Fuel 78 (1999) 781–793

CO2 and steam-gasification in a high-pressure wire-mesh reactor: the

reactivity of Daw Mill coal and combustion reactivity of its chars
R.C. Messenböck, D.R. Dugwell, R. Kandiyoti*
Department of Chemical Engineering and Chemical Technology, Imperial College (University of London), London SW7 2BY, UK
Received 24 August 1998; accepted 26 November 1998

Abstract
Interrelationships between extents of coal gasification, char gasification and combustion reactivities have been examined as a function of
CO2 and steam pressure and holding time. Experiments have been carried out in a high-pressure wire-mesh reactor equipped with a steam
injection facility. Evidence has been presented linking minima in weight loss vs. reactive gas pressure curves with deactivation as a result of
secondary char deposition. At longer times, extents of gasification were about 2–3 times higher in steam compared to CO2. With increasing
reactivity of the ambient gas, the minimum in the weight loss vs. pressure curve appears only at the shortest reaction times. At higher
pressures, reactivities between zero and 10 s were lower than those between 10 and 20 s. These data are novel and support the suggestion that
a relatively unreactive layer of re-polymerised tar tends to slow down the gasification of the main body of the char in the initial stages – until
it is itself consumed. Combustion reactivities of pyrolysis and gasification chars decrease with increasing pressure. When exposed to a
temperature of 1000⬚C, combustion reactivities of chars were found drop rapidly within about 10 s to relatively low and stable values. The
end values were independent of pressure and composition of the reactive gas. The results are relevant to the design of pilot and commercial
scale reactors. On the basis of limited available evidence, it appears that secondary char deposition caused by tar re-polymerisation plays an
increasingly significant effect with increasing particle size. 䉷 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Coal gasification; Char combustion reactivities; Tar re-polymerisation; Steam gasification

1. Introduction work, rapid and inexpensive bench scale experiments are

In combined cycle processes, with low temperature air/
steam gasification ( ⬃ 950⬚C–1050⬚C) to generate fuel gas
for the gas turbine, 25%–35% of the feed coal is normally
recovered as residual char. The gasification reactivity of this
solid residue is minimal; these chars are usually sent to a
combustor, to raise steam for additional power generation in
a second (steam) turbine. However, calculation shows that
overall cycle efficiencies could be improved by increasing
the proportion of coal consumed in the gasifier, i.e. by
increasing the amount of fuel gas fed to the turbine per
unit of feed coal [1].
There appear to be good reasons for linking the formation
of relatively unreactive residues in these pilot-scale gasifiers
to the use of relatively large feed coal particle sizes. The
challenge would appear to be the formulation of alternative
fluidised bed gasifier operating strategies which would
allow the use of smaller particle sizes. Within this frame-
* Corresponding author. Tel.: ⫹ 44 171 594 5581; fax: ⫹ 44 171 594
5604.
E-mail address: r.kandiyoti@ic.ac.uk (R. Kandiyoti)
0016-2361/99/$ - see front matter 䉷 1999 Elsevier Science Ltd. All rights reserved.
PII: S0016-236 1(98)00221-X
normally expected to provide background information on
fuel behaviour. The utility of bench scale data to provide
the necessary data, however, depends on the ability of
laboratory reactors to mimic essential reaction parameters
of larger scale plant. In the case of gasification, the usual
methodology of attempting to relate laboratory work to pilot
scale operation has in the past faced a number of difficult
issues.
Numerous investigations on the gasification of coal with
carbon dioxide and/or steam have been conducted in ther-
mogravimetric (TGA) balances (cf. e.g. Refs. [2,3]). TGA
instruments are convenient for continuously recording
changes of weight loss with time and usually give good
repeatability. However, (i) heating rates are lower than
those encountered in fluidised bed reactors and (ii) particle
stacking on the TGA-pan affects the outcome of experi-
ments; furthermore, (iii) carrier gas is usually allowed to
flow around the TGA-furnace and not through the sample
stack. Compared to fast heating rate experiments conducted
using (more realistically) segregated particles [4,5], all three
effects lead to tar loss by re-condensation on heated fuel
solids. The proportion of volatile loss appears to be
782 R.C. Messenböck et al. / Fuel 78 (1999) 781–793

