I[~U

mE*, TNEERw

Fuel Vol. 74 No. 12, pp. 1812-1822, 1995

H
N

Copyright 1995 Elsevier Science Ltd

Printed in Great Britain. All rights reserved
0016-2361/95/$9.05 + 0.00

0016-2361(95)00142-5

Influence of mineral matter

pyrolysis characteristics

on biomass

K. Raveendran*, Anuradda Ganesh* and Kartic C. Khilart

*Energy Systems Engineering, Department of Mechanical Engineering,
tDepartment of Chemical Engineering, Indian Institute of Technology, Bombay-400 076,
India
(Received 14 October 1994)
Studies on wood and twelve other types of biomass showed that in general, deashing increased the volatile
yield, initial decomposition temperature and rate of pyrolysis. However, coir pith, groundnut shell and rice
husk showed an increase in char yield on deashing, which is attributed to their high lignin, potassium and
zinc contents. These results were supported by studies on salt-impregnated, acid-soaked and synthetic
biomass. A correlation was developed to predict the influence of ash on volatile yield. On deashing, liquid
yield increased and gas yield decreased for all the biomass studied. The active surface area increased on
deashing. The heating value of the liquid increased, whereas the increase in char heating value was only
marginal.
(Keywords: biomass; pyrolysis; mineral matter)

Biomass is now well recognized as a potential renewable

source of energy. Thermochemical conversion of biomass is one of the most common and convenient routes
for conversion into energy. This includes combustion,
gasification, liquefaction and carbonization. In all these
processes, pyrolysis plays a key role in the reaction
kinetics and hence in reactor design and determining
product distribution, composition and properties.
In the last two decades, extensive studies have been
conducted to understand the complexity of pyrolysis. To
obtain optimal conditions for the desired products, much
work has gone into studying the effects of process
variables and the product distribution. The effect of
feedstock properties has recently been identified as one of
the key research areas 1. This paper reports the results of
studies on the effect of mineral matter present in biomass
on the pyrolysis characteristics, product distribution and
product properties.
Different biomass fuels contain mineral matter in
various amounts. Fuels such as wood and coconut shell
contain < 1 wt% whereas straw and husks contain up to
25wt%. Generally the main elemental constituents of
biomass minerals are Si, Ca, K, Na and Mg, with smaller
amounts of S, P, Fe, Mn and A1. these constituents occur
as oxides, silicates, carbonates, sulfates, chlorides and
phosphates. The influence of composition on ash
deformation and fusion temperatures for various biomass has been studied by Osrnan 2 . Ganesh 3 studied the
influence of silica in rice husk and rice straw on their
combustion and gasification characteristics and reported
that above 1146K, silica in biomass traps the carbon
particles, making it unavailable for conversion.
The catalytic role of mineral matter in char formation

1812

Fuel 1995 Volume 74 Number 12

has also often been reported. Shafizadez et al. 4 found

that inorganic salts suppress the formation of tar and
favour char-forming secondary reactions. Feldmann
et al. s found that mixing of wood ash or calcium oxide
with wood increased the yield of liquid products. The
pyrolysis studies conducted by Gray et al. 6 on deashed
wood waste showed 92% increase in tar yield and 34%
and 33% reduction in aqueous and gaseous products
respectively. Madorsky et al. 7 showed that addition of
0.14% N a O H could increase the char yield by up to 4%.
Essig et al. 8 demonstrated a 235% increase in char yield
on addition of 0.1% NaC1 to cellulose. These studies
indicate that small amounts of inorganic material, as is
present in the biomass, are sufficient to alter the pyrolysis
behaviour to a large extent.
However, most of the studies reported pertain to
woody biomass, and the influence on product properties
remains uninvestigated. The investigations reported here
were aimed towards understanding the influence of ash
on product distribution and the individual product
characterization.

EXPERIMENTAL
S a m p l e selection and preparation
Feedstock properties. Thirteen commonly available

types of biomass in the Bombay region were selected.

Their proximate analyses, ultimate analyses, heating
values and bulk densities are presented in Table 1, and
their component analyses in Table 2. Their ash compositions, determined by the standard geological
rock analysis procedure 9't using inductively coupled

Influence of mineral matter on biomass pyrolysis. K. Raveendran et al.

Table 1

Properties of biomass
Proximate analysis (wt%)

Bagasse
Coconut coir
Coconut shell
Coir pith
Corn cob
Corn stalks
Cotton gin waste
Groundnut shell
Millet husk
Rice husk
Rice straw
Subabul wood
Wheat straw

Ultimate analysis (wt% db)

VM (daf)

Ash (db)

HHV a
(MJ kg-1)

Density
(kg m - ' )

84.2
82.8
80.2
73.3
85.4
80.1
88.0
83.0
80.7
81.6
80.2
85.6
83.9

2.9
0.9
0.7
7.1
2.8
6.8
5.4
5.9
18.1
23.5
19.8
0.9
11.2

43.8
47.6
50.2
44.0
47.6
41.9
42.7
48.3
42.7
38.9
36.9
48.2
47.5

5.8
5.7
5.7
4.7
5.0
5.3
6.0
5.7
6.0
5.1
5,0
5.9
5.4

0.4
0.2
0.0
0.7
0.0
0.0
0.1
0.8
0.1
0.6
0.4
0.0
0.1

47. l
45.6
43.4
43.4
44.6
46.0
49.5
39.4
33.0
32.0
37.9
45.1
35.8

16.29
14.67
20.50
18.07
15.65
16.54
17.48
18.65
17.48
15.29
16.78
19.78
17.99

111
151
661
94
188
129
109
299
201
617
259
259
222

Higher heating value

Table 2

Component analysis of biomass (wt% db)

Bagasse
Coconut coir
Coconut shell
Coir pith
Corn cob
Corn stalks
Cotton gin waste
Groundnut shell
Millet husk
Rice husk
Rice straw
Subabul wood
Wheat straw

