You are on page 1of 6

Chemistry

of deposit formation
gasif ication syngas cooler
Duane

in a coal

Brooker

Texaco R&D, PO Box 509,


(Received
31 March 1992;

Beacon, NY 12508, USA


revised 29 June 1992)

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)

The first commercial


integrated
gasification
combined
cycle (IGCC)
coal gasification
plant was successfully
demonstrated
at Southern
California
Edisons
Cool
Water power station
in Daggett,
California,
USA,
between 1984 and 1989l. The facility used the Texaco
coal gasification
process,
Combustion
Engineering
syngas coolers (waste heat boilers),
and a General
Electric gas turbine. As typical of conventional
coal-fired
boilers, fouling of the water wall tubes occurred. Soot
blowers were used effectively to control the ash deposition
in most areas of the syngas coolers.
At present, very little information
exists for fouling
under pressurized, reducing conditions to assist in future
gasification plant design. Sample probes which have been
used to obtain ash in commercial
coal boilers cannot
readily be used in the syngas coolers. The operating
pressure, long residence time, and complex chemistry of
the system make bench-scale testing and thermodynamic
calculations very difficult, especially without knowing the
actual mineral species forming in the gasifier. Therefore,
to gain a better understanding
of the fouling and the
potential for fly-ash deposition, samples.of scale, deposits
and unsintered
fly-ash were removed
from different
locations
in a commercial
gasification
plant during
different run periods to determine
the extent to which
temperature,
slurry ash chemistry and fluid flow affected
the deposit chemistry. These samples were then analysed
with an electron microprobe,
scanning electron microscope, X-ray diffraction unit, induction-coupled
plasma
spectroscopy
and reflective light microscopy.
PROCESS

CONFIGURATION

The Cool Water


gasification
project
used SUFCo
(western US bituminous)
coal as the primary feed. The

coal gasifiers operating temperature


was approximately
1300C at a pressure of 4.1 MPa. Alternate coal test runs
using Pittsburgh no. 8, Illinois no. 6 and Lemington coals
were also conducted.
Primary conversion
of the coal to
syngas occurred in the gasifier (Figure i ). After exiting
the gasifier, the syngas entered a radiant syngas cooler
where the syngas was cooled from 1200C by a single
pass water wall. The syngas then passed through the
convection syngas cooler which cooled the gas to 340C.
After the syngas cooler, the gas went through the gas
clean-up section which consisted of a carbon scrubber
and a cold solvent sulfur removal unit.
The Texaco gasification
process transports
the coal
into the reaction
vessel as a water-suspended
slurry.
Conversion
of the coal particles results in a reducing
atmosphere (PO, = 10-l ; Ps, = lop5 atm) with H, and
CO being the dominant
gas phases. The majority of the
mineral matter within the coal forms spherical particles,
similar to conventional
coal-fired boilers2,3. Most of the
ash is captured on the refractory wall of the gasifier where
a molten slag layer forms. The volatile species, such as
sodium, potassium,
chlorine, fluorine and sulfur, pass
through the gasifier with the syngas. At the exit of the
gasifier, slag droplets are formed which fall through the
radiant cooler into a pool of water at the bottom of the
unit (radiant sump). The mineral matter that does not
impact on the gasifier wall will either become entrained
in the syngas, if the particle size is below 10 pm, or drop
into the radiant sump along with the slag droplets. Our
caIculations indicate the residence time for particles under
10 pm in the radiant cooler to be approximately
2 min.
Analyses have indicated that some of the volatile species
form soluble salts with the sump water, and that the
water can evaporate during gasification, possibly forming
submicrometre
inorganic particles. Also, the sump water

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

may be used for making the coal slurry, thus increasing


the level of calcium, fluorine, chlorine and sodium in the
feed.