Fig. 1. Steam injection unit and the wire-mesh reactor: (1) water reservoir; (2) filter; (3) displacement pump; (4) steam heater; (5), (6) on/off valves; (7) steam
by-pass collector; (8) sweep gas; (9) safety valve; (10) flow control valve; (11) gas heater; (12) non-return valve; (13) mixing point of steam and gas; (14) wire
mesh reactor; (15) countercurrent condenser; (16) flow control valve; (17) water collector; (18) cold trap; (19), (20) flowmeter; (21) transformer; (22)
watchdog. P-pressure, T-temperature, C-controller, I-indicator; full lines stand for tubing, dash-dot for thermocouple lines, dash-dot-dot for electric current
lines. (Published by permission of Energy and Fuels).

relatively small, usually of the order of several percent and
never more than 8%–10%. However, there is evidence
strongly suggesting that re-condensed tars tend to form a
relatively unreactive residue, overlaying chars evolved from
the main body of coal particles [6,7] (also see following
text). Gasification and combustion reactivities of chars are
known to change rapidly and significantly with changes in
pyrolysis related parameters [8,9]. Meticulous scrutiny of
modes of sample devolatilisation is therefore essential if
bench scale experiments are to be used in visualising and
eventually predicting the outcome of pilot and commercial
scale gasifier operation.
Relatively rapid heating has in fact been attempted in
TGA instruments, by lowering a sample basket into the
heated zone [2]. However, this configuration does not
appear to avoid tar re-condensation caused by particle stack-
ing. Our own experiments show that very high gas velocities
(several meters per second) are required through shallow
stacked sample beds for removing volatiles with an effi-
ciency nearly matching experiments where particles are
segregated [4]. Rapid heating of TGA-pans would also be
likely to give rise to temperature gradients across the sample
basket; inevitably, not all particles would be heated at the
same high rates.
To avoid these pyrolysis related effects, numerous bench-
scale gasification experiments have been carried out by
successively pyrolysing the coal and gasifying the resultant
char in different vessels [10–22]. Typically, this is done by
pyrolysing the coal sample in a small fluidised bed, followed
by TGA-based experiments conducted to determine the
reactivities of the chars. However, early work [16] clearly
suggested that steam gasification rates could change (by up
to 30% in their case), depending on the conditions of the
preceding pyrolysis step. There is also more recent evidence
[8,16,21,23–26] showing that different gasification reactiv-
ities are obtained from coal chars prepared from the same
coals, but under different pyrolysis conditions. In particular,
soaking samples at high temperatures during char prepara-
tion leads to thermal ‘annealing’ of the char and tends to
distort results [8]. Chitsera et al. [27] have observed that
longer soak times during pyrolysis at elevated temperatures
and pressures, as well as sample ageing under ambient
conditions, tend to lower steam reactivities of chars. In the
same vein, using a TGA-instrument for gasification in steam
between 1000⬚C–1300⬚C, Peng et.al. [2] have reported
reactivities of in-situ generated chars up to six times greater
than those of the corresponding ex situ generated samples.
We have shown elsewhere [8,28] how deliberate manip-
ulation of reaction parameters during char preparation can
affect the CO2-gasification reactivity of coals and chars. We
 R.C. Messenböck et al. / Fuel 78 (1999) 781–793
have also shown that nearly identical CO2-gasification
conversions and char reactivities could be obtained in two
bench-scale reactors of very different configuration: a wire-
mesh instrument (see following text) and a fluidised bed
reactor [29]. The two reactors were both operated at high
heating rates and under regimes requiring particle segrega-
tion (as opposed to stacking). In these experiments, extents
of gasification have been evaluated by subtracting weight
loss during pyrolysis from total conversion during gasifica-
tion, carried out under similar reaction conditions. More
recently, we have reported on the development of a steam
injection facility for carrying out steam-gasification experi-
ments in the high-pressure wire-mesh reactor [6]. The
present paper examines interrelationships between extents
of gasification and char reactivities as a function of reaction
pressure and holding time. Experiments were carried out in
the high-pressure wire-mesh reactor operated with steam or
CO2 injection. Following earlier reports [30] suggesting that
the steam not only increases weight loss and tar yield, but
also enhances the reactivity of resultant chars, morphologies