Table 3

Ash

Holocellulose

Cellulose

Hemicellulose

Lignin

Extractives

Total
(holo)

Total
(hemi)

2.9
0.8
0.7
7.1
2.8
6.8
5.4
5.9
18.1
23.5
19.8
0.9
11.2

65.0
67.0
67.0
40.6
68.2
63.5
90.2
55.6
50.6
49.4
52.3
65.9
55.8

41.3
47.7
36.3
28.6
40.3
42.7
77.8
35.7
33.3
31.3
37.0
39.8
30.5

22.6
25.9
25.1
15.3
28.7
23.6
16.0
18.7
26.9
24.3
22.7
24.0
28.9

18.3
17.8
28.7
31.2
16.6
17.5
0.0
30.2
14.0
14.3
13.6
24.7
16.4

13.7
6.8
8.3
15.8
15.4
9.8
1.1
10.3
10.8
8.4
13.1
9.7
13.4

99.9
111.7
98.7
94.8
102.9
97.6
86.7
102.0
96.5
96.5
98.8
101.2
96.7

98.8
99.0
100.1
98.1
101.8
100.5
100.2
100.7
104.1
101.8
106.2
99.0
100.4

Ash composition of biomass: major elements (ppmw dry biomass)

Bagasse
Coconut coir
Coconut shell
Coir pith
Corn cob
Corn stalks
Cotton gin waste
Ground nut shell
Millet husk
Rice husk
Rice straw
Subabul wood
Wheat straw

A1

Ca

Fe

Mg

Na

Si

1518
477
1501
3126
182
4686
3737
12 970
6255
1793
4772
6025
7666

125
187
115
837
24
518
746
1092
1020
533
205
614
132

6261
532
389
8095
1693
5924
4924
3547
11 140
1612
6283
1170
4329

93
1758
1243
10 564
141
6463
1298
467
1427
132
5106
92
7861

2682
2438
1965
26 283
9366
32
7094
17 690
3860
9061
5402
614
28 930

284
47
94
1170
445
2127
736
278
1267
337
752
100
214

17 340
2990
256
13 050
9857
13 400
13 000
10 960
150 840
220690
174 510
195
44440

148
73
1653
1911
3642
2455

p l a s m a - a t o m i c e m i s s i o n s p e c t r o s c o p y a r e p r e s e n t e d in
Tables 3 a n d 4.

Sample preparation. T o u n d e r s t a n d t h e i n f l u e n c e
of mineral matter, two types of sample were studied:
(1) d e m i n e r a l i z e d b i o m a s s ; (2) s y n t h e t i c b i o m a s s . T o
confirm the results, studies were also carried out on
salt-impregnated and acid-soaked samples of selected
b i o m a s s t y p e s . T h e s a m p l e s w e r e p r e p a r e d as f o l l o w s .
Demineralization was carried out in two stages. In the
first s t a g e , b i o m a s s s a m p l e s w i t h p a r t i c l e size r a n g i n g
f r o m 100 t o 2 5 0 m m w e r e t r e a t e d w i t h 1 0 % HC1 a t 6 0 C

for 48h with constant stirring. In the second stage,

b i o m a s s o f h i g h e r silica c o n t e n t w a s f u r t h e r t r e a t e d w i t h
aqueous 5% NaOH for 1 h at 90C. Samples were then
w a s h e d w i t h d i s t i l l e d w a t e r , filtered, d r i e d a n d s t o r e d .
Synthetic biomass samples were prepared by mixing
the individual biomass constituents (cellulose, lignin,
x y l a n , e x t r a c t i v e s a n d a s h ) , in p r o p e r p r o p o r t i o n s .
Extractives were isolated from each biomass type
a c c o r d i n g t o T A P P I s t a n d a r d T 11 m . T h e a s h w a s
obtained by burning corresponding biomass in a muffle
furnace, The proportions of the individual constituents
were taken from the component analyses. To simulate

Fuel 1995 Volume 74 Number 12

1813

Influence of mineral matter on biomass pyrolysis." K. Raveendran et al.

Table 4

Ash composition of biomass: trace elements (ppmw dry biomass)

Biomass

Co

Cr

Bagasse
Coconut coir
Coconut shell

0.6
0.5
3.2
8.0
2.3
-

Coir pith

Corn cob
Corn stalks
Cotton gin waste
Groundnut shell
Millet husk
Rice husk
Rice straw
Subabul wood
Wheat straw

Cu

2.0
0.3
0.2
11
6
-

Mn

Ni

18

16

60

16

68
5
1239
T ~
32
T
11
T
21
T
1
7

4
1
27
19
12
38
44
38
108
463
2
25

2
13
22
6
13

64
35
476
15
564
58
299
317
163
221
66
787

25
9
40
11
32
22
52
94
1244
47
40
18

10
lI
49
32
45
1
25

Zn

a Present in trace amount

...... . . .

m'-'-N

, ' ',,'- '

['l:',>q

','';,

-:-',

8 CLEANING PORT

1 ROTAHETER

9 PRODUCT VAPOUR

2 GAS HEATER

10 TEMPERATURE CONTROLLER

3 PYROLYSIS REACTOR
(ELECTRICAL FURNACEI

11 TEMPERATURE INDICATOR

4 CERAMIC WOOL
INSULATION

13 CHILLED WATER TANK

5 HEATING EkE MENT

15 CONDENSING TRAIN

6 CERAMIC TUBE

, ,;.

