Conversion and Fouling-Devolatilization and Char Kinetics

The objective of the devolatilization and char kinetics effort is to a) measure pyrolysis kinetics
for various density and size fractions of Pittsburgh #8 and at high temperature and pressure, b)
characterize the changes of char particles in the pyrolysis (early stages), including particle size,
density, and char reactivity in CO2 and mineral matter transformations and c) identify the critical
conversion(s) at which the particle fragmentation occurs.
A report contains data obtained during the period of July to September, 2013. Chars obtained at
atmospheric pressure were characterized for conversion, BET surface area, and particle size
distribution. Gas formation kinetics and intrinsic kinetics of char analysis will be reported after
obtaining the CHNS of the chars.
Conversion of coal during gasification was evaluated based on ash tracer technique. Conversion
was calculated based on the following equation [1]:
Ao ( 100A ' )
W = 100[1 A ' ( 100Ao ) ]
where W is weight loss in daf basis. Ao is the proximate (ASTM) ash yield of dry coal. A' is the
proximate ash yield of the dry char. The conversion of each density fractions at various
temperatures is shown in Figure 2. Further investigation is needed for this observation. The other
interesting trend to be noted is the lack of synergy exhibited by the whole coal as the whole coal
conversion is more or less the weighted average of the individual conversions of the
corresponding density fractions.
a) Particle size distribution of chars measured
The changes occurring in particle size of the chars during pyrolysis and gasification were
determined using Microtrac laser diffraction analyzer. The chars/coals were dispersed in water
medium with 1% (v/v) Triton-X dispersant before feeding into the analyzer. Particle size
distribution measurements were repeated at least twice. The particle size distribution of PS3 and
PS6 samples at three different temperatures are shown in figures 3 and 4. It is evident from the
figure 3 that effect of temperature on the particle size distribution is negligible for the PS3 size
fractions. The important thing to note here is that the PSD analyzer assumes the particles to
spherical. Deviation from sphericity severely affects the PSD of the samples. This is very much
the case for PS3 samples. However, a clear trend emerges for PS6 samples (75-106 m). Earlier
studies have reported that char swelling and fragmentation takes place primarily during the
pyrolysis. With increase in conversion, more and more fine particles are generated. In the case of
SG1 samples, PSD of chars generated at 1793 K are finer than chars generated at 1573 K.
Moreover, the char conversions also suggest that the char particles are predominantly undergoing
gasification. However, BSG2PS6 shows an interesting trend. There is little difference in PSD of
chars generated at three different temperatures. This indicates that the chars have undergone

swelling without much fragmentation at higher temperatures. It is likely that a lot of medium
porous chars might have formed during the process. The high porosity chars are known to
fragment during pyrolysis while the medium porosity chars turn into high porosity chars before
fragmentation. Char conversions also suggest that the pyrolysis is not complete for SG2.
Therefore, it is likely that high porosity chars might have fragmented in the early stages leaving
behind medium porosity chars of similar distribution. In the case of SG3 char samples there is
little differentiation in PSD of chars and coal indicating lack of swelling and fragmentation. SEM
analyses were performed on the chars to observe the porosity of chars formed. The images are
shown in the Figure 5. The images show the presence of thick-walled cenospheres in SG2
fraction which are more likely to consume at the later stages of the gasification instead of
fragmentation.