A PREDICTION OF COAL ASH SLAGGING UNDER

THE GASIFICATION CONDITION

FOR PREPRINTS OF THE AMERICAN CHEMICAL SOCIETY
DIVISION OF FUEL CHEMISTRY
Hyun-Taek Kim and Han-jin Bae
Energy Department, Ajou University
San 5, Wonchun-Dong, Padal-gu, Suwon, 442-749, Korea
Shi-Hyun Lee
Korea Institute of Energy Research
71-2, Jang-Dong, Yusong-gu, Daejon, 305-343, Korea
ABSTRACT
Several candidate samples for coal gasification are experimented with proximate, ultimate and ash
composition analysis and the fusion temperatures of coal ashes are determined with data from
analysis. The effect of flux addition is also evaluated to find the optimum quantity for slagging
condition, while considering negative effect of CaO addition on gasification reaction. In order to
further expand the variety of candidate coals and the performance in an entrained-bed, the effect of
ash fusion temperature drop is evaluated when blending coals. The results of the experiment
suggested that optimum compositions of CaO flux are IO%, 20% with Alaska and Datong coal,
respectively. However, the optimum value of blending ratio is not known when Posco coal is
blended with candidate coals.
INTRODUCTION
As the need for electric power increases in Korea, large amounts of imported coal will he utilized
in the future. One of the candidate technologies for producing electricity from coal in an
environmentally sound manner and high efficiency is IGCC (integrated gasification combined
cycle). In a slagging-type IGCC processes, ashes in the coal are cohered and formed slag which is
discarded through the bottom of the gasifier. Slagging behavior of coal ash can be enhanced by
adding a reduction agent such as limestone and dolomite.
The objective of this study is to predict the slagging and fluid behavior of various coal ashes for the
optimum slag removal condition slagging-type IGCC power plants from the physical and chemical
characteristics of original coals. The effect of flux addition is studied with candidate coal ash
samples to evaluate optimum quantity of flux addition considering negative effect of CaO addition
in the coal gasification reaction. The change of ash fusion temperature is also studied to find the
optimum blending ratio of Posco coal with Datong coal and Alaska coal. The experimental values
of ash fusion temperatures are compared with calculated values so that predictional methodology
of ash slagging behavior will be verified within our experimental range. Another objective of the
study is to prevent clogging of slag at the bottom of the gasifier which occurs due to solidation of
melted slag. The result of this study will be used to determine optimum operation conditions of a 3
T/D slagging-type gasifier which is located in Ajou University, Korea.

I1

SLAGGING BEHAVIOR IN COAL GASIFIER

Slag in the coal gasifier means the melt of coal ash which has constant viscosity and flow along the
wall of gasifier. In order to remove ash by the slagging operation, the temperature of the gasifier
should be maintained above the fusion temperature of the coal ash. Formed slag should easily flow
down to the exit of the gasifier. To maintain this condition, viscosity of the slag should be
maintained under the 100 poise [I]. Many empirical equations based on experimental data are
proposed in order to explain relationship of chemical composition ofcoal ash and slag viscosity (-51.
In the present investigation, Urbain and Watt & Fereday equations are utilized in calculating slag
viscosity which give reliable values under 100 poise.

(a) Prediction of slag viscosity

Ash slag viscosity can be predicted by Urbain or Watt & Fereday relation. The Urbain equation, in
which composition of each slag component is expressed in mole fraction, is derived from CaO-AI,O,
S O , three components system. The Urbain equation, as in Eqn (I), is mainly used to determine slag
viscosity of low rank coal ash.