and combustion reactivities of chars prepared during steam
and CO2-gasification were examined in some detail.
2. Experimental
The wire-mesh reactor: The wire-mesh reactor equipped
with steam injection used in this study has been described
elsewhere [6,31,32]. Briefly, a folded wire-mesh is placed
between two water cooled electrodes, one of them spring-
loaded. The mesh serves as resistance heater for the sample
(typically 5–7 mg), spread as a monolayer. Two thermocou-
ples are placed in the reaction zone, to monitor lateral
temperature variations in the sample holding part of the
mesh. The temperature is monitored 100 times a second
and the heating current across the mesh adjusted using on-
line three-term control. During an experiment, a stream of
gas is passed through the sample holding part of the mesh to
remove evolving volatiles and to suppress secondary reac-
tions of the volatiles. Product gases are passed through a
cooled tar trap for capture and recovery.
A diagram of the reactor system and ancillaries, including
the new steam injection facility is presented in Fig. 1. Modi-
fications for operation in CO2 and steam have been recently
described in Ref. [6], and will only be summarised here.
Operation with steam injection ordinarily leads to
condensation on internal surfaces of the reactor, as all
components except the mesh itself are normally kept at
ambient temperature. In the present design, such condensa-
tion has been avoided by directing the steam through a
preheated flow path, which includes the mesh itself. Before
the run, steam was raised continuously and discarded
through a bypass line (Fig. 1: (6) and (7)). During operation,
the steam and helium heaters were set at 300⬚C, with typical
steam and helium delivery temperatures of about 280⬚C and
250⬚C, respectively. The temperature of the mixture varied
783
between 260⬚C–270⬚C; the steam condensation temperature
at 20 bar (maximum steam pressure used) is 212.4⬚C.
Before triggering a run, the mesh was electrically preheated
to 300⬚C. To carry out a run, steam was switched into the
wire-mesh cell and contacted with the coal sample only
instants before the temperature of the sample was ramped.
Time–temperature plots from experiments with steam
injection have shown levels of temperature stability
comparable to those observed during experiments with
‘dry’ gases [6].
In the present study, samples were heated at 1000⬚C s ⫺1
to 1000⬚C and held at peak temperature between 0 and 60 s.
The effect of pressure was investigated in a range between
1–30 bar. During pyrolysis (in helium) and CO2 gasifica-
tion, the gas stream flowed through the mesh at a velocity of
0.1 m s ⫺1. In ‘steam-gasification’, a steam: helium (80 : 20)
mixture was used; the He-flow rate was set at 0.02 m s ⫺1 to
achieve 0.1 m s ⫺1 for the total flow of gas.
Sample: Daw Mill (a UK noncaking) coal was used: vitri-
nite 66% (v/v, mmf), exinite 13% (v/v, mmf), inertinite 21%
(v/v, mmf); vitrinite reflectance: 0.6. Proximate analysis:
moisture 6.1% (a.d.), ash 4.4% (a.d.), fixed carbon 53.8%
(a.d.), volatile matter 39.9% (d.a.f.). Elemental composition
(% w/w d.a.f.): carbon 80.1, hydrogen 4.7, nitrogen 1.3,
oxygen (by difference) 11.5; organic sulphur 1.12% (d.b.),
sulphate sulphur ⬍0.1% (d.b.), pyritic sulphur 0.28% (d.b.).
The sample (particle size: 106–150 mm) was dried for 18 h
at 50⬚C under vacuum and stored under nitrogen until
required. Results have been calculated on a dry ash free
(d.a.f.) basis.
Gasification reactivities: In this work, ‘extents of gasifi-
cation’ were calculated by subtracting sample weight loss
recorded during a pyrolysis experiment from the weight loss
observed during a gasification run, performed under other-
wise identical experimental conditions (heating rate,
temperature, hold-time and pressure).
G%t ˆ ‰TV…Gasification†t ⫺ TV…Pyrolysis†t Š;
where TV denotes the total volatile yield and t denotes time.
‘Gasification reactivities’ were calculated, from this data, by
determining the extent of gasification per second during
specific hold-time intervals (e.g. 0–10 s or 20–60 s):
TV…Gasification†t2 ⫺ TV…Gasification†t1
dG%t2 ˆ :
t2 ⫺ t1
Relative char combustion reactivity determinations: An
isothermal method was used. The pan of a Perkin-Elmer
TGA7 thermogravimetric analyser was charged with about
1.5 mg of char and heated at 25⬚C min ⫺1 to 500⬚C in nitro-
gen flowing at 40 ml min ⫺1. Once a constant weight was
established at 500⬚C, the flow was switched to air; following
virtually complete combustion at 500⬚C, the temperature
was raised to 850⬚C to determine the ash content of the
sample. The maximum value of the first derivative of the
weight vs. time curve was taken as the relative combustion
784 R.C. Messenböck et al. / Fuel 78 (1999) 781–793

