Professional Documents
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of deposit formation
gasif ication syngas cooler
Duane
in a coal
Brooker
During entrained slagging coal gasification utilizing syngas coolers (waste heat boilers), submicrometre
to 10 pm spherical ash particles can be deposited as a fouling layer on the water wall tubes. Unlike
conventional pulverized-coal-fired boilers, the conditions within the gasification process are reducing
(P,, = lo-;
Ps, = lo- atm). Metal sulfides along with fluoride and chloride compounds
have been
identified on the water wall and on the outer surfaces of the fly-ash particles, whereas alkali sulfates and
iron oxide compounds
are commonly repeated in layers responsible
for fouling in the convection
and
superheater
sections of coal-fired boilers. Once the initial fouling layer is formed, fly ash can adhere to it
if an improper soot blowing design is chosen. The hardness and size of the deposit is a function of ash
chemistry and fluid dynamics.
(Keywords: deposition; coal; gasification)
CONFIGURATION
001t%2361,'93/05/0665~6
( 1993 Butterworth-Heinemann
Ltd
Fuel 1993
Volume
72 Number
665
Chemistry
of deposit
formation:
D. Brooker
RESULTS
T = 1300~~
Casifier
t
Radiant
Syngas
T=1200C
Convection
syngas
syngas
COOIW
cooler
,-
/T=36oT
) To gas
clean-up
Figure
Cool Water
plant process
configuration
SAMPLES
A section
(30 x 60 cm) of water wall tubing
was
torch-cut from the radiant syngas cooler with the scale
and deposit attached. The deposit consisted of a layer
(2.5 cm thick) of medium grey, well bonded ash on the
tube membrane,
and a layer (2 mm thick) on the tube.
Heat transfer calculations
and thermocouple
measurements indicated that the maximum
metal temperatures
were 300C on the tube and 565C on the membrane
(metal between the tubes).
Epoxy was applied over the deposit prior to cutting
the section in order to keep the scale from flaking off the
tube. The material on the membrane
was much better
bonded to the metal than was the material on the tube.
The water wall was then cross-sectioned,
mounted
in
epoxy, and polished
using standard
reflective
light
polishing
procedures.
Pieces of the deposit were also
removed from the tube prior to cutting, to avoid wetting
and submitted
for scanning
electron
the deposit,
microscopy/energy
dispersive
X-ray
spectrometry
(SEM/EDS)
analysis.
Additional
samples taken consisted of loose ash and
deposits formed in other areas of the gasifier. A large
number of samples were analysed in the unit to gain a
statistical data base; thus it was possible to determine
the nature of changes through
the cross-sections
of
deposits, and how changes in temperature
through the
unit affected deposit chemistry. Most of the results in
this paper concentrate
only on the deposit on the water
wall.
666
Fuel 1993
Volume
72 Number
X-ray diffraction
(XRD)
analysis
was done on the
deposits from both the tube and membrane
(Table 1).
Additional
XRD analyses were carried out on samples
scraped from the deposit at distances of l-2.5, 4.5-6.5
and 10.5-12.5 mm from the membrane, to determine how
the deposit changed with temperature.
The scale on the
tube consisted
of iron sulfide (Fe, -,S, pyrrhotite),
calcium
fluoride
(CaF,,
fluorite),
sodium
chloride
(NaCl, halite) and glass. Calcium
sulfate hydroxide
(CaSO,.H,O,
gypsum)
was identified
against
the
membrane,
but not against the tube. Minor fases found
in other areas of the tube against the water-cooled
wall
include
zinc sulfide (ZnS),
silicon dioxide
(SiO,),
galena ( PbS ), and calcium/magnesium
alumina silica
hydroxide hydrates. Moving away from the membrane,
the fluorite,
pyrrhotite
and
halite
gradually
disappeared
and either calcium magnesium
iron silicate
augite),
calcium magnesium
iron
(Ca(Fe,Mg)Si,O,,
alumina silicate (Ca(Fe,Mg,Al)(Si,Al),O,,
fassaite) or
calcium alumina silicate (Ca,Al,SiO,,
gehlenite) became
the dominant
crystalline
fase. Minor
fases identified in the deposits included
sodium alumina
silicate
(NaAlSiO,)
and
calcium
alumina
silicate
((Ca,Na)(Al,Si),O,).
XRD analysis on other scales throughout
the syngas
cooler yielded similar results, including the identification
of iron sulfide on the surface of a grafite tube that
was installed as part of a material testing programme.
Very thin ( ~0.5 mm) iron sulfide-rich layers were also
identified
within the middle of several deposits. The
fouling layers on the tubes within the radiant
and
convection coolers were similar in appearance except for
the identification
of calcite (CaCO,)
in several samples
from the convection tubes. However, the fly-ash deposits
within the radiant cooler were much more crystalline
than the deposits removed from the convection coolers,
suggesting that below 700C the fly-ash particles did not
Pable 1
XRD results
Phases
Major
Minor
Scale on tubes
fluorite
pyrrhotite
glass
halite
augite
Scale on membrane
fluorite
pyrrhotite
glass
gypsum
halite?
Ash;
fluorite
pyrrhotite
glass
halite
Ca-Si-O-OH
glass
fluorite
halite
augite
unidentified
glass
augite
Loose ash
glass
quartz
SUFCo
quartz (28% )
illite (30%)
kaolinite (9%)
calcite (7% )
ankerite (2-5%)
pyrite (2-5%)
unidentified (lC-15%)
Sample
description
1 mm from membrane
coal
0. Brooker
Fuel 1993
Volume
72 Number
667
Chemistry
of deposit
formation:
(SEM/EDS,
D. Brooker
Table 2
Ash chemistry
wt%)
(results
normalized
Element
SUFCo
slurry
SUFCo
slag*
SUFCo
fly ash
(110)
_
3.4
1.8
12.2
40.2
(100)
5.1
3.0
2.1
12.6
50.6
_
_
0.4
17.1
1.1
6.4
0.9
24.6
0.3
6.0
to 100%
F
Na
Mg
Al
Si
Cl
S
K
Ca
Ti
Fe
2.5
2.4
11.8
53.2
all others
2.0
1.9
23.3
2.4
12.5
0.1
0.5
12
25
_
_
_
_
10.3
1.7
10.2
24.6
1.7
7.4
0.8
24.6
0.9
17.9
4.3
1.7
13.0
39.2
_
4.1
1.9
11.9
36.5
_
1.7
1.9
20.5
1.7
16.0
2.3
1.7
22.1
2.3
13.3
_
_
29.2
_
_
70.8
2.5
5.3
_
28.1
_
2.7
_
60.5
ICAP analysis
8
Beam
Figure 4 SEM
photomicrograph
showing
the sharp
transition
boundary
between the top of the iron sulfide-rich
scale, and the
overlying
fly-ash-rich
deposit.
Small bladed
crystals,
typical
of
sulfate minerals, can be observed at the base of the ash layer and on
several of the fly-ash particles
668
Fuel 1993
Volume
72 Number
traverse
(urn)
Chemistry
of deposit formation:
0. Brooker
Fuel 1993
Volume
72 Number
669
Chemistry
of deposit
of commercial
understanding
formation:
plant deposits
of the deposits.
D. Brooker
in order
to improve
our
4
5
REFERENCES
I
2
670
Fuel 1993
Volume
72 Number