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

Ash ; 5 mm from membrane

glass

fluorite
halite
augite
unidentified

Ash ; 10 mm from membrane

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

Chemistry of deposit formation:

0. Brooker

devitrify, regardless of exposure time. Only during higher


temperature
SUFCo coal gasification runs were crystalline deposits noticed in the convection
deposits. XRD
analyses of the loose ash identified minor amounts
of
quartz,
with the remainder
of the material
being
amorphous
glass.
A cross-section
of the unmounted
membrane
deposit
was analysed on an Amray scanning electron microscope
equipped
with a Kevex
energy
dispersive
X-ray
spectrometer
to verify the elemental partitioning
within
the deposit, indicated by XRD. The SEM images revealed
that the deposit consisted of three distinct layers (Figure
2) : (i) a 50 pm thick layer of iron sulfide scale with
the crystallografic
c-axis oriented perpendicular
to the
tube ; (ii) a 500 pm thick layer of very fine-grained
iron
sulfide containing
spherical fly-ash particles embedded
within it along with scale (Figure 3); and (iii) the
remainder of the deposit consisted primarily of spherical
fly-ash particles d 10 pm (Figure 4).
The initial layer appears to be corrosion
scale, as
suggested by the occurrence
of iron oxide scale as its
base, which has typically been observed in corrosion scale
removed from other metallurgical
samples throughout
the gasifier. EDS analysis of the scale also revealed
approximately
1% chromium,
which is reasonable
because the tubes were fabricated from a low alloy steel.
The SEM photograph
(Figure 3) taken at the contact
between the first and second layer illustrates an abrupt
change from dense, oriented crystals of iron sulfide to
a fine-grained
iron sulfide scale containing
ash particles
and small pieces of scale. The fly-ash makes
up
approximately
25 ~01% of the layer. Reflective microscopy of the material did not reveal any crystal growth
or preferred orientation
of the iron sulfide. Throughout
the 500 pm thickness of the scale, no segregation or size
distribution
of the ash particles occurred.
Additional
SEM data (Figure 4) revealed that at
approximately
500 pm from the tube, the iron sulfiderich layer abruptly
changed to a silicate-rich
layer. At
the base (tube side) of this layer, several of the ash
particles appeared
to have very fine (submicrometre)
bladed growth on their outside, which is the typical
crystal morphology
for alkali or iron sulfates. The small

Figure 3 SEM photomicrograph


showing a close-up view of the iron
sulfide-rich layer. This can be further subdivided
into a dense lower
section consisting of oriented iron sulfide crystals with no ash (bottom
part of photograph),
and a thicker upper section of ash particles
embedded in the iron sulfide

Figure 2 SEM photomicrograph


of a cross-section
through
the
deposit adhering to the membrane
between the water wall tubes. The
dense bottom layer, which is approximately
500 nrn thick, consists
mainly of iron sulfide. A porous fly-ash-rich
layer overlies the iron
sulfide

size of these crystals did not allow EDS analysis of their


composition
on our SEM/EDS
system.
The chemical analyses by EDS (standardless,
atomic
number-absorption-fluorescence
corrected),
for the
different deposition layers are given in Table 2 along with
the SUFCo ash chemistry. As expected from XRD data
and SEM photographs,
the iron and sulfur content
decreased
from the water-cooled
surface to the gas
surface, and the silica, alumina and calcium increased.
The analysis at 6 mm, which was high in sodium, chlorine
and calcium, agrees with the XRD results of fluorite,
halite and gypsum being present. The reduced silica
content of the deposit outer surface is also in agreement

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%

; elements below Na not analysed)


Distance

F
Na
Mg
Al
Si
Cl
S
K
Ca
Ti
Fe

2.5
2.4
11.8
53.2

ppm, wet chemical analysis;


*Average of three areas

all others

2.0
1.9
23.3
2.4
12.5

from water wall (mm)

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

with analysis of other deposits in the system, which


indicates that the deposits have a lower silica content
than the loose ash and slag.
A nine-channel
ARL electron microprobe
was used to
obtain more accurate chemical analysis on the 5-10 ,um
diameter fly-ash particles. Elemental mapping indicates
that iron and sulfur were enriched on the outside of
most ash particles (Figure 5). Some sodium enrichment
was also noted. Fluorine
and chlorine concentrations
were scattered
through
the ash particles.
No other
enrichment
of elements was noted on the outside of the
particles.
To determine the sintering point of the bulk deposit
and loose ash, tests were conducted
under reducing
atmospheres
using the change in electrical resistance
versus temperature
to determine the formation of a fluid
phase3,4. In both sets of samples, a well defined break
in the resistivity curve was noted at 650C and a poorly
defined break was seen at 510C implying
that two
separate fluid phases had formed.
DISCUSSION
Much has been written over the past years on fouling
and deposit built-up in conventional
coal-fired boilers5sh.

