Advanced Chemical Analyses as

Indicators for Coal Fouling and Slagging

Larry Baxter
Brigham Young University
Provo, UT 84602

21st Annual ACERC Conference

February 28, 2007

Origins of Coal

H:C Molar Ratio

2.0

1.5

Cellulose
Grass
Wood
Peat

1.0

anthracite
bituminous coal
subbituminous coal
semianthracite
lignite
peat
biomass

Lignin

Lignite
Subbituminous Coal
Bituminous Coal
Semianthracite

0.5

Anthracite

average values

0.0
0.0

0.2

Average Biomass

0.4

0.6

O:C Molar Ratio

0.8

1.0

Ash Impacts Boiler Design

1.3D

H
W

High-rank Coal

1.4H
1.3W

Low-rank Coal

Chemical Fractionation
Water
Raw Fuel

- 20 g
sample

-5g
sample

Unleached

Fuel

Ammonium
Acetate

Stage 1

Washed
Fuel

Water Washing
Water
Leachate
After Water

Stage 2
Water-Soluble Salts
and Loosely Bound
(Chemisorbed) Material

-5g
sample

Ammonium
Acetate Leaching

Hydrochloric
Acid

Organically Bound
Material

Oxides, Sulfides,
Silicates, and other
Compounds Insoluble
in Acid Remain in the
Residual Material.

Stage 3

- 20 g
sample

After
Ammonium
Acetate

Acetate
Leachate
- 20 g
sample

-5g
sample

Hydrochloric
Acid Leaching

Washed and
Leached Fuel
After
Hydrochloric
Acid

Acid-Soluble Salts,
(Carbonates and Sulfates
but not Sulfides or Sulfites)

Sample Preparation
Flow Chart

Acid
Leachate
- 20 g
sample

-5g
sample

Samples for
Elemental Analyses

Samples for
Moisture Analyses

Illi
no

is

#9

(1

in

#1

ck
y

ck

#6

Ba
s

ke
r

High-melting Clays
Sulfates
Alk & Alk Earth Hydroxides
Iron Oxides
Silica

tu

tu

Ke
n

Ke
n

is

na

Illi
no

Ha
n

D
ec

R
ol
an

da

te

Fraction of Total Mass

W
yo

Bu
t

ite

ite

Li
gn

Li
gn

le

la
h

el

Ea
g

Be
u

M
ig
u

1.2

#6
Bl
(2
in
d
)
Ea
C
an
st
er
yo
n
n
Ke
Pi
nt
tt s
uc
bu
ky
rg
Up
#8
pe
r F ( 2)
re
Pi
ep
tt s
or
bu
t
rg
Pi
#
tt s
8
(3
bu
)
rg
Po
#8
ca
(1
ho
)
nt
as
#3

