash conditions. Furthermore, it approaches the cold gas efciency maximum with increasing ash content.
The same analysis is carried out for the 2.0 m3(H2 + CO STP)/
kg(waf) iso-line in Fig. 9. Again, the shift towards the 100% coal
corner with increasing ash content is obvious. Due to the increasing combustion of syngas for ash heating, the area of syngas yields
>2.0 m3(H2 + CO STP)/kg(waf) is signicantly reduced with increasing ash content. All slagging gasiers cannot approach the high
syngas yield area at 45 wt.%(wf) ash, since it is located below the
ash uid temperature. Also the HTW gasier does not operate close
to the syngas yield maximum.
Since the ternary diagram demonstrates only the thermodynamic potential, the veried gasier models were used to accomplish a sensitivity analysis of the ash content. Fig. 10 exhibits the
results for cold gas efciency which are in general consistent with
the observations from Fig. 8. While the slurry fed GE system shows
the strongest decrease of cold gas efciency with increasing ash
content, the effect is mitigated for the ConocoPhillips gasier due
to the chemical quench. The dry fed systems (Shell, Siemens,
HTW) operate at the same cold gas efciency decreasing slightly
with increasing ash content. At 45 wt.%(wf) ash, the HTW gasier
exceeds all other systems. The same tendencies can be found for
the syngas yield shown in Fig. 11. The only exception is the HTW
gasier which exhibits the lowest syngas yield at 5 wt.%(wf)
slightly increasing with increasing ash content. This can be explained by the increasing CH4 conversion caused by higher O2 consumption at higher ash content.

Syngas yield (m(H2+CO STP)/kg(waf))

25

25

Ash fluid
temperatures
3

2.0 m (H2+CO STP)/kg(waf)

Maximum
syngas yield

Maximum
cold gas efficiency
75

75
25

0
50

75

100

25

50

75

100

South African Coal with variable ash content (wt %)

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

M. Grbner, B. Meyer / Fuel xxx (2012) xxxxxx

Coal type
/
South African
/
Pittsburgh #8

25

t%
)

Maximum
syngas yield

50

)
t%

(w

(w

O2

accompanied by the higher ash content make any moderator


redundant. Hence, any steam addition would cause a temperature
drop which must be counteracted by increased O2 supply in order
to maintain slagging conditions at 1550 C. Consequently, any
steam injection to dry feed single stage slagging processes causes
losses in cold gas efciency as stated earlier.
Due to the extended area of high cold gas efciency for Pittsburgh #8 coal, all gasiers operate at a higher level of cold gas efciency while ConocoPhillips and HTW approach the maximum.
Looking at the syngas yield in Fig. 13, the benecial effect of coal
rank is signicant. The area of syngas yields >2.0 m3(H2 + CO STP)/
kg(waf) experiences a broad extension incorporating all gasiers
except the HTW system.

GE
GE
ConocoPhillips
ConocoPhillips
Shell
Shell
Siemens
Siemens
HTW
HTW

75

50

25

Ash fliud temperatures

3.8. Optimum user diagram

2.0 m (H2+CO STP)/kg(waf)

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

Maximum H2+CO yield

(m(H2+CO STP)/kg(input, waf))

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

Oxygen consumption O2/Coal


(m(STP)/kg)

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

Sticky ash zone

1200

1200

1000

1000

800

800

Temperature (C)

75

600

600
0

Steam/oxygen H2O/O2 (kg/m(STP))

H2/CO ratio (mol/mol)

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

M. Grbner, B. Meyer / Fuel xxx (2012) xxxxxx

to a temperature of 1135 C. At constant temperature a molar H2/


CO ratio of 0.6 with an oxygen consumption of 0.385 m3(STP)/kg
can be found. The information might be used to design a new system or to adjust an existing gasier, e.g. the HTW system, in order
to increase the syngas yield towards the theoretical maximum.
4. Conclusion
A new type of ternary diagram for comprehensive evaluation of
gasication processes was developed using the example of ash-rich
South African coal. Depending on the three independent variables
O2, H2O, and coal mass ow, an assessment of temperature, carbon
conversion, cold gas efciency, dry methane content, syngas yield,
H2/CO ratio and selectivity of carbon conversion was accomplished. The diagram allows one to distinguish operating regions
for single-stage entrained-ow, uidized-bed and dry ash xedbed processes and provides a wide-spread overview at one glance.
It is capable to evaluate multi-stage processes by simple mixing
lines. The ConocoPhillips, GE, Shell, Siemens, and HTW technologies were incorporated in the diagram as a result of generic model
setup. The Lurgi xed-bed dry bottom gasier was located based
on operating experiences of similar German ash-rich hard coal
[20]. The main ndings are as follows:
 The maximum theoretical cold gas efciency at 30 bar of 87.4%
was identied at 980 C and the maximum syngas yield of
2.09 m3(H2 + CO STP)/kg(waf) was found at 1135 C.
 Only uid-bed processes (e.g. HTW) and two-stage processes
(e.g. ConocoPhillips) have the potential to reach the global
maximum.
 Fluid-bed processes indicate a potential of H2/CO ratios up to
1.5 at specic syngas productions of 2.0 m3(H2 + CO STP)/
kg(waf) incorporating a part of the CO shift conversion into
the gasier.
 The generic models of mature Siemens and Shell technology
predict cold gas efciencies and syngas yields close to the thermodynamic maximum while in all other cases signicant
improvements are possible.
 The variation of the ash content between 5 and 45 wt.%(wf)
revealed a shift of the cold gas efciency and syngas yield maxima to lower temperatures with increasing ash content, which
is unfavorable for all single stage slagging entrained ow
processes.
 The comparison of the South African coal to a Pittsburgh #8 coal
of higher rank exhibits that higher rank and lower ash content
cause a signicant extension of the high syngas yield and cold
gas efciency areas permitting higher operational exibility
and steam injection for cold gas efciency increase.
 A simplied user diagram for a pressure range from 1 to 100 bar
and a temperature range from 600 to 1500 C was developed in
order to congure processes to achieve optimum performance.

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