668

Fuel 1993

Volume

72 Number

traverse

(urn)

Figure 5 Electron microprobe


traverse of a single 8 pm fly-ash particle
showing
the distribution
of iron (W), sulfur (* ) and sodium
( 0 ) through a polished cross-section of the particle. The other elements
were excluded based on the absence of any trends

Generally, fouling begins on the tubes due to alkaline or


iron sulfate deposition
followed by the deposition
of
low melting alkaline silicates. If the dense scaling layers
are not removed, the temperature
on the outer surface
can become high enough to allow ash particles to form
a massive deposit.
Usually
the sulfur and alkaline
content of the coal, along with boiler design (throughput,
velocity,
tube location
and spacing,
soot blower
placement) are critical factors to determine the extent of
deposit formation.
As with a conventional
coal-fired
boiler, the ash
build-up
on the syngas cooler tubes consists of two
fases: (i) a thin fouling layer caused by the deposition
of submicrometre
particles formed from the condensation
of volatile, low-melting
sulfides and halogen phases,
along with small ash particles against the cooled metal
by Brownian diffusion or thermophoresic
effects ; and (ii )
the deposition of siliceous ash particles which are initially
bonded together by iron sulfide and later by sintering
once they collide against the tubes. In the low-velocity
zones of the coolers, only loose ash settled on the initial
fouling layer, and the ash was readily removed by soot
blowers or fell off by gravity. In the more turbulent
regions, fly-ash particles did adhere, forming a deposit

Chemistry

which was more difficult to remove by soot blowers until


the proper soot blowing design was identified.
The analyses indicated
that the initial fouling layer
consisted of iron sulfide, halite and fluorite. Calcium
sulfate and silica hydrates were present and are thought
to have formed during downtime,
because both phases
are thermodynamically
unstable
under the reducing
atmosphere
and high gasifier temperature
found during
operations.
At shutdown,
water from the sump in the
bottom of the radiant cooler may condense against the
tubes and generate
sulfuric
acid from the partial
oxidation
of iron sulfide. The sulfuric acid would be
neutralized
by the calcium within the fly-ash. The halite
could also form in a similar way, if hydrochloric
acid
formed
at shutdown
and combined
with sodium.
Alternatively,
both sodium and chlorine
are readily
available from the coal and could react to form halite at
the bottom
of the radiant
cooler which was later
incorporated
in the deposit. The random scattering
of
both the halite and gypsum suggests that their formation
was episodic or due to local conditions
in the gasifier.
Initially,
it was believed that the iron sulfide layer
found at the bottom
of the deposit originated
as a
corrosion product from the iron in the tubes combining
with the hydrogen
sulfide from the syngas. However,
tube measurements
indicated that very little corrosion
( ~250 pm per year) occurred while the iron sulfiderich layer was 500 pm thick. During each shutdown, the
tubes were cleaned, and a new 500 pm thick layer of
sulfide was found to have formed. Also indicative
of
the iron sulfide depositing
from the gas fase, was the
occurrence
of discrete iron sulfide layers in the middle
of several silica-rich layers and on the grafite tube, with
each location being at least 2.5 cm from the metal tube.
The identification
of iron sulfide on the outside of many
ash particles
would suggest that the iron sulfide is
forming in the gasifier as submicrometre
particles or from
the reaction of the hydrogen
sulfide in the gas with
other iron-rich
fases in the gas or on the fly-ash
originating from pyrite particles in the coal. The very fine
nature of the iron sulfide in the scale would suggest
fume particles.
One of the few studies
of ash deposition
under
reducing
conditions
indicated
that iron sulfide was
primarily responsible
for slag droplets adhering to iron
sulfide scale on metal tubes. However, this testing was
done at temperatures
above the melting point of iron
sulfide, whereas the syngas cooler operated below the
melting point (1083C under standard
conditions)
of
pyrrhotite.
Phase diagrams
indicate that iron sulfide
and a liquid sulfur can exist as low as 743C, but this
is also higher than the gas temperature
in the deposit
location and does not concur with the initial sintering
temperature.
Microprobe
analyses of the fly-ash outer
surfaces did not detect a significant amount of any other
element to form a low-melting eutectic with the iron and
sulfur.
Fluorine-rich
minerals are not common
in SUFCo
coal. During recycling of the grey water, the concentration of both fluorine and calcium increased in the slurry,
causing higher levels of these elements than in the original
coal. Still, the widespread occurrence of calcium fluoride
was unexpected. This suggests that the formation of CaF,
may be similar to the iron sulfide: either HF forms in
the gas and reacts with volatilized
calcium to form
submicrometre
particles, or submicrometre
particles of

of deposit formation:

0. Brooker

CaF, form during gasification.