Fig. 2. Total volatile yields in CO2 gasification (1000⬚C s ⫺1, 1000⬚C, CO2).

reactivity of the char: photo-micrographs were recorded in a JEOL JSM-T220A

  scanning electron microscope operated at 15 kV.
1 dW
Rmax ˆ ⫺ 兩
W0 dt max
3. Results and discussion
where t is time, W0 is the initial and W the time dependent
char weight. Figs. 2 and 3 present the effect of pressure and of hold-
In this work, only single determinations have been time at peak temperature, on conversions of Daw Mill coal
reported; repeatabilities are usually high and well within during gasification with CO2 and steam, respectively [6].
^ 5% of the measured reactivity value (one repeated result Samples were heated at 1000⬚C s ⫺1 to 1000⬚C.
of the 10 s, 10 bar run is given in Fig. 7). Under pyrolysis conditions (not shown; cf. Ref. [6]), the
Scanning electron microscopy: Samples were mounted weight loss was observed to decline steadily with increasing
on brass stubs and gold plated. Scanning electron pressure; the overall change over the 1–30 bar range was

Fig. 3. Total volatile yields in steam gasification (1000⬚C s ⫺1, 1000⬚C, Steam).
 R.C. Messenböck et al. / Fuel 78 (1999) 781–793 785

Fig. 4. Extent of CO2 gasification (1000⬚C s ⫺1, 1000⬚C, CO2).

about eight percent. Extensive particle melting could be
observed at pressures above 10 bar. At all pressures, a
small increase in weight loss from zero to 10 s hold-time
could be observed, but the 60 s hold-time runs gave virtually
the same results as runs with 10 s holding.
The CO2-gasification experiments over the pressure range
(1–30 bar; Fig. 2) were carried out with ‘zero’ seconds
holding (i.e. heatup only) and with 10, 20 and 60 s holding
at the peak temperature (1000⬚C). In CO2, relatively little
gasification took place during heatup and the curve for
‘zero’ holding was qualitatively similar to data from
pyrolysis experiments.
Fig. 2 shows that, with 10 s holding at 1000⬚C, the sample
weight loss curve as a function of increasing pressure traced

Fig. 5. Extent of steam gasification (1000⬚C s ⫺1, 1000⬚C, Steam).

786 R.C. Messenböck et al. / Fuel 78 (1999) 781–793

Fig. 6. CO2 gasification reactivity (1000⬚C s ⫺1, 1000⬚C, CO2).