Sa
n

Inorganic Classes
Low-melting Clays
Carbonates
Phosphates
Pyrite

0.8

0.6

0.4

0.2

Alkali Metals in Coals

Averages of 6696 Fuel Analysis

on

ur

ur

ah

sb

sb

oc

i tt

i tt

ta

#8

#8

#3

(2

(1

(3

1
ck

#1

#8

)
oa

(2
C

tu

y
en
g

ur

rn
sb

te

#6

ck

oo

is

tu

en

i tt

as

ne

#9

A t o m ic a l l y D is p e r s e d

ig

20%

no

ck

(1

in

A c id S o l u b l e

co

tu

#6

as

30%

as

en

is

ke

an

ec

ol

te

R e s id u a l

Illi

no

na

ut

da

te

i te

ni

gn

ig

yo

le

Li

lL

ag

an

Illi

ue

la

ig

eu

an

40%

Percent S odium

Atomically Dispersed Sodium

100%

90%

80%

70%

60%

50%

10%

0%

G
as

tu

ta

#8

#8

#3

(2

(1

(3

ck

oa

#1

#8

en

A t o m ic a lly D is p e r s e d

on

ur

ur

ur

ck

(2

#9

60%

ah

sb

sb

sb

rn

tu

oo

#6

ck

(1

in

A c id S o lu b le

oc

i tt

i tt

i tt

te

en

is

tu

#6

as

70%

as

ne

no

en

is

ke

an

ec

ol

te

80%

ig

Illi

no

na

ut

da

te

i te

ni

gn

ig

yo

le

Li

lL

ag

an

Illi

ue

la

ig

eu

an

co

Percent Potassium

Atomically Distributed Potassium

100%

90%

R e s id u a l

50%

40%

30%

20%

10%

0%

Illi
no

is

#9

(1

in

#1

ck
y

ck

#6

Ba
s

ke
r

High-melting Clays
Sulfates
Alk & Alk Earth Hydroxides
Iron Oxides
Silica

tu

tu

Ke
n

Ke
n

is

na

Illi
no

Ha
n

D
ec

R
ol
an

da

te

Fraction of Total Mass

W
yo

Bu
t

ite

ite

Li
gn

Li
gn

le

la
h

el

Ea
g

Be
u

M
ig
u

1.2

#6
Bl
(2
in
d
)
Ea
C
an
st
er
yo
n
n
Ke
Pi
nt
tt s
uc
bu
ky
rg
Up
#8
pe
r F ( 2)
re
Pi
ep
tt s
or
bu
t
rg
Pi
#
tt s
8
(3
bu
)
rg
Po
#8
ca
(1
ho
)
nt
as
#3

Sa
n

Inorganic Classes
Low-melting Clays
Carbonates
Phosphates
Pyrite

0.8

0.6

0.4

0.2

Major Transformations Summary

Kaolinite
500 C

2H2O

metakaolinite (Al2O3 - 2SiO2)

925 C

SiO2

(clay lattice
destroyed)

silicon spinel (2Al2O3 - 3SiO2)

1100 C

SiO2

Illite

Biotite

950 C

lattice destroyed
at 1100 C

quartz
(SiO2)

spinel*
amorphous
(Al2O3 - MgO)
glass**

spinel
(Fe3O4) or
(MgO - Fe2O3)

1050 C

SiO2
(cristobalite)

mullite (3Al2O3 - 2SiO2)

May not be completely

liquid until 1800 C.
Other members in the kaolinite group,
(i.e. livesite and metahalloysite) are
thought to undergo similar changes.

1100 C
mullite
(3Al2O3 2SiO2)

1300 C
1400 C

1500 C
glass + olivine

liquid glass

liquid glass

1400 C
only glass + corundum
(Al2O3)

1500 C
liquid glass

* Formed from aluminum and magnesium

from middle layers of lattice.
** Formed from alkali and SiO2 from the
outer layers of lattice.

Pyrites

Quartz

Oxidizing
CO2

475 C

Reducing
S, SO2

FeS, Fe2(SO4)3, FeO

525 C
CaO liquid
2570 C

mullite
(3Al2O3 2SiO2)

1200 C
glass formed

Calcite

1000
to 1100 C

lattice destroyed at
940 - 980C

1050 C
alumina or spinel

1:1 mullite-type phase (Al2O3 - 3SiO2)

>1400 C

leucite
(K2O - Al2O3 4SiO2)

Muscovite

Fe2O3
liquid
1600 C

S, SO2

700 C

S, H2S

temperature
inversion
950 C

S, H2S

SiO2 liquid
1723 C

Fe
(partial melt)
970 C

* Temperatures sensitive to mineral

and carbon impurities

Fe

Traditional Analyses
1700

Blind Canyon
Eastern Kentucky
Pittsburgh #8 (2)

1500
1400
1300
1200
1100

Flu
id

Sph
eric
al

He
mis
phe
rica
l

.D
ef.