1107

In q = In A + In T + 103B/T-A

(1)

in equation(I), T is the absolute temperature, A and B are functions of the chemical composition of
the ash, and q is the viscosity in poise. Parameter A has different value with the quantity of silica
in slag. If the quantity of silica is minimal, slag viscosity can be expanded from Eqns (2)-(13).
A=mT+b

b= -I.8244(1O3m)+0.9416
1O3m=-55.3649F+37.9I86
F=

CaO
CaO + M g O + N a 2 0 + K 2 0

In A = - (0.2693B+I 1.6725)
B= B,+B, (SiO,) + B, @io2) +B,(SiO,)
Bo= 13.8+39.9355a - 4 4 . 0 4 9 ~ ~ ~
B,= 30.481-1 1 7 . 1 5 0 5 +
~ 129.9987 a2
B,= - 40.9429 +234.0486a - 300.04 a2
B,= 60.7619-1 53.9276a+211.1616 a2
e=-

M+AI,O,

M = CaO+MgO+Na,O+K,O+Fe0+2Ti0,+3SO,

(13)

Meanwhile, in the case of medium silica quantity, Eqn(14)-(16) are used instead of Eqns. (3)-(5)

b= -2.0356(103m)+1,1094
-I .3101~+9.9279
F=B(AI,O,+ FeO)
When the silica quantity is high in slag, similarly Eqns.(17)-(19) are used instead of Eqns(3)-(5).
b= -1 .7737(103m)+0.0509
103m=-1.7264F+8.4404

F=

SiO,

CaO +MgO +Na,O + K 2 0

(19)

Using the Urbain equations in calculating slag viscosity of low rank coal, silica content should be
cautiously determined. Silica content mostly affect the B value . In the case of a B value located in
the boundary, the larger value is chosen. The experimental result of Watt and Fereday is accepted
to determined a reliable relationship between the viscosity of slag and temperature. They proposed
Eqn (20), which is derived from regression analysis of experimental data by Hoy et al [6].
1 07m

Log,,rl=-

(T- 1 50),

+c2

In Eqn. (20), m represents (0.00835 Si02 + 0.00601 AI,O, -1.09) where total percent of (SO,
+A1203+Fe,O,+CaO+MgO) equals 100% and C, is (0.0415Si02+0.0192 AI,O, +0.0276 Fe,O,+
0.0160CaO-3.92). q is viscosity in poise and T is in OC. This empirical equation is the best fit when
the coal ash component is throughly melted so that no crystal exists. Prediction of slag viscosity is
correct in the ash component range of Table 1.
The Urbain Watt and Fereday Equation utilized chemical composition of the ash derived by ASTM
methods to predict ash fluidity behavior but not the exact behavior of ash fusiodslagging. Calculated
viscosity data are represented for Alaska and Datong coal in Table 2 and 3.
(b) Prediction of critical viscosity temperature
Liquid phase slag behaves as a Newtonian fluid and, when decreasing temperature, it passes through

1108

the pseudo-plastic state before solidification. Tlie separation from solid phase depends on the
compositioii of slag. When the transition takes place from liquid state to the solid state, the
temperature is call Critical Viscosity Temperature (Tcv). Watt [6] derived the equation which is
related to chemical composition and Tcv in Eqn(21).
Tcv= 2990-1470(SiO,/AI,O,) + 360(Si02/A1,0,)2-14.7(Fq0,+CaO+Mg0)+
0.15(Fe2O,+CaO+MgO)'

(21)