T T HER NO COUPLE

Tb

12 CONDENSER TUBE
1/, WATER CIRCULATION PUMP
16 GAS FLOW METER

7 SAMPLE BOAT

:.:'Y,;.:

Figure 1

Schematic of the biomass pyrolyser

demineralized biomass, ash was excluded from the

mixture.
Potassium chloride was impregnated into demineralized coir pith, rice husk and groundnut shell at different
concentrations. These biomass types were chosen on the
basis of the results reported below. Biomass samples
(1 tool, ~25 g) were soaked for 48 h in KC1 solutions of
strength 0.01 and 0.36 g ml-Z at room temperature. Zinc
chloride was similarly impregnated into the same
biomass types, using 0.01 and 1.0 g ml-~ solutions. The
amounts of salts impregnated were determined by ash
analysis.

Thermal analysis
Dynamic t.g.a, studies were carried out with a thermal
analyser on untreated, demineralized and synthetic
biomass samples at a heating rate of 5 0 K m i n -1 in a
nitrogen flow.

1814

Fuel 1995 Volume 74 Number 12

Pyrolysis
Experiments were conducted in a packed bed pyrolyser
designed for the purpose, with provision for collecting
the pyrolysis products. Figure I shows a schematic of the
pyrolysis reactor.
Based on the results of the thermal analysis, five
representative biomass types were selected for further
investigations using this reactor. Isothermal experiments
in a nitrogen flow at 773 K were conducted on 10-25 g
samples of each of these five biomass samples, both
untreated and demineralized. The volatiles evolved were
collected and quenched in a train of flasks immersed in
an ice bath. The remaining non-condensable gases were
passed through a flow meter. The experiment was
continued until the evolution of gases ceased. The
furnace was then switched off and the remaining char
was cooled in the nitrogen flow to room temperature and
then weighed. The tar yield was obtained from the

Influence of mineral matter on biomass pyrolysis. K. Raveendran et al.

1.0

0,8-

....

CORN

2-0

Untreated

Oeashed

"~\. V I

=1.5

1.0 o,
o 0.~-

straws and husks are characterized by ash of high silica

content (90-95 wt%). Wood ash is characterized by high
Ca (70wt%), Mg (14wt%) and K (7wt%) contents,
whereas coconut coir ash has high K (36 wt%) and Na
(13wt%) contents. The ash of bagasse, corn cob and
corn stalks has high K, Mg and Ca contents. It can also
be seen that rice husk, groundnut shell, coir pith and
wheat straw have high K contents, and rice husk in
particular contains ~100 times as much Zn as the other
biomass types.

150 200 2;0

300 3'50

4'00 t,50

Temperature({;

Figure 2

5'00 5'50

6'00 6"50

700

T.g.a. and d.t.g, curves of untreated and demineralized corn

cob

difference in the weight of the flasks before and after the

experiment. The yield was obtained by difference.
Repeatable results were achieved.
The char and liquid products were tested for properties including ultimate analysis, heating value, iodine
adsorption of char and BET surface area of char.
RESULTS AND DISCUSSION

Tables 3 and 4 in conjunction with Table 1 show that the

Table 5

Thermal analysis
Influence of demineralization.
Representative t.g.a.
and d.t.g, curves for untreated and demineralized biomass are presented in Figure 2. The changes in volatile
and char yields on demineralization, as well as the
changes in maximum rate of pyrolysis and incipient
devolatilization temperature for all the biomass types
are shown in Table 5.
Table 5 clearly brings out the influence of mineral
matter. It can be seen that the removal of mineral matter
increases the yield of volatiles except for coir pith,
groundnut shell and rice husk. Demineralization
increases the maximum rate of devolatilization and the
initial decomposition temperature in all cases. The
exceptional behaviour of the above three biomass types
may be explained on the following grounds.
Rice husk, groundnut shell and coir pith can be seen to

Influence of demineralization on pyrolysis: t.g.a, studies

Yield (wt%) b

Bagasse
Coconut coir
Coconut shell
Coir pith
Corncob
Corn stalks
Cotton gin waste
G r o u n d n u t shell
Millet husk
Rice husk
Rice straw

Subabul wood
Wheat straw

Relative change (%)

State a

Volatiles

Char

Max. devol.
rate (wt% K -])

U
D

79.7
81.4

20.3
18.6

0.92
1.27

2.2

-8.5

U
D

69.8
70.8

30.2
29.2

0.80
1.28

1.3

U
D

70.7
72.7

29.3
27.3

0.75
1.01

2.80

U
D

56.8
52.2

43.2
47.8

0.56
0.50

U
D

73.5
88.8

26.5
11.2

U
D

70.9
77.0

U
D

Volatiles

Char

Max. rate

Temperature (K)"
IDT

IPT

TMR

39.4

483
528

688
708

677
673

-3.0

58.9

513
548

673
713

672
678

-6.6

35.2

518
533

678
718

615
620

-8.2

10.8

-11.0

483
513

663
948

622
633

1.08
1.64

20.8

-57.7

51.5

533
558

653
698

603
660

29.1
28.0

1.14
1.95

8.6

-0.2

58.9

498
533

653
683

634
639

80.6
89.4

19.4
10.6

1.31
1.86

10.8

-45.1

36.1

523
553

688
693

679
684

U
D

68.7
66.7

31.3
33.3

0.67
0.75

-2.9

6.3

12.1

493
513

683
673

662
668

U
D

70.1
80.6

29.9
19.4

0.88
1.48

15.0

-16.2

68.4

523
503

663
683

653
658

U
D

70.0
66.2

30.0
33.8

0.84
1.07

-5.1

12.6

26.9

518
543

663
693

666
668

U
D
DD a

74.7
82.1
81.6

25.3
17.9
18.4

1.03
1.31
1.27

9.9
9.3

-29.3
-27.4

27.0
23.3

518
548
523

673
703
693

651
653
655

U
D

75.4
77.3

24.6
22.7

0.97
1.27

2.4

-7.3

30.8

U
D

72.8
75.1

27.2
24.9

0.90
1.21

3.2

-8.5

34.3

498
528
493
518

603
728
663
668

672
688
604
617

a U, untreated; D, demineralized
b D a f biomass basis
( IDT, initial decomposition; IPT, involution point; T M R , max. rate
a Alkali-treated after acid treatment

Fuel 1995 Volume 74 Number 12

1815

Influence of mineral matter on biomass pyrolysis: K. Raveendran et al.