a shallow minimum near 10 bar. Consistent with earlier curve after the minimum (e.g. in the 10 s curve in Fig. 2) is
findings from hydropyrolysis, the initial decline is thought likely to reflect both an increase in the reactivity of the gas
to reflect the suppression of devolatilisation by the physical and the (at least) partial elimination of the layer of re-poly-
effect of pressure, followed at higher pressures by the even- merised tar deposit. Between 20–60 s, these effects are no
tual increase in weight loss through the greater reactivity of longer observable; the monotonically rising weight loss
the ambient gas [32,33]. However, recent work has enabled profile indicates that longer reaction times override effects
extension of this explanation to include the role of second- owing to low reactivity of the ambient gas and of the re-
ary char deposition [6] as follows. polymerised char.
In the presence of both H2 and CO2, the decline in volatile In contrast to the CO2-gasification results, the steam-gasi-
release observed with increasing pressure at high heating fication data in Fig. 3 showed no evidence of a minimum in
rates has been accompanied by loss of tar release weight loss with increasing pressure. At longer times
[32,34,35]. The tars appear mostly to re-polymerise to a (ⱖ 10 s) trends were analogous to those observed for CO2-
char, with partial cracking leading to some additional gas gasification at longer times – reflecting the faster reaction
release. It is thought likely that the minimum in weight loss between the carbonaceous material and steam. At 20 bar,
discussed earlier is also associated with loss of sample reac- the sample was almost completely consumed after 20 s,
tivity owing to this secondary char deposition. Combustion leaving nothing but a few ash particles in the sample holder.
reactivities of hydropyrolysis chars have been found to go Extents of gasification: In order to distinguish between
through a minimum [34], and those of chars prepared in CO2 pyrolytic weight loss and fuel consumption by the reactive
and steam steadily decline (over a smaller pressure range). gas in these experiments, parallel tests were carried out in
Accordingly, the rising edge of the weight loss vs. pressure helium under otherwise similar conditions. Figs. 4 and 5
present the ‘extent of gasification’ in CO2 and steam, respec-
tively, (weight loss in pyrolysis subtracted from weight loss
Table 1
Extent of gasification after heatup (1000⬚C s ⫺1, 1000⬚C, 0 s)
in gasification) as a function of pressure and hold-time at
1000⬚C. The initial delay of gasification owing to low reac-
Gas Pressure (bar) Extent of gasification (%, d.a.f) tivities can be observed for CO2 at 10 and 20 bar (the curves
somewhat disguise the effect). At longer times, the initial
CO2 1 4.5
CO2 10 2.0 increase in the ‘extent of gasification’ with pressure was
CO2 20 3.3 marked but appeared to slow down as total sample
CO2 30 3.3 consumption was approached.
Steam 1 2.8 Table 1 shows the pressure dependence of the extent of
Steam 10 1.7
gasification at 0-second hold-time (i.e. heatup only). Both
Steam 20 4.8
sets of data (steam and CO2) showed a minimum around
 R.C. Messenböck et al. / Fuel 78 (1999) 781–793 787

Table 2 down the gasification of the main body of the char in the
Extent of gasification after 20 s hold-time (1000⬚C s ⫺1, 1000⬚C, 20 s) initial stages – until it is itself consumed. Above 20 s the
Gas Pressure (bar) Extent of gasification (%, d.a.f) reactivity decreases slowly – reflecting the relatively small
amount of sample left behind. Various ways to calculate
CO2 1 12.1 gasification reactivities are possible. While the usual
CO2 10 24.4
concept is based on the sample weight loss per original
CO2 20 34.3
CO2 30 41.9 sample mass and therefore decreases monotonically, basic
Steam 1 20.6 mathematical considerations show that the rate of gasifica-
Steam 10 48.3 tion based on mass loss per actually existing mass at that
Steam 20 54.4 time tends to flatten out and to become independent of hold-
time after 10 s.
In the case of experiments at 1 bar, gasification reactiv-
10 bar at relatively small extents of gasification; clearly, for ities in both steam and CO2 were observed to decrease stea-
very short times at high temperature, the greater reactivity dily with holding time at 1000⬚C (Table 3). At twenty bar
of steam cannot be fully observed. This trend would have (Table 4), gasification reactivities look slightly different:
been difficult to depict in weight-loss vs. pressure diagrams The carbon dioxide reactivity appears to go through a maxi-
(as in Figs. 2 and 3). As expected, the minimum is not mum at 10 bar, the low value at 10 s reflecting the low
observed at longer times (Table 2), where extents of gasifi- reactivity of residual tars, whilst in steam, this less reactive
cation were about 2–3 times higher in steam compared to layer appears to have been removed much more quickly,
CO2. The extent of gasification increased from 20.6% to leaving almost no char to be gasified after 10 s; the gasifica-
54.4% with steam pressure increasing from 1 to 20 bar. tion reactivities after 10 s appear rather small.
Char gasification reactivities: Fig. 6 presents ‘gasifica- Relative char combustion reactivities: Relative combus-
tion reactivities’ (defined earlier), reflecting average rates of tion reactivities of the chars were determined in a TGA-
weight loss by gasification during specified time intervals: instrument by the standard ‘isothermal’ method described
e.g. the point shown at 10 s indicates the average reactivity in the ‘Experimental’ section. Fig. 7 presents combustion
between 0–10 s. At atmospheric pressure, the gasification reactivities of Daw Mill coal chars recovered from CO2-
reactivity was observed to decrease monotonically with gasification experiments, as a function of pressure and
time. At intermediate pressures, reactivities between zero hold-time.
and 10 s were lower than those between 10 and 20 s, Chars from the 0-second holding experiments (at 1000⬚C)
while at high pressure a continuous decrease was observed. showed a rapid drop with increasing pressure; as outlined
These data are novel and support the suggestion that a rela- previously, the effect appears linked to tar re-deposition and
tively unreactive layer of re-polymerised tar tends to slow re-polymerisation within pyrolysing particles during heatup.