In Eqn (2 I), Tcvis in "C, and the total percent of asli coniponent of SiO, ,AI,O,, Fe,O,, CaO and
MgO equals 100. Because of the limitation in using this equation, Tcv can be assigned as a
hemispherical temperature determined by tlie ash fusion temperature plus 9 3 T [7].
EXPERIMENT OF ASH SLAGGING CHARACTERISTICS
Three different coal samples are utilized for ash fusion teniperature and as11 fluidity behavior.
Proximate and ultimate analysis of coal samples are illustrated in Table 4.
From tlie experimental data of ash fusion determination, relationsliip fouling and slagging can be
made from the coal combustion and gasification reactions. Determination of not only which coal is
tlie best candidate for gasifier or combustor but also whether the dry or wet asli treatment method
is appropriate for coal benification. It is well-known that the difference of fusion temperature are
related to the degree of fouling and slagging. 'l'he greater the temperature ditlerence between IDT
and FT, tlie slower tlie fouling rate so that the intensity of fouling is decrease because more pores
are gcnerated in the fouling process.
Tlic fusion tcmperaturc of samples has been measured by using the asli fusion deterininator (LECO600). Tlie cones were manufacturcd to pyramidal shapc, height I9mm. base 6.5mm. Thc tcmpcraturc
of 39OoC,starting temperature of 538"C, final temperature of 1600C and heating condition and air
in oxidizing condition. Table 5 illustrates the nieasuremeiit results of ash temperature of candidate
coal while adding CaO as fluxing agent. Ash fusion temperature is decreased with CaO addition until
a certain limit but it is increased after that limit because excess addition of CaO results in higher
fusion temperature. Table 6 shows the change of tlic asli fusion temperature with mixing ratio and
Table 7 shows fusion teniperature change with the coniposition of surrounding gas.

Because ash viscosity measurement is performed in a nitrogen atmosphere, fusion tenipcrature

changes with the composition of tlie surrounding gas are evaluated as in Figure 1. Tcv ineasurcd in
nitrogen is lower than the Tcvi n air because Fe acted as strong Iluxing agent in the high temperature
range. Fusion temperature in a rcducing atmospliere is lower tlian that in the oxidation atmosplicre.
The reason is that iron, which plays a significant role i n asli slagging, exists as Fe,O, in an oxidizing
environnient but FeO or Fe in reducing one. Actually, the fusion temperature of pure Fe,O, is
1560"C, FeO is 1420C and Fe is 1275C.From Table 7, fusion temperature with N, as a surrounding
gas is located in the midpoint between those in reduction and oxidation conditions. This result
implies that Fe acts as fluxing agent in the inert enviroiiment. AT i n Table 5, wliicli is difference
between fluidization temperature and initial dcforiiiation tempcralurc is the index which estimates
tlie degree ofslagging. If AT is small, fusion t a k a place suddcnly and thin layer of fusion slag is
generated. Therefore, to carry out tlie optimal slagging in the gasifier, a candidate coal should be
chosen that has an ash composition resulting i n a lower AI' value.

From figure 2 and 3, fusion temperature of Alaska, Datong and Posco coal are mininiuin when IO%,
20% and 30% CaO is added respectively. Also, AT value of Alaska, Datong, Posco coals is
niinimuin when 20%, 20%, and 40% CaO is added respectively. Figure 4 shows the rcsults if fusion
temperature measurement when mixing Posco coal with Datong and Alaska coals from 10% to 50%,
fusion temperatures increased with mixing ratio.

SUMMARY
The ob.jectives of this study arc minimi&ition ofthe negative effccts of CaO addition to iiiaiiitaiii a
slagging state and expanding the various candidate coals by use of the blending method. We
considered the effect of degree of fusion by means of CaO addition and coal blending related with
standard coals (Alaska, Datong) and a comparison coal (Posco). First, from the result of fusion
temperature measurements when Posco coal with Datong and Alaska coals, fusion temperature is
minimum when 10% of CaO is added to Alaska coal, 20% to Datong coal and 50% to Posco coal.

