ESCA AND F T I R S T U D I E S OF BITUMINOUS COAL

Cara L . W e i t z s a c k e r , James J . Schmidt

Joseph A . G a r d e l l a , J r .
Department o f C h e m i s t r y and S u r f a c e Science C e n t e r
U n i v e r s i t y o f B u f f a l o , SUNY, B u f f a l o , NY 1 4 2 1 4
ABSTRACT

B i t u m i n o u s c o a l f r o m t h e I l l i n o i s #6, Upper F r e e p o r t ,
P i t t s b u r g h and Kentucky #9 seams were examined by E l e c t r o n
S p e c t r o s c o p y f o r Chemical A n a l y s i s (ESCA) and F o u r i e r
T r a n s f o r m I n f r a r e d Spectroscopy ( F T I R ) .
These c o a l s were
s t o r e d under v a r i o u s c o n d i t i o n s ( a i r , Na, mine w a t e r ) and
r e c e i v e d i n forms p r o g r e s s i n g f r o m raw t o ash - removed c o a l ,
ESCA was u t i l i z e d t o d e t e r m i n e
(raw, m i l l e d , processed).
s u r f a c e e l e m e n t a l c o m p o s i t i o n and f u n c t i o n a l groups w i t h
S u l f u r and
p a r t i c u l a r a t t e n t i o n g i v e n t o C , O , N and S.
o x i d i z e d c o a l models have been examined t o d e t e r m i n e t h e
s u l f u r and c a r b o n s p e c i e s p r e s e n t a t t h e s u r f a c e .
FTIR has
been used t o c o r r e l a t e f u n c t i o n a l group assignments w i t h t h e
ESCA r e s u l t s .
INTRODUCTION

The s u r f a c e c o m p o s i t i o n c h a r a c t e r i s t i c s o f c o a l a r e
important t o the behavior o f coal i n various processing
techniques.
T h i s s t u d y f o c u s e s on t h e s u r f a c e o f c o a l i n
powder f o r m , w i t h emphasis on t h e e l e m e n t a l c o m p o s i t i o n o f
t h e s u r f a c e o f c o a l , and t h e f u n c t i o n a l i t y of C , 0, N and S .
One i n t e r e s t i n g a p p l i c a t i o n o f t h i s i n f o r m a t i o n would be t o
s t u d y t h e w e t t a b i l i t y o f c o a l , o f concern i n agglomeration i n
v a r i o u s c l e a n i n g processes.
Agglomerated c o a l c o u l d be
separated from mineral m a t t e r . ( l , 2 )
B o t h ESCA and F T I R were used i n t h e s t u d y o f f o u r
bituminous coals.
These c o a l s were t a k e n f r o m t h e I l l i n o i s
# 6 , Kentucky #9, P i t t s b u r g h and Upper F r e e p o r t seams.
The
ROM c o a l s were s t o r e d under t h r e e c o n d i t i o n s - i n a m b i e n t
a i r , mine s i t e t a p w a t e r and d r y n i t r o g e n .
P o r t i o n s o f these
samples were a l s o m i l l e d and p r o c e s s e d ( m i n e r a l m a t t e r
removed), and t h e s e were t h e n a n a l y z e d .
These samples w i l l
s e r v e as r e f e r e n c e samples f o r an o n g o i n g a g i n g e x p e r i m e n t t o
be d e s c r i b e d i n l a t e r p a p e r s .
EXPERIMENTAL
Raw, m i l l e d and p r o c e s s e d Coals were r e c e i v e d under N2
i n sealed b o t t l e s from O tis c a I n d u s t r i e s , Lt d.
Raw c o a l s
were a n a l y z e d as r e c e i v e d .
M i l l e d and processed c o a l s had t o
be vacuum d r i e d t o remove w a t e r and w a t e r / p e n t a n e
A l l samples were s t o r e d under d r y NA when
respectively.
received

545

Vacuum d r y i n g was done on a g l a s s vacuum l i n e .