Fig. 7. Combustion reactivity of CO2-chars (chars: 1000⬚C s ⫺1, 1000⬚C, CO2).

788 R.C. Messenböck et al. / Fuel 78 (1999) 781–793

Table 3 Table 5
Gasification reactivity at 1 bar (1000⬚C s ⫺1, 1000⬚C, 1 bar) Relative combustion reactivities of pyrolysis chars determined isothermally
in TGA at 500⬚C (chars: 1000⬚C s ⫺1, 850⬚C and 1000⬚C, He)
Gas Hold-time (s) Gasification reactivity (%, d.a.f)
Temperature (⬚C) Pressure (bar) Hold-time (s) Combustion
CO2 10 0.39 reactivity (%
CO2 20 0.23 min ⫺1, d.a.f)
CO2 60 0.06
Steam 10 1.12 850 1 10 3.93
Steam 20 0.53 850 30 10 1.47
Steam 60 0.31 1000 1 0 2.53
1000 10 0 2.35
1000 20 0 2.35
1000 30 0 2.29
A wider range of pressures (up to 80 bar) had been used in 1000 1 10 1.90
previous work where a full minimum had been observed (as 1000 10 10 1.18
a function of pressure at constant holding time) in the 1000 20 10 1.03
combustion reactivity of hydropyrolysis chars. Differences 1000 30 10 1.01
1000 1 60 1.26
between reactivities of chars other than those from 0-second
1000 10 60 1.00
holding experiments were small and only marginally greater 1000 20 60 0.77
than experimental repeatability: above 10 s holding the 1000 30 60 0.71
reactivities appeared to be almost independent of holding
time and pressure.
The observed link between deactivation of chars and helium are presented in Table 5, showing a clear decrease in
increasing temperatures is well established (cf. e.g. Ref. combustion reactivity with time. Comparison with Fig. 7
[36]). Combustion reactivities of two chars that were gasi- suggests this drop to be – apparently – independent of the
fied for 10 s at 850⬚C, under otherwise identical conditions chemical composition of the ambient gaseous medium. The
were considerably higher. However, the often used descrip- reactivities of the chars pyrolysed for 10 s at 850⬚C confirm
tions of the phenomenon in terms of ‘annealing’ of the earlier findings in respect of the effect of temperature on
chars, or ‘loss of active sites’ are admittedly non-specific. reactivities.
More detailed work in terms of dominant molecular Table 6 presents relative combustion reactivities of chars
mechanisms may be both interesting and useful. from the steam-gasification experiments. At 20 bar, not
These data are useful in indicating the time required for enough char was left after the 20 s steam-gasification
reaching a point beyond which chars do not significantly experiments, to conduct combustion reactivity determina-
deactivate further; the results are relevant to the design of tions. The effect of pressure (causing secondary char deposi-
pilot and commercial scale reactors. It is also relevant to tion) and time at 1000⬚C in reducing reactivities may be
point out that combustion reactivities of chars recovered clearly observed. After 10 s holding at 1000⬚C, the 10 bar
from the ABGC reactor (3 mm top-size coal feed) were chars gave relative reactivities of the order of 0.5% min ⫺1,
found to be half (or less) as reactive again as chars prepared by far the lowest values measured for any of these chars. It
from the present study starting with sample size (106– may be noted that 0-second hold-time reactivities of the
150 mm) [9,37]. Judging on the basis of the available steam-gasification chars were comparatively high, and
evidence, it would appear that secondary char deposition considerably higher compared to 0-second hold-time chars
owing to tar re-polymerisation plays an increasingly signif-
icant effect with increasing particle size. However, there
Table 6
appears to be a clear need to investigate further the relation- Relative combustion reactivities of steam gasification chars determined
ship between starting sample particle size and rapid drops isothermally in TGA at 500⬚C (chars: 1000⬚C s ⫺1, 1000⬚C, Steam)
observed in the reactivity of the resultant chars.
Combustion reactivities of chars prepared by pyrolysis in Pressure (bar) Hold-time (s) Combustion
reactivity (%
min ⫺1, d.a.f)
Table 4
Gasification reactivity at 20 bar (1000⬚C s ⫺1, 1000⬚C, 20 bar) 1 0 4.10
1 10 2.32
Gas Hold-time (s) Gasification reactivity (%, d.a.f) 1 20 1.50
1 60 1.36
CO2 10 1.37 10 0 3.65
CO2 20 1.60 10 10 0.47
CO2 60 0.22 10 20 0.35
Steam 10 4.41 10 60 0.30
Steam 20 0.72 20 0 3.20
Steam 60 0.00 20 10 0.92
 R.C. Messenböck et al. / Fuel 78 (1999) 781–793 789