1000
Init

Temperature (C)

1600

Major Chemical Species

1.2

Kaolinite
D olom ite
C alcium H ydroxide
Potassium H ydroxide
Anorthite

Fraction of Inorganic Mass

Illite
M elanterite
G ibbsite
M agnetite
Albite

H ydroxy Apatite
G ypsum
M agnesium H ydroxide
H em atite
O pal

C alcite
G lauberite
Sodium H ydroxide
Pyrite
Silica

0.8

0.6

0.4

0.2

d
an
R
ol

k
da
yo

e
gl
Ea

Bu
tte

ite
gn
Li

ul
ah

Be

D
ec
ke
an
r
na
Ba
Bl
si
ac
n
k
Th
un
de
Ill
r
in
oi
s
#6
Ke
(1
)
nt
uc
ky
#1
Ke
1
nt
uc
ky
#9
Ill
in
oi
s
#6
Bl
(2
in
)
d
Ea
C
an
st
yo
er
n
n
Ke
nt
Pi
uc
tts
ky
bu
rg
#8
U
pp
(2
)
er
Fr
ee
Pi
po
tts
rt
bu
rg
#8
Pi
tts
(3
)
bu
rg
#8
Po
(1
ca
)
ho
nt
as
#3

Sa

M
ig
ue

lL

ig

ni
te

Complete Species Descriptions

100%

Percent of Inorganic Mass

80%

60%

40%

20%

Sa
n

M
ig
ue
lL
Be
ig
ni
ul
te
ah
Li
gn
Ea
ite
gl
e
Bu
tte
W
yo
da
k
R
ol
an
d
D
e
H
an cke
r
na
Bl
ac Bas
k
Th in
un
Ill
de
in
oi
r
s
#6
Ke
(
nt
uc 1)
ky
Ke
#1
1
nt
uc
ky
Ill
in
#9
oi
s
#6
Bl
i
(2
Ea nd
)
C
st
an
er
y
n
Ke on
Pi
tts ntu
ck
bu
y
r
g
U
#
pp
8
er
(2
)
Fr
Pi
e
ep
tts
bu
or
t
rg
Pi
#8
tts
(3
bu
)
r
Po g #
8
ca
ho (1)
nt
as
#3

0%

Silica
Olivine
Metakaolinite
Magnetite
Spinel
Pyrrhotite
Hydroxy Apatite
Calcium Pyrophosphate
Mullite
Kaolinite
Montmorillonite
Muscovite
Sanidine
Albite
Anorthite
Illite
Pyrite
Calcium Phosphate
Rutile
Opal
Aluminium
Siderite
Hematite
Magnesite
Calcite
Dolomite
Iron Hydroxide
Titanium Hydroxide
Aluminum Hydroxide
Gibbsite
Silicon Hydroxide
Magnesium Hydroxide
Calcium Hydroxide
Potassium Hydroxide
Sodium Hydroxide
Hydrochloric Acid
Magnesium Chloride
Calcium Chloride
Halite
Sylvite
Potassium Carbonate
Sodium Carbonate
Mirabilite
Arcanite
Epsomite
Gypsum
Melanterite
Glauberite
Potassium Metasilicate
Sodium Metasilicate

Individual Species Reactions

kmol

File: C:\HSC4\Ca.OGI

1.0
CaSO4*2H2O

CaSO4

0.9
0.8

Amount

0.7
0.6
0.5
0.4
0.3
0.2
CaSO4*0.5H2O

0.1
0.0
0

100

200

300

Temperature, C

400

Temperature
C
500

Gypsum Typifies Sulfates

kmol
1.0

File: C:\HSC4\Ca.OGI

CaSO4*2H2O

CaSO4

CaO

0.9
0.8

Amount

0.7
0.6
0.5
0.4

Small amount
Of Liquid Forms
During Decomposition

0.3
0.2

CaSO4*0.5H2O

0.1
0.0
0

500

1000

Temperature, C

1500

Temperature
2000 C

Kaolinite Forms Little Liquid

kmol

File: C:\HSC4\Kaolinit.OGI

2.0

SiO2

Amount

1.5

Al2O3*2SiO2*2H2O

1.0

Al2O3*SiO2(S)