15.0

I
BG-BAGASSE
CN-CASHEWNUT SHELL

ACB

CR-COCONUT

COIR

CS-COCONUT SHELL
MH
A

10.0 ~
~

CP-COIR
CB-CORN
CS-CORN

PITH
COB
STALKS
CW-COTTONGIN WASTE
GS-GROUNDNUT SHELL
MH- MILLET HUSK
R H - R I C E HUSK
R S - R I C E STRAW
WD-WO00
WS- WH EAT STRAW

CW

A
A

RS
~ ~

CT

o 5.0"
o
c

.A WS

--

~ 0.0.
u

SE=2"29
Y - - 0 . 9 6 4 xX.,7.192

I
I
I

-5.0.

&.0
7.5
9.0
Ligninl.0952XK 1.3727 Xz0.0996

I I i
14.0

15.0

Change in volatiles versus product of lignin, potassium and zinc contents

1.00 ~

1.00 I ~ ~

1.00

ORIGINAL ]
--~ "~"- SYNTHETIC 0.75

0.75

u
O
u.

cg

I i I I I I I I I [ I I I I i , i l I l i i i I I I i I I

-1.1

"',,.A

I
I
I
I

-I0.0

Figure 3

RH

0.50 /

~ll

I
~

75.0 -";.=o ~
O

0.50

e"

1.00

OEASHED

~J~ll~ --~-~-- SYNTHETIC - 0.75

WrT.0UTAs.
i

50.0-

-0.50

O
tO1

025

0.25

.~ 25.0-

o,25

O
>

0.00

Figure 4

:a.~.
150 250
i

450 C)
I

350
Temperature(

0.~
700

I-n.-.~
I

150

250

- - ,--'a--D--n-$.~~
nt~ I "
I
!
I
I
I v.vv
350 450 550 650 700
Temperature(C)

T.g.a. curves of natural and synthetic biomass pyrolysis

have high lignin contents (Table 2). It is known from

the literature TM and the authors' studies that on
pyrolysis, lignin gives a higher char yield than cellulose
or hemicellulose. Further, potassium, which is exceptionally high in these three kinds of biomass, is known to
be a strong catalyst for char gasification 12 15, promoting
the gasification of char by CO 2 and H20. It can be
understood that since CO 2 and H20 are primary

1816

0.00

Fuel 1995 Volume 74 Number 12

products of pyrolysis, in the presence of potassium they

react with the char (present in high yield initially in these
cases because of the high lignin content) to form CO and
H2, thereby decreasing the char yield. In other biomass
types, not only is there less potassium but also less lignin.
In wheat straw, even though the potassium content is
high, because of the lower lignin content the char yield
does not increase on demineralization.

Influence of mineral matter on biomass pyrolysis." K. Raveendran et al.

Table 6 Influence of salt impregnation on pyrolysis: t.g.a, studies
Relative change (%)b

Yield (wt%f
Volatiles

Char

Max. devol.
rate (wt % K- l )

86.5
62.6
99.0
63.4
56.8
52.2

13.5
37.4
1.0
36.6
43.2
47.8

0.80
0.99
0.69
0.43
0.56
0.50

65.7
19.9
89.7
21.5
8.9
-

-71.7
-21.8
-97.9
-23.4
-9.7

79.3
74.6
98.6
70.8
68.7
66.7

20.7
25.4
1.4
29.2
31.3
33.3

1.04
1.12
0.68
0.57
0.67
0.75

18.9
11.8
47.8
6.1
3.0

80.7
76.6
97.9
77.7
70.0
66.2

19.3
23.4
2.1
22.3
30.0
33.8

1.06
1.15
0.66
0.45
0.84
1.07

21.9
15.6
47.8
17.4
5.7

Volatiles

Char

Temperature (K)c

Max. rate

IDT

IPT

TMR

59.9
98.5
38.0
13.1
12.4

483
463
698
503
483
513

683
693
953
778
663
948

370
365
883
693
622
633

-37.9
-23.6
-95.6
-12.2
-6.0

38.4
48.8
-8.8
-23.5
-10.8

493
493
693
493
493
513

683
683
943
773
683
673

653
643
883
583
662
668

-42.9
-30.7
-93.8
-34.1
-11.2
-

- 1.4
7.5
-38.3
-58.2
-21.2
-

533
533
723
603
518
543

603
603
953
883
703
673

658
653
883
773
666
668

Coirpith
KCI (H)a
(L)~
ZnCI2 (H)
(L)
Untreated
Demineralized

Groundnut shell
KC1 (H)
(L)
ZnC12 (H)
(L)
Untreated
Demineralized

Rice husk
KC1 (H)
(L)
ZnCI2 (H)
(L)
Untreated
Demineralized

a H, high, L, low, concentration of solution (0.36 and 0.01 gml J for KC1, 1.0 and 0.1 gml -j for ZnCI2)
b Compared with the demineralized biomass

Table 7

Influence of ash on pyrolysis in reactor

Yield (wt% daf)

Coir pith
Corn cob
Groundnut shell
Rice husk
Wood

Relative change (%)

State

Vol.