Table 7 chars. For each gas, four photographs are presented, a short
Relative combustion reactivities of 0 s hold-time chars determined isother- and long hold-time run for a high and a low pressure experi-
mally in TGA at 500⬚C (chars: 1000⬚C s ⫺1, 1000⬚C, 0 s)
ment.
Gas Pressure (bar) Combustion Figs. 8 and 9 show the effect of hold-time during pyro-
reactivity (% lysis at atmospheric pressure. The structure of the char was
min ⫺1, d.a.f) not found to change significantly between 0-second holding
He 1 2.53 and 60 s at 1000⬚C. Particles tended to form a network, with
He 10 2.35 their original size (106–150 mm) still recognisable. Differ-
He 20 2.35 ences between short and long holding at 30 bar (Figs. 10 and
He 30 2.29 11, respectively) were also relatively small. However
CO2 1 2.29
comparing the morphologies of the high pressure pyrolysis
CO2 10 2.20
CO2 20 1.85 chars with those from atmospheric pressure pyrolysis
CO2 30 1.08 revealed striking differences. Chars from the higher pressure
Steam 1 4.10 experiments clearly show evidence of greater fluidity during
Steam 10 3.65 heatup, with the sample no longer showing evidence of the
Steam 20 3.20
original particle size distribution; the imprint of the mesh on
these larger agglomerated particles is may be clearly
from pyrolysis and CO2-gasification (Table 7) – in some observed. Increased fluidity during heating at higher pres-
cases by a factor of two. These findings are consistent sures is well known and is thought to be directly related to
with our previous work showing greater reactivities of lower levels of tar release and the deposition of secondary
chars prepared in helium compared to gasification in CO2 char. As a result of the small amounts of char left after
– as well as mirroring the effect observed with increasing experiments, surface area determinations were impossible
pressure [28]. They also indicate that the higher conversions to conduct.
in steam-gasification were not only owing to the more reac- Figs. 12 and 13 show the effect of hold-time on chars
tive gasification medium itself but also to the greater reac- gasified under CO2 at atmospheric pressure. Whilst origi-
tivity of the char gasified in steam – as previously suggested nal particle sizes were still discernible, the char from the
in Ref. [30]. 60 s experiment showed a more porous surface, owing to
Table 8 presents the effect of hold-time at 1000⬚C on the increased conversion in gasification (conversions:
relative char reactivity in isolation from pressure effects: 53.9% after 0 s and 62.7% after 60 s). In the case of
all chars were prepared at atmospheric pressure. As the thirty bar CO2-experiments (Figs. 14 and 15, respec-
expected, the steam-gasification chars were the most reac- tively) hold-time effects were easier to observe than in
tive at up to 10 s and chars from carbon dioxide gasification pyrolysis. The sixty second char was found to have a
always least reactive. At this pressure, all char reactivities very porous, spongy structure. Again, the structure of
reached relatively stable values after about 10–20 s at the residual agglomerated mass did not reflect the sizes
1000⬚C. Relatively little difference could be found between of the original particles at all.
char reactivities after 60 s, irrespective of the composition The chars from steam-gasification at atmospheric pres-
of the gaseous medium and levels of conversion. sure (Figs. 16 and 17), did not appear to agglomerate at
Scanning electron microscopy of the chars: The follow- all. Even after 60 s some of the particles showed some
ing figures present SEM photomicrographs of some of the rough surfaces, indicating that they did not soften or melt
to the same degree as their pyrolysis or CO2-gasification
Table 8 counterparts. Fig. 17 shows, in the top right corner, that
Relative combustion reactivities of 1 bar chars determined isothermally in
TGA at 500⬚C (chars: 1000⬚C s ⫺1, 1000⬚C, 1 bar)
although the particles look smooth and unchanged in
size, a structure with large pores has evolved. However,
Gas Hold-time (s) Combustion at twenty bar (Figs. 18 and 19) the original sizes and
reactivity (% structures of the coal particles could not be discerned:
min ⫺1, d.a.f)
the char held for ten seconds (no 20 s char was left for
He 0 2.53 characterisation) appears to have more rough edges and
He 10 1.90 pores than the zero second char. On the whole the two
He 60 1.26 chars appear rather similar. This is not very surprising, as
CO2 0 2.29
in steam gasification at twenty bar (Table 1), the gasifi-
CO2 10 1.09
CO2 20 0.91 cation conversion was quite high.
CO2 60 1.02
Steam 0 4.10
Steam 10 2.32 4. Summary and conclusions
Steam 20 1.50
Steam 60 1.36
Interrelationships between extents of gasification, char
790 R.C. Messenböck et al. / Fuel 78 (1999) 781–793