The lack of iron sulfide
and calcium fluoride in the loose ash would suggest very
low concentrations
in the syngas.
EDS elemental correlations
were made to determine
whether the amount of volatile elements (mainly Na, K,
F and Cl) in the feed could account for changes in scaling
and deposition rates. Changes in these elements occurred
during recycle operations
(when carbonaceous
material
from the grey water system was sent back to the grinding
facilities for gasification ). Variations
in sodium content
did not appear to change the deposition rate. However,
the hardness and density of the deposit did increase with
increased sodium content. This suggests that sodium was
not a primary factor in fouling or deposit build-up, but
it did decrease
the sintering
point of the deposit,
necessitating
a change in soot blower cycling. No
correlation
was noted between chlorine
and sodium
contents,
but some areas that did have high sodium
contents
had high chlorine contents.
Changes in the
calcium content of the feed did not affect deposit growth
rate, but did change the type of mineral crystallizing
(augite and gehlenite) from the fly ash. No correlation
was noted
with potassium
for SUFCo
coal, but
enrichment
next to the water wall was noted in another
Texaco gasifier which used a high potassium coal.
The chemical composition
of the deposit versus coal
chemistry and loose ash indicates several differences. The
silica content within the bulk of the deposit decreased as
compared to the coal ash and slag. The most likely cause
of the lower silica content is vaporization
of silica from
the deposit by the hot syngas which contains
both
hydrogen and steam. Calculations
indicate that the rate
of loss is dependent on exposure time to the syngas and
temperature.
It should be noted that the inner layer (tube
side) of the deposits has a similar silica concentration
as
the loose fly-ash due to lower temperatures.
Elemental
correlation
also indicates
that the iron
concentration
increased within the deposit along with
the sodium content as compared to the slag (Table 2).
The higher iron content,
as mentioned
previously,
is
consistent
with iron sulfide-rich
particles causing ash
particles to adhere to each other. The higher iron content
of the loose ash that was removed from the coolers
suggests that there is a partitioning
within the gasifier
between the particles forming the slag droplets and the
fly-ash. No other elements gave a correlation
between
the slag and deposits.
CONCLUSIONS
The reducing conditions
found during coal gasification
versus coal-fired
boilers create a new assemblage
of
mineralogic
fases which can foul boiler tubes, but the
physical deposition mechanisms remain the same. Instead
of alkali sulfates, iron sulfide becomes the most likely
source for scaling on the tubes. In both systems, iron,
sulfur,
alkalis
and
chlorine
may cause
potential
problems if their concentrations
in the coal are too high.
Information
from the Cool Water gasification project has
shown that changes in the chlorine and sodium content
can affect deposit strength leading to less effective soot
blowing. By proper design of the syngas cooler, soot
blowers can be used to remove the fly-ash on the water
wall of the boilers prior to sintering of the ash to form
a deposit. Additional
information
needs to be generated
using thermodynamics,
bench-scale testing and analysis

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

Cool Water Coal Gasification


Program : Fifth Progress Report
EPRI Report AP-5931, Palo Alto, 1988
Graham, K. A., Helble, J., Kang, S. G., Sarofim, A. F. and Beer,
J. M. Mineral Matter and Ash Deposition from Coal (Eds R.
W. Bryers and K. S. Vorres), United Engineering Trustees. New
York, 1990, p. 165

Fuel 1993

Volume

72 Number

Raask, E. Mineral Impurities in Coal Combustion;


Behavior,
Problems,
and Remedial
Measures,
Hemisphere
Publishing,
Washington,
1985
Tangsathitkulchai,
M. PhD Thesis Pennsylvania
State University,
1985
Elliot, M. A. (Ed.) Chemistry
of Coal Utilization;
Second
Supplementary
Volume, Wiley, New York, 1981
Bryers, R. W. and Vorres, K. S. (Eds) Mineral Matter and Ash
Deposition from Coal, United Engineering Trustees, New York,
1990
Austin,
L. G., Kinneman,
W. P., Abbott,
M. F. and
Tangsathitkulchai,
M. Ash Deposition
in Syngas Coolers of
Slagging Gasifiers, EPRI AP-3806, Palo Alto, 1984