Samples
were m a n i p u l a t e d u n d e r d r y N2 when l o a d e d i n vacuum t u b e s
A
and when t h e d r i e d c o a l was removed f r o m t h e vacuum t u b e .
l i q u i d n i t r o g e n t r a p was used t o p r e v e n t pump o i l from
b a c k s t r e a m i n g o n t o t h e samples.
Samples were evacuated a t
A f t e r vacuum d r y i n g a l l
room t e m p e r a t u r e f o r f i v e h o u r s .
t h r e e t y p e s o f samples were t r e a t e d t h e same f o r sample
A i r exposure has been m i n i m i z e d t o l e s s t h a n
preparations.
t w o m i n u t e s f o r t h e t r a n s f e r o f samples i n t o i n s t r u m e n t s .
ESCA s p e c t r a were r e c o r d e d on P h y s i c a l E l e c t r o n i c s Model
- r a y s o u r c e (1253.6 e V ) . E x p e r i m e n t a l
5100 w i t h a Mg K,,=X
c o n d i t i o n s o f t h e X - ray were 300 W , 15 kV and 20 mA.
Base
p r e s s u r e o f t h e i n s t r u m e n t was 2 x 10 ( - 9 ) t o r r and o p e r a t i n g
p r e s s u r e ranged f r o m 1 x 10 ( - 7 ) t o 2 x 10 ( - 8 ) t o r r
d e p e n d i n g on t h e sample.
The pass e n e r g y was 35 eV f o r h i g h
r e s o l u t i o n n a r r o w scans.
A l l s p e c t r a were t a k e n u s i n g a 45O
take - o f f angle.
The sampling d e p t h a t t h i s t a k e - o f f
a n g l e was a p p r o x i m a t e l y 60 A .
F o r ESCA a n a l y s i s sample p r e p a r a t i o n was accomplished b y
p r e s s i n g c o a l powder o n t o double - s i d e d s t i c k y tape on a
sample s t a g e .
The c o a l was t r a n s f e r r e d i m m e d i a t e l y t o t h e
i n t r o d u c t i o n chamber o f t h e i n s t r u m e n t and pumped down f o r
one h o u r b e f o r e b e i n g moved i n t o t h e m a i n chamber f o r
analysis.
Wide s c a n s p e c t r a were t a k e n f o r 1 5
20 m i n u t e s ,
f o l l o w e d by h i g h r e s o l u t i o n n a r r o w r e g i o n scans f o r a t o t a l
There was no e v i d e n c e o f sample damage a f t e r
o f 50 m i n u t e s .
6 5 - 70 m i n u t e s under t h e X
ray.
I n f r a r e d s p e c t r a were a c q u i r e d on two d i f f e r e n t F T I R
s y s t e m s . The f i r s t system was a N i c o l e t 7 1 9 9 A F T I R
S p e c t r o m e t e r w i t h a n MCT d e t e c t o r .
The bench was purged w i t h
dry a i r .
S p e c t r a were taken w i t h 1000 s c a n s .
The second
i n s t r u m e n t was a M a t t s o n A l p h a C e n t a u r i w i t h a DTGS d e t e c t o r .
The bench was p u r g e d w i t h d r y N3.
S p e c t r a a c q u i r e d were t h e
r e s u l t o f 3 2 scans.
Samples f o r F T I R were p r e p a r e d by K B r m u l l .
A p p r o x i m a t e l y .42g K B r was mixed w i t h . O D 6
,019 o f c o a l .
The m u l l was p r e s s e d i n t o a K B r p e l l e t u s i n g a 13mm d i e u n d e r
8000 p s i f o r 45 - 60 seconds.

RESULTS AND D I S C U S S I O N

F o r t h i s s t u d y , seven samples f r o m each o f t h e f o u r

seams were a n a l y z e d .
I n each sample s e t , t h r e e samples were
raw c o a l ( s t o r e d under a i r , Ns o r w a t e r ) , two were m i l l e d
( a i r s t o r e d ) and t w o were p r o c e s s e d ( s t o r e d under a i r and
N a ) . T a b l e s 1 - 3 show s u r f a c e a t o m i c c o n c e n t r a t i o n r e s u l t s
f r o m ESCA a n a l y s i s .
Common t o e v e r y one o f t h e s e samples was
t h e d e t e c t i o n o f C,O, and N.
S u l f u r was n o t d e t e c t a b l e on
t h e s u r f a c e o f t h r e e o f t h e raw samples.
O t h e r elements
Na was f o u n d i n b o t h t h e
f o u n d were A l , S i , Na, Fe and K .
Fe and K were o n l y
I l l i n o i s # 6 and Upper F r e e p o r t c o a l s .
f o u n d i n one o f t h e I l l i n o i s raw samples.
I n o r g a n i c e l e m e n t s were d e t e c t e d i n t h e g r e a t e s t
q u a n t i t i e s i n t h e raw samples.
The p e r c e n t s u r f a c e a t o m i c
54 6

concentrations decreased slightly after milling and decreased

significantly after the coal was processed. In the processed
samples, the inorganics were reduced to less than 1 % or, in
many cases, were no longer detectable.
The storage conditions of the raw coals only showed a
significant difference in the Illinois #6 and Upper Freeport
coals. In the Kentucky # 9 and Pittsburgh coals, the
resultant % surface atomic concentrations were consistent
through all three storage conditions. See Table 1 . The two
milled samples of Illinois #6 also showed inconsistency in
the % surface atomic concentrations. For the other three
coals, % surface atomic concentrations of the two milled
samples were approximately equal. See Table 2. In the
processed coals, the % surface atomic concentration o f carbon
was 85 - 8 8 % through all four coals. The % surface atomic
concentration of oxygen was 10 - 12 % . Nitrogen remained
consistent through all storage and processing steps, with a %
surface atomic concentration of approximately 1 - 2 % . The %
S remaining in the processed coals varied from .50 - 1 . 1 %.
See Table 3 .
In ESCA analysis, differential charging of the inorganic
and organic species in the coals was noted. Standards
consisting of mineral matter from each mine were run to
determine the charge correcting for the inorganics. Si, A l ,
Na, K , Fe and inorganic S were corrected using S i (SiO,),
binding energy 103.4 eV. The organic species (C, 0, N and
organic S ) were charge corrected using C 1 s (hydrocarbon),
binding energy 285.0 eV.
\
1,