Char

Liquid

Gas

U
D
U
D
U
D
U
D
U
D

70.5
68.7
79.9
87.1
72.9
72.5
82.7
75.6
80.7
86.4

29.5
31.3
20.1
12.9
27.1
27.5
17.3
24.4
19.3
13.6

29.4
36.2
37.4
43.4
40.5
45.9
41.2
57.4
22.6
40.1

41.0
32.5
42.5
43.6
32.5
26.6
41.5
18.2
58.0
46.4

I n a similar m a n n e r , the presence o f zinc ( k n o w n to be

a good activating agent) in rice husk as well as the high
lignin c o n t e n t explain the increase in char yield o n
d e m i n e r a l i z a t i o n . The c o m b i n e d influence of potassium,
zinc a n d high lignin c o n t e n t is represented in Figure 3.
The following correlation was developed for this
behaviour:
A V = -0.964(L

l'095v.-xKl'3727V0.0996"~./x
Z
)+

7.192

where A V = change in percentage yield o f volatiles due

to d e m i n e r a l i z a t i o n , L = lignin c o n t e n t ( w t % ) o f biomass, X~: = fraction o f p o t a s s i u m in silica-free ash, a n d
Xz -- fraction o f zinc in silica-free ash. This correlation
was o b t a i n e d by n o n - l i n e a r o p t i m i z a t i o n for these
biomass types with a s t a n d a r d error o f 2.29. To validate
this correlation, a further b i o m a s s type, n a m e l y cashew
n u t shell, was studied. The change in percentage yield o f
volatiles o b t a i n e d experimentally was - 7 . 3 7 a n d the
m o d e l prediction was - 7 . 2 2 . This correlation can there-

Vol.

Char

Liquid

Gas

-2.4

5.5

23.1

-20.8

8.9

-35.6

16.0

-3.2

-0.5

1.5

13.4

-9.1

-8.6

41.3

39.3

-56.2

7.1

-29.8

76.9

-20.1

fore be used to predict the influence of m i n e r a l m a t t e r

satisfactorily.
As can be seen in Figure 3, zero on the y-axis,
representing n o change in volatile matter, corresponds to
a value o f 7.5 o n the x-axis. W h e n the value of the
p r o d u c t in brackets in the above correlation exceeds 7.5,
therefore, the change in yield o f volatiles is negative.

Synthetic biomass studies. Figure 4 compares the t.g.a.

a n d d.t.g, curves of synthetic a n d untreated representative
b i o m a s s (coir pith). The pyrolysis characteristics of the
synthetic biomass m a t c h those of the n a t u r a l one well.
This is true for all the biomass types tested. These results
confirm the definite role played by m i n e r a l matter,
irrespective of its structure a n d other properties, in the
pyrolysis of the biomass.
Influence of salt impregnation. The specific pyrolysis
b e h a v i o u r o f g r o u n d n u t shell, rice husk a n d coir pith

Fuel 1995 Volume 74 Number 12

1817

Influence of mineral matter on biomass pyrolysis." K. Raveendran et al.

Table 8 Influence of chloride salt impregnation on pyrolysis in reactor
Relative change (%)"

Salt
impregnated
(wt%)

Yield (wt% daf)

Volatiles

Char

Liquid

Gas

Volatiles

Char

Liquid

52.9
9.7
18.8
2.8
-

80.5
75.6
90.1
83.6
70.5
68.7

19.5
24.4
9.9
16.4
29.5
31.3

24.2
28.4
25.9
29.4
29.4
36.2

56.2
47.2
64.2
54.2
41.0
32.5

17.1
10.0
31.1
21.7
-2.5

-37.6
-22.0
-28.5
-19.0
-5.5

-33.1
-21.7
-28.5
-19.0
-18.8

73.1
45.4
97.6
67.0
26.2

54.0
3.3
13.9
2.6
-

76.7
73.8
90.8
76.4
72.9
72.5

23.3
26.2
9.2
23.6
27.1
27.5

34.3
39.3
18.9
26.8
40.5
45.9

42.5
34.5
71.9
50.4
32.4
26.6

5.8
1.8
25.1
5.3
0.5

-15.3
-4.7
-66.3
-14.1
-1.5

-25.4
-14.4
-58.9
-41.6
-11.8

59.5
29.6
170.0
89.3
21.7

27.6
1.7
9.8
1.5
-

77.4
77.0
87.1
78.1
82.7
75.6

22.6
23.0
12.9
21.9
17.3
24.4

35.1
42.2
38.4
30.0
41.2
57.4

42.3
34.8
48.8
48.1
41.5
18.2

2.4
1.9
15.3
3.4
9.5

-7.5
-5.9
-47.3
-10.5
-29.2

-38.8
-26.4
-33.1
-47.7
-28.2

132.2
91.2
167.9
164.3
128.2

Gas

Coir pith
KC1 (H)a
(L) a
ZnC12 (H)
(L)
Untreated
Demineralized

Groundnut shell
KCI (H)
(L)
ZnC12 (H)
(L)
Untreated
Demineralized

Rice husk
KCI (H)
(L)
ZnC12 (H)
(L)
Untreated
Demineralized

a Compared with demineralized biomass

Table 9 Influence of carbonate salt impregnation on pyrolysis in reactor

Salt
impregnated
(wt%)

Yield (wt% daf)

Relative change (%)a

Volatiles

Char

Liquid

Gas

Volatiles

Char

Liquid

Gas

49.4
6.8
39.5
11.8

68.3
73.7
83.9
75.3
72.9
72.5

31.7
26.3
16.1
24.7
27.1
27.5

6.1
10.0
5.9
16.7
40.5
45.9

62.2
63.7
78.0
58.6
32.4
26.6

-5.9
1.6
15.1
3.8
0.5

15.6
-4.3
-41.4
-10.0
-1.5

-86.8
-78.1
-87.2
-63.6
-11.8

133.6
139.2
193.0
120.1
21.7

33.3
11.1
22.8
6.5
-

71.7
86.7
78.4
78.0
82.7
75.6

28.3
13.3
21.6
22.0
17.3
24.4

5.5
11.9
5.5
13.9
41.2
57.4

66.2
74.8
72.9
60.0
41.5
18.2

-5.1
14.7
3.8
2.1
9.5

15.6
-45.5
-11.8
-6.4
-29.2

-90.4
-79.4
-90.4
-75.7
-28.2

263.9
311.0
300.8
230.0
128.2

Groundnut shell
KzCO 3 (H)
(L)
ZnCO 3 (H)
(L)
Untreated
Demineralized

Rice husk
KzCO 3 (H)
(L)
ZnCO3 (H)
(L)
Untreated
Demineralized

a Compared with demineralized biomass

w a s f u r t h e r i n v e s t i g a t e d b y studies c o n d u c t e d w i t h salti m p r e g n a t e d b i o m a s s . B e c a u s e o f the r e l a t i v e l y h i g h K