Fig. 8. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 0 s, He, 1 bar). Fig. 11. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 60 s, He, 30 bar).

Fig. 9. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 60 s, He, 1 bar). Fig. 12. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 0 s, CO2, 1 bar).

Fig. 10. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 0 s, He, 30 bar). Fig. 13. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 60 s, CO2, 1 bar).
 R.C. Messenböck et al. / Fuel 78 (1999) 781–793 791

Fig. 14. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 0 s, CO2, 30 bar). Fig. 17. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 60 s, steam, 1 bar).

Fig. 15. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 60 s, CO2, 30 bar). Fig. 18. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 0 s, steam, 20 bar).

Fig. 16. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 0 s, steam, 1 bar). Fig. 19. Daw Mill (1000⬚C s ⫺1, 1000⬚C, 10 s, steam, 20 bar).
792 R.C. Messenböck et al. / Fuel 78 (1999) 781–793

gasification and combustion reactivities have been exam- to the greater reactivity of the char gasified in steam – as
ined as a function of CO2 and steam pressure and hold- previously suggested in Ref. [30].
ing time. Experiments have been carried out in a high-
SEM photomicrographs showed clear correspondence
pressure wire-mesh reactor equipped with a steam injec-
between char porosity and char reactivity; at high pressures,
tion facility.
fluidity, low tar yields and low char reactivities all happened
1. The suppression of tar release under pressure is known to at the same time.
lead to re-deposition and re-polymerisation in the form of
relatively unreactive chars. Evidence has been presented
linking minima in weight loss vs. reactive gas pressure Acknowledgements
curves with deactivation caused by secondary char
deposition. At longer reaction times, these effects are Support for this work by the European Union under
no longer observable; monotonically rising weight loss Contract Nos. JOF3/CT95/0018 and ECSC 7220-ED/075,
profiles suggest that that longer reaction times override and the British Coal Utilisation Research Association
effects caused by low reactivity of the ambient gas and of (BCURA)/Department of Trade and Industry (DTI) under
the re-polymerised char. Contract No. B38 is gratefully acknowledged. Mitsui
At short times, extents of gasification were about 2–3 Babcock Energy Ltd are thanked for providing the samples.
times higher in steam compared to CO2. With increasing
reactivity of the ambient gas, the minimum in the weight
loss vs. pressure curve appears only at the shortest reac-
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