1109

For POSCOcoal, we could estimate that fusion temperature is minimized by an increase of CaO
content, because we varied the content of CaO from I O to 50%. Also, when standard coal is blended
with 10-50%of comparison coal, fusion temperature is minimized with blending of 10% comparison
coal and increases with increasing blending ratio.
From the above experiments, we decided the optimal addition value. Fusion temperatures of Alaska,
Datong and Posco coals are minimum when IO%, 20% and 30% CaO is added respectively. In the
case of blending, there isnt a value which can satisfy viscosity less than 100 poise, because Alaska
and Datong coals have viscosities greater than 100 poise at 1400C. Therefore, we should determine
a more suitable coal in using blcnding mcthod. Also, we should measure viscosity using reduction
gas in order to explain exactly the viscous flow and fusion of coal ash in the gasifier.
REFERENCES
[I] C.L. Senior and S. Srinivasachar, Viscosity ofAsh Particles in Combustion System for
Particle Sticking, Energy & Fuel, P277-283, 1995
[2] William T. Reid, The Relation of Mineral Combustion to Slagging, Fouling and Erosion
During and after Combustion, Prog. Energy Combustion. Sci, Vol IO, 1984
[3] Frank E. Huggins and Gerald P. Huffman, Correlation Between Ash Fusion Temperature
and Ternary Equilibrium Phase Diagrams, Fuel, Vol. 60, 1981
[4] Steve A. Benson, Inorganic Transformation and Ash Deposition During Combustion, 1991
[5] H.H. Schobert & E.K.Diehl, Flow Properties of Low-rank Ash Slags : Implications for
Slagging Gasification, Fuel, Vo1.64,1985
[6] Eric Raask, Mineral Impurities in Coal Combustion, P. 121-135
[7] H.J. Pac, A Prediction Study on the Slagging and Fluid Behavior of Coal Ash under the
Gasifier Condition. 1997

Silica

SiO, /AI,O,

FqO,

CaO

MgO

40-80 w t y o

1.4-2.4

3-30 wt%

2-30 wt%

1-30wt%

wt%

1110

Ultimate Analysis (wt%)

Proximate Analysis (wt%)

'

Coal

Alaska

V.M.

F.C.

Ash

I1

5.09

44.85

35.64

14.42

54.40

4.55

40.24

0.64

0.17

27.35

0.66

0.60

11.08

3.61

0.56

Datong

6.87

29.30

Posco

1.58

30.11

'

54.65

9.18

67.08

4.31

58.32

9.99

71.05

3.71

%CaO (reducing condition)

P

Coal

10%

20%

30%

40%

50%

1165

1143

1187

1256

1406

1413

ST

1176

1163

1200

1275

1471

1525

HT

1212

1183

1211

1289

1527

1535

FT

1287

1208

1218

1344

1529

1537

AFT("C)

Raw

IDT

Alaska

123

AT (FT-IDT)
Datong

IDT

1178

HT

IDT

31

88

123

124

1166

1256

1406

1413

1222

1188

1201

1282

1289

1535

143

35

88

121

124

1193

1219

1257

1380

ST

1420

1278

1215

1234

1268

1440

1460

1308

1243

1245

1275

1467

FT

1519

1379

1317

1260

1286

1486

I150

134

124

41

1176

1261

29

106

. Alaska

I Oxidation

N,

Reduction

1537

1245

Datong

1520
1527

1369

Coal

AFT~C)

1344

HT

AT(FT-IDT)

IDT

184

AT (FT-IDT)
Posco

1268
1362

FT

65
1139

1279

Reduction

1164

I N,
I

Oxidation

1191

1210

~~

1230

ST
HT
FT

1279
1315

1268

1362

1376

I I76

I300
1327

1386

1111

I224

1212

1287

1231

1269

1298

1278

1307

Table 7 Influence of atmospheric condition on ash melting temperature

1440

!1
I

P:A
v
P:O

1360

I4O0

1320

'E

1280

1400

1600

1800

'1060 2060 30!70 40kO 5060'

Blending Ratio

Temperature, K

Fig. 1 Effect of atmospheric condition on

slag viscosity (A: in air, B: in nitrogen).

Fig. 2: Behavior of ash fusion drop due

to blending coal.

200

1600

F'
Q
o

Alaska

100

20 3b 40
CaO Addition, %

10

Alaska

1400
W

-t-

Datong

+E

Posco

._ 1200

Posco

Datong

LL
3

1000

5b

CaO Addition, %

Fig. 3: Behavior of ash fusion temperature

drop due to adding flux.

Fig. 4: Influence of CaO content on

ash melting temperature.

1112