c o n t e n t s o f g r o u n d n u t shell, c o i r p i t h a n d rice h u s k
(Table 3) a n d the h i g h Z n c o n t e n t o f rice h u s k (Table
4 ), p o t a s s i u m a n d zinc salts w e r e u s e d f o r i m p r e g n a t i o n .
T h e results are c o m p a r e d w i t h t h o s e for the u n t r e a t e d
a n d d e m i n e r a l i z e d o r i g i n a l b i o m a s s in Table 6.
Table 6 s h o w s that, o n i m p r e g n a t i o n w i t h e i t h e r KC1
o r ZnC12, at b o t h l o w a n d h i g h c o n c e n t r a t i o n s , the yield
o f v o l a t i l e s i n c r e a s e s for all t h r e e b i o m a s s t y p e s t h e r e b y
r e d u c i n g the c h a r yield. It is e v i d e n t f r o m these results
t h a t t h e p o t a s s i u m a n d zinc p r e s e n t in the u n t r e a t e d
b i o m a s s i n f l u e n c e the f o r m a t i o n o f volatiles, so t h a t o n
d e m i n e r a l i z a t i o n , g r o u n d n u t shell, c o i r p i t h a n d rice
h u s k yield less volatiles. T h e initial d e c o m p o s i t i o n
t e m p e r a t u r e d e c r e a s e s o n KC1 i m p r e g n a t i o n . I n c o n t r a s t ,

1818

Fue11995 Volume 74 Number12

Table 10 Crystallinity index of biomass

Crystallinity index
Biomass

Untreated

Demineralized

Change
in Crl (%)

Coir pith
Corn cob
Groundnut shell
Rice husk
Wood

8.7
34.6
25.0
43.6
44.0

12.5
32.3
50.1
53.3
41.8

43.2
-6.6
100.0
22.2
-5.1

ZnC12 i m p r e g n a t i o n n o t o n l y i n c r e a s e s t h e d e c o m p o s i t i o n t e m p e r a t u r e b u t i n c r e a s e s it m o r e , t h e h i g h e r the salt

c o n c e n t r a t i o n . It is c l e a r f r o m this t h a t the shift in
decomposition temperature observed on demineraliza-

Influence of mineral matter on biomass pyrolysis. K. Raveendran et al.

Table

11 Char adsorption properties

Coir pith
Corn cob
Groundnut shell
Rice husk

Wood
Standard c

State

InZdexb

12
adsorbed
(wt%)

U
D
U
D
U
D
U
D
DD a
U
D
-

1.56
2.07
1.20
2.89
0.89
2.01
2.09
1.62
3.20
0.72
0.75
4.18

29.9
39.8
23.0
55.5
19.6
43.0
44.6
34.6
61.3
15.5
16.1
98.0

Change
in 12
adsorbed
(%)

12
index
(daf)

12
adsorbed
(daf)

BET
area
(m2g J)

22.4

1.77
2.26
1.49
3.51
1.11
2.18
6.42
6.59

33.9
45.2
28.5
67.3
24.4
46.6
137.1
140.8

470
625
381
500
277
375
260
340

3.9

0.75
0.76

16.2
16.2

234
252

32.9
141.4
119.0

Change
in BET
area (%)
32.6
31.2
35.4
30.8

7.7

"Alkali-treated after acid treatment

b i2 adsorbed (g) from standard 12 solution (2.7gml I) by 0.5g of carbon
c AR-grade activated carbon

Table 12 Higher heating value (MJkg

products

Coir pith
Corn cob
Groundnut shell
Rice husk
Wood

daf) of biomass pyrolysis

State

Biomass Char

Liquids

Gas~

U
D
U
D
U
D
U
D
U
D

19.46
16.11
19.82
19.98
19.95

18.66
22.33
23.81
24.19
23.62
26.15
22.45
23.72
24.94
28.54

16.06
10.51
05.19
08.01
10.00
02.97
07.42
07.13
16.61
11.28

24.97
26.19
28.59
26.35
27.43
29.76
44.24
30.96
24.13
24.24

a By difference
tion can be a t t r i b u t e d to the presence of i n o r g a n i c
material.

b~uence of demineralization. The results o b t a i n e d ,

Table 7, show a similar trend to that in the t.g.a, experiments. The m a i n findings are:
(1) as observed in t h e r m a l analysis, the char yield
increases o n d e m i n e r a l i z a t i o n o f the coir pith, g r o u n d n u t
shell a n d rice husk;
(2) again, the char yield decreases o n d e m i n e r a l i z a t i o n o f
the other two representative materials;
(3) the increase in char yield o n d e m i n e r a l i z a t i o n is m u c h
greater for rice husk t h a n for coir pith a n d g r o u n d n u t
shell;
(4) there is a substantial increase in liquid yield for all five
materials, r a n g i n g from 77% for wood to 13% for
g r o u n d n u t shell; c o n s e q u e n t l y there is a decrease in gas
yield.
These results are of m a j o r significance for increased
liquids p r o d u c t i o n a n d o p t i m i z i n g the p r o d u c t i o n of
b o t h liquids a n d char.