Al2O3

0.5

*3Al2O3*2SiO2
0.0
0

500

1000

1500

Temperature, C

2000

Temperature
C
2500

Illite (Muscovite)
kmol

File: C:\HSC4\IlliteD.OGI

1.0
Al2O3
KAlSi3O8

KAl3Si3O10(OH)2
0.9
0.8

Amount

0.7

Begins forming liquid at

relatively low temperatures

0.6
0.5
0.4
SiO2
0.3
KAlSiO4
Al2O3*SiO2(S)

0.2
0.1

KAlSi3O8(M)

0.0
0

500

1000

1500

Temperature, C

2000

Temperature
C
2500

Pyrite Forms Liquid

kmol

File: C:\HSC4\Fes2.OGI

2.0

1.5
Fe0.877S

Amount

Begins to melt here

FeS
FeS2

1.0

0.5

FeO

Fe2(SO4)3

0.0
0

500

1000

Temperature, C

1500

Temperature
C
2000

Deposition Mechanisms

Inertial Impaction

moving
particle

steam
tube

deposit

Eddy Impaction

moving
particle

steam
tube

deposit

Most Mass Impacts

Thermophoresis

+
small
(< 5 m)
particles

steam
tube

deposit

Thermophoresis?

Condensation

vapors

steam
tube

deposit

Condensation

Chemical Reaction

gases

steam
tube

deposit

Gases React with Deposits

Status of Chemical Fractionation

Incorporated into (nearly) commercial software
Analysis developed as VBA code and incorporated into
Access could easily be incorporated into Excel
ASTM Ruggedness tests
Repeatability (ability of a single lab to get similar results) done
Reproducibility (ability of different labs to get similar results)
underway welcome volunteer labs (need about 6 more)

Have database of about 50 coals representing most

ranks, mostly bituminous and subbituminous, and
mostly US fuels.

EB/Ken 9

Roland/Ill 6

Pitt8/Decker

San Miguel
Lignite

Beulah Lignite

Eagle Butte

Wyodak

Decker

Roland

Ill #6 (1)

Hanna Basin

Kentucky #9

Kentucky #11

Blind Canyon

E. Kentucky

Pitt #8 (2)

Pitt #8 (1)

Upper Freeport

Pocahantas #3

Percent Error in Residual Mass

Si Tracer Errors in H2O Step

0.007

0.006

0.005

0.004

0.003

0.002

0.001

EB/Ken 9

Roland/Ill 6

Pitt8/Decker

San Miguel
Lignite

Beulah Lignite

Eagle Butte

Wyodak

Decker

Roland

Ill #6 (1)

Hanna Basin

Kentucky #9

Kentucky #11

Blind Canyon

E. Kentucky

Pitt #8 (2)

Pitt #8 (1)

Upper Freeport

Pocahantas #3

Percent Error in Residual Mass

Si Tracer Errors in AmAc Step

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

EB/Ken 9

Roland/Ill 6

Pitt8/Decker

San Miguel
Lignite

Beulah Lignite

Eagle Butte

Wyodak

Decker

Roland

Ill #6 (1)

Hanna Basin

Kentucky #9

Kentucky #11

Blind Canyon

E. Kentucky

Pitt #8 (2)

Pitt #8 (1)

Upper Freeport

Pocahantas #3

Percent Error in Residual Mass

Si Errors in HCl Step

8

Leachate vs Solids Analysis: H2O

Mass Percent in Leachate [-]

60
50

As Analyzed

40

Based on Solids

30
20
10
0
Si

Al

Ti

Fe

Ca

Mg

Na

Leachate vs Solids Analysis: AmAc

Mass Percent in Leachate [-]

90
80
70

As Analyzed

60

Based on Solids

50
40
30
20
10
0
Si

Al

Ti

Fe

Ca

Mg

Na

Leachate vs Solids Analysis: HCl

Mass Percent in Leachate [-]

40
35
30
25

As Analyzed

20

Based on Solids

15
10
5
0
Si

Al

Ti

Fe

Ca

Mg

Na

Deposition Rates Are Modeled

Inertial impaction
Important for deposit mass
Best quantified
Eddy impaction
Generally small contributor
Largely empirical models
Thermophoresis
Huge theoretical literature
Data comparisons not
satisfying
Condensation
Good theory, but complex
for practical conditions
Chemical reaction
Complex in condensed
phase

Cofiring Deposition

Deposition Rates Vary Widely

Cofiring biomass can
lead to either decrease
or increase in deposition
rates.
Cofiring decreases
deposition relative to
neat fuels.