ir

The C 1 s region was curve fitted to five bands ( 3 , 4 ) .

See Table 4 and Figure 1 . The initial band was set after
standards o f graphite were analyzed. This peak was at a
binding energy of 284.6 eV. Oxidized coal was also analyzed
to solidify the assignments of the carbon / oxygen species.
Quantitation was done based on the curve fits. See Table 5.
From raw to processed coal, a decrease is seen in the
elemental / graphitic C and an increase in the aliphatic /
aromatic C. C - 0 remained consistent, while C = 0 varied
widely.
Sulfur has also been found to be present in inorganic
and organic species. The inorganic sulfur is postulated to
be sulfate compounds. In many samples, nitrogen appears as a
broad peak at approximately 400 eV. Pyridine and pyrrole ( 5 )
appear at approximately 398,8 and 400.2 eV. It is postulated
that both of these could be present.
Transmission FTIR spectra of all samples were collected.
Correlations between F T I R and ESCA results support the
observations of changing surface composition as raw coals
went through processing. Peaks assigned to inorganics such
as silicates vary in intensity proportional to the quantities
found by ESCA. Similiar correlations are found with the
54 7

organics.
CONCLUSIONS
ESCA and FTIR are useful methods in the analysis of coal
surfaces. Composition and surface functionality can be
elucidated. FTIR can be used to correlate these results
deeper into the sample by transmission experiments.
ACKNOWLEDGEMENTS
Support for this work has been provided by the
Department of Energy under Contract # DE - AC22 - 87PC79880
DOE Pittsburgh Energy Technology Center w i t h a subcontract to
Otisca Industries Ltd.
REFERENCES
1. Schobert, H . H . , Coal The Energy Source o f the Past and
Future; American Chemical Society: Washington DC 1987
2 . Frederick Simmons; private communications

3. Perry, D. L. and Grint, A., FUEL 1983, 62, 1024

1033

Wandass, J. H . ; Gardella,Jr., J. A.; Weinberg, N. L.;

Bolster, M . E.; Salvati,Jr., L. J. Electochem. S O C . 1987,
134 ( 1 1 1 , 2734 - 2739

4.

5 . Bartle, K . D . ; Perry, D . L.; Wallace, Fuel Process.

Technol. 1987, 15, 351 - 361

548

TABLE 1
K e n t u c k y Raw

I l l i n o i s Raw

C
0
N
S
A1
Si
Na
Fe
K

A i r

43
40
1.1
.30
5.0
9.2
1.4

23
51

___

Water
33
48
1.1

.60
_--

_--

7.9
15
1.9
3.1
.89

6.5
11
1.4

A i r

71
21
2.0
1.1
2.4
3.2

69
22
1.8
1.2
2.6
3.5

-__

---

-----

I 11i n o i s

N
S
A1
Si
Na

66
27
1.5
.45
2.2
4.4
.86

54
35
1.5
.67
3.4
5.9
.50

--_____

_-_
-----

I11 in o i s

Pittsburgh
M i 1l e d

71
22
1 .o
1.2
1.2
2.8

TABLE 3

TABLE 2

Water

72
22
1.5
.54
2.0
3.3

---

A i r
85
12
1.2
.72

72
22
1.5
..62
2.1
3.5

___
.92
---

___

upper
Freepor t
Processed
N
A i r
N
85
86
88
12
9.1
9.4
1.5
1.8
1.4
.52
1.1
.86
.74
1.o
* 44
.55

___
___

---

___

-_-

TABLE 4
I

284.2 eV

g r a p h i t i c / elemental C

285.0 eV

hydrocarbon ( a l i p h a t i c o r
aromatic)

I1

I11

,. 286.6

I V

,. 290.5

eV

c - 0

288.0 eV

c = o

eV

COOH,

549

c a r b o n a t e o r fl to lT

shakeup

TABLE 5
% C

Species by Curve Fitting

Illinois # 6

Raw

Milled

13.85

2.61

2.43

I1

58.22

67.21

70.70

I11

19.24

17.25

18.26

IV

7.02

9.46

3.88

1.67

3.41

4.73

Processed

Figure 1
C 1 s Region

Illinois 1 6 Milled Coal

9
8

550