Pyrolysis
To verify the above results, the three exceptional
materials (coir pith, rice husk a n d g r o u n d n u t shell) a n d
two other typical representative materials (wood a n d
c o r n c o b ) were used for further studies with the packed
bed pyrolyser, in the u n t r e a t e d , demineralized a n d salti m p r e g n a t e d forms.

Influence of salt impregnation. The results, Table 8,

again show a similar trend to that o b t a i n e d in the t.g.a.
experiments. It can be observed that
(1) salt i m p r e g n a t i o n of demineralized biomass reduces
the char yield for all three samples studied (coir pith,
g r o u n d n u t shell a n d rice husk);

Table 13 Distribution of energy in biomass pyrolysis products

Energy (%)

Coir pith
Corn cob
Groundnut shell
Rice husk
Wood

Change in energy (%)

State

Char

Liquids

Gas

U
D
U
D
U
D
U

37.9
42.1
35.6
21.2
37.4
41.2
38.3
37.9
23.4
16.5

28.2
39.3
49.4
53.2
44.7
54.0
46.3
50.3
28.3
57.3

33.8
18.6
15.0
25.7
17.9
04.8
15.4
11.8
48.3
26.2

U
D

Char

Liquids

Gas

I 1.0

39.2

-45.0

-40.6

7.6

71.8

10.1

20.9

-73.6

- 1.2

8.7

-23.4

-29.5

102.5

-45.8

Fuel 1995 Volume 74 Number 12

1819

Influence of mineral matter on biomass pyrolysis." K. Raveendran et al.

Table 14

Elemental analysis of pyrolysis products

Composition (wt% daf)

Change (%)

Ratio

O"

H/C

O/C

2.4
2.1
2.4
2.3
2.4
2.2
3.2
2.4
2.4
1.8

14.1
20.9
11.8
17.0
17.7
16.8
08.2
38.0
13.8
13.0

0.028
0.028
0.028
0.029
0.030
0.027
0.036
0.041
0.029
0.022

0.17
0.27
0.14
0.21
0.22
0.21
0.09
0.64
0.17
0.15

47.0
50.2
54.6
53.5
55.4
34.2
41.2
48.9
16.7
53.2

6.0
6.4
6.3
6.5
7.3
7.8
7.4
6.1
7.4
6.3

46.9
43.5
39.1
39.5
34.6
57.1
51.2
44.2
75.8
40.5

0.13
0.13
0.12
0.12
0.13
0.23
0.18
0.12
0.44
0.12

14.4
7.0
14.3
35.4
23.1
51.0
44.6
46.5
49.3
34.0

6.4
6.6
7.0
4.7
7.4
6.8
7.5
14.3
6.5
6.7

70.1
67.2
79.1
60.8
71.1
41.3
46.3
38.9
44.2
59.3

0.45
0.95
0.49
0.13
0.32
0.13
0.17
0.31
0.13
0.20

State

U
D
U
D
U
D
U
D
U
D

83.6
76.7
85.3
79.5
78.9
80.0
88.8
59.5
83.7
84.7

U
D
U
D
U
D
U
D
U
D
U
D
U
D
U
D
U
D
U
D

H/C

O/C

Char

Coir pith
Corn cob
G.nut shell
Rice husk
Wood

-8.2

-9.3

48.6

-1.4

62.0

-6.8

-3.3

43.5

3.7

53.3

1.4

-8.8

4.9

9.9

-6.3

-36.4

-24.4

361.0

12.7

587.4

1.2

-25.1

-5.9

-25.9

-7.0

6.7

5.5

-7.2

-1.2

-13.0

-2.0

2.0

1.0

4.1

3.1

-38.2

7.0

65.3

118.6

-17.7

218.2

Liquid
Coir Pith
Corn cob
G.nut shell
Rice husk
Wood

1.00

0.87
0.72
0.74
0.62
1.67

73

167.3

-13.7

-30.6

-54.3

-14.7

-46.6

-59.7

-83.2

-51.8

2.3

-4.1

112.2

98.9

147.3

-33.2

-23.1

-73.0

-68.9

120.6

-7.9

-41.9

-58.2

-73.6

4.1

89.5

-16.1

83.2

-19.4

31.0

3.1

34.3

49.4

93.8

1.24

0.90
0.54
0.76

Gas<`
Coir pith
Corn cob
G.nut shell
Rice husk
Wood

4.87
9.69
5.52
1.72
3.07
0.81
1.04

0.84
O.90
1.74

a By difference
(2) on salt i m p r e g n a t i o n , the liquid decreases (by ~ 2 0 6 0 % ) a n d the gas yield increases in all cases;
(3) in general, ZnCI2 in high c o n c e n t r a t i o n increases the
gas yield (by 170%) a n d reduces the liquid yield (by
59%);

(4) the reduction in liquid yield is greater at higher salt

concentration, except in the case of rice husk impregnated with ZnC12.
T o ensure t h a t the influence on pyrolysis p r o d u c t
d i s t r i b u t i o n was due to the c a t i o n (zinc o r p o t a s s i u m )
a n d n o t to the a n i o n ( c h l o r i d e - - z i n c c h l o r i d e forms a n
acid solution16), e x p e r i m e n t s wee c o n d u c t e d with acids o a k e d samples o f coir pith, g r o u n d n u t shell a n d rice
husk, at two c o n c e n t r a t i o n s . O n l y m a r g i n a l changes in
yields o f volatiles a n d c h a r were p r o d u c e d . It is relevant
to state here t h a t neither salt d e c o m p o s e s o r e v a p o r a t e s
below 923 K 17, so the weight losses o b s e r v e d are p u r e l y
due to b i o m a s s d e c o m p o s i t i o n .
E x p e r i m e n t s were also c o n d u c t e d with K z C O 3 a n d
ZnCO3, a g a i n to e m p h a s i z e the role o f the c a t i o n r a t h e r
t h a n the a n i o n in pyrolysis. T h e results o b t a i n e d are
p r e s e n t e d in Table 9. A s can be seen, the t r e n d is the same
for b o t h chloride a n d c a r b o n a t e salts. T h e changes in
volatiles a n d c h a r yields are similar. These results suggest
that the effect o f salt i m p r e g n a t i o n is m a i n l y due to the
c a t i o n loading.