Oxygen Mass Fraction Contours

Oxygen Isosurfaces

Cloud (Particle) Trajectories

Mechanisms Shift With Size

100%
80%
Thermo

60%

Eddy

40%

Inertial

20%

Particle size [um]

150

142

134

126

119

111

103

95

87

79

72

64

56

48

40

32

25

17

0%
1

Relative importance [%]

Relative importance of deposition mechanisms, Tu 5%

Deposition Rate: First SH

0.4
Inertial (left axis)
Eddy+thermo (right axis)

140

0.35

120

0.3

100

0.25

80

0.2

60

0.15

40

0.1

20

0.05

0
0

0.25

0.5

0.75
Location [m]

1.25

1.5

Deposition flux [kg/day/m2]

Deposition flux [kg/day/m2]

160

Sulfur Affects Chlorine Exposure

BL Mechanisms
Inertial deposition flux [g/m2/h]

BL deposition flux [g/m2/h]

Vapor Deposition
Vapor deposition flux [g/m2/h]

Radiative Properties Are Important

2200

1000

2000

800

1800
0.75

1600

0.5

400

1400
0.35

1200

1000
0.0

200

0.2
Emissivity
Lower Limit

0.2

0.4

0.6

Deposit Porosity

0.8

1.0

600

Heat Flux [kW/m ]

Deposit Surface Temperature [K]

Deposit surface
temperature and heat flux
depend strongly on
thermal conductivity and
emissivity.
Between the theoretical
bounds or thermal
conductivity lies a large
variation in performance.
It is essential that in situ
thermal conductivity data
are collected.

In Situ Conductivity Data

Fuel Stopped,
Sintering Increased

1.0

0.8
0.8
0.6
0.6
0.4

0.4
Deposit

0.2

thermal conductivity
thickness

0.0

0.2
0.0

50

100

150
Time [min]

200

250

300

Thickness [mm]

Normalized Thermal Conductivity [-]

1.0

Strength vs. Porosity

35
30

UoT data
maximum
minimum
current model

Strength (MPa)

25
20
15
10
5
0
0.0

0.2

0.4

0.6

Porosity

0.8

1.0

Emissivity Is Difficult
J
I 1
i

r(i,e)

I 2

(a)

dIi'

r(i',e)

e I 4

(d)

i'

(b)

I 3

e''

i''

(c)

e' dI
e'
r(i,e')

r(i,e'')

I 5

r(i'',e)

(e)

Theoretically rigorous
approaches are being
attempted to describe
emissivities.
Fundamental data (optical
constants) are in
significant disagreement.
New optical constants are
being calculated using
several approaches.

In Situ Experimental Data

Chlorine Dominates Aerosol Formation

d(M/Mo)/dln(d)

10

0.15% Cl, 0.19% Alkali

0.01% Cl, 0.14% Alkali

1
0.1
0.01

0.001
0.1

Chenevert

1
aerodynamic diameter, m

10

Chlorine Controls Aerosol Amount

0.12% Cl, 0.17% Alkali
0.01% Cl, 0.09% Alkali

d(M/Mo)/dln(d)

10

0.16% Cl, 0.25% Alkali

0.01% Cl, 0.48 % Alkali

1
0.1
0.01

0.001
0.1

Chenevert

1
aerodynamic diameter, m

10

High-chlorine Aerosol Composition

S
2%

Si
13%

Cl
45%

Al
4%Ca
5%

Na
17%
K
14%

Chenevert

Low-chlorine Aerosol Composition

Na
6%

K
9%

S
5%

Si
45%

Ca
20%
Mg
3%

Chenevert

Al
12%

Mechanisms Combine