1820

Fuel 1995 Volume 74 Number 12

X-ray diffraction studies. U n t r e a t e d a n d d e m i n e r a lized b i o m a s s a n d c h a r were e x a m i n e d by X R D . The

crystalline fraction o f cellulose expressed as the crystallinity index (CrI) was c a l c u l a t e d b a s e d on the m e t h o d
suggested by Segal et al. 18 a n d L o e b a n d Sega119. Table
10 shows the crystallinity index for b o t h u n t r e a t e d a n d
d e m i n e r a l i z e d biomass.
It can be seen t h a t the crystallinity o f rice husk, coir
pith a n d g r o u n d n u t shell increased on d e m i n e r a l i z a t i o n .
W e i n s t e i n a n d B r o i d o z a n d B r o i d o a n d W e i n s t e i n 21
suggested t h a t the c h a r - f o r m i n g pyrolysis reactions in
cellulose occur preferentially in m o r e crystalline regions
t h a n in a m o r p h o u s regions. T h e inter-ring cross-linking
enhances c h a r f o r m a t i o n , a n d this occurs preferentially
in the m o r e o r d e r e d crystalline region. The r e p o r t e d
increase in c h a r yield has been in the region o f 3 - 5 % .
H o w e v e r , the increase in c h a r on d e m i n e r a l i z a t i o n
c a n n o t be a t t r i b u t e d solely to this increase in crystallinity
w i t h o u t m o r e detailed analysis.
Properties of the products
Adsorptive properties of char.

The iodine a d s o r p t i o n
test was c a r r i e d o u t using the s t a n d a r d p r o c e d u r e 22
for the c h a r s f r o m u n t r e a t e d , d e m i n e r a l i z e d a n d salti m p r e g n a t e d biomass. T h e results are presented in Table
11, f r o m which it can be seen t h a t on d e m i n e r a l i z a t i o n ,

Influence of mineral matter on biomass pyrolysis: K. Raveendran et al.

iodine adsorption by the char increases in most instances,

the greatest increases being obtained with corn cob and
groundnut shell.
The BET measurements show an increase in surface
area on demineralization. It is interesting to note that the
increase in surface area is similar (~30%) in almost all
instances. Demineralized coir pith char has the highest
surface area, followed by demineralized corn cob and
groundnut shell. Wood shows very low iodine adsorption and BET surface area.
It is well established that pores are developed during
pyrolysis23-26, depending on the amount of volatiles
released and the rate of their evolution for a given
biomass. On the other hand, it is also known that the
volatiles released undergo condensation reactions, forming deposits on the pores or pore mouths developed.
As observed earlier (Table 5), the amount of volatiles
released and their rate of evolution increase on demineralization. An increase in rate reduces the residence time
of the volatile matter in the pores, consequently reducing
condensation in the pores. This explains the increases in
both char adsorptivity and liquids yield. These results are
of importance for obtaining a high char yield and a high
active surface area for activated carbon manufacture.

Heating value. The heating values of the chars and

liquids were measured and that of the gases was obtained
by difference. Table 12 presents the results. As can be
seen, the higher heating value of biomass on the dry
ash-free basis is similar for coir pith, groundnut shell,
rice husk and wood. However, the heating values of
the products are different for different types of biomass.
The heating value of the char increases marginally on
demineralization, except for corn cob. The heating value
of the liquids increases in all cases through demineralization, consequently reducing the heating value of the
gases in almost all cases. The distribution of energy in
the products is shown in Table 13. More of the energy
is transferred to the liquid fraction, except for coir pith,
which has more energy in the char. These results indicate
that coir pith could be a potential raw material for char
(or activated carbon) manufacture. For liquefaction,
corn cob, groundnut shell and rice husk may be preferred
to wood, but wood is a good feedstock for gasification.
These data are also of importance in selection of a
product for supplying heat for the pyrolysis process itself.
Elemental composition. Elemental analyses were carried out on the chars and liquids from the untreated and
demineralized biomass. The elemental composition of
the gases was calculated based on the gas yield. The
results are presented in Table 14.
The increase in the hydrogen content in gases for
demineralized rice husk is almost 50% and the highest.
The basic composition of the liquids is very similar to
that of the original biomass. This is true for both
untreated and demineralized material, in accordance
with reports in the literature 27'z8. For groundnut shell
and rice husk the O/H ratio increases on demineralization, whereas it decreases for wood and coir pith.

present in biomass fuels; cobalt, chromium, copper,

manganese, nickel, sulfur and zinc are present in smaller
amounts.
The yield of volatiles, the devolatilization rate and the
initial decomposition temperature increase on demineralization for most of the kinds of biomass tested; rice
husk, groundnut shell and coir pith are exceptions. The
difference in behaviour of these three materials is
attributed to their high potassium (and/or zinc) content
in combination with a high lignin content. A correlation
has been developed to express this effect. In other words,
the mineral matter of biomass, in combination with the
organic composition, plays a major role in determining
pyrolysis product distribution and product properties.
ACKNOWLEDGEMENTS
The authors wish to thank Professor Wolfgang Klose,
FG Thermodynamik, Kassel University, Germany, for
useful discussions and valuable suggestions. They also
thank Mr N. Ganasekaran and Mr A. Sundaresan,
research scholars in the Chemistry Department, for their
help in obtaining the XRD patterns and Miss Bakul Rao,
operator, RISC, liT Bombay, for help in ICP-AES
analysis.

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CONCLUSIONS
Sodium, potassium, calcium, magnesium, iron, phosphorus, aluminium and silicon are the major elements

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