Indi an Jou rnal of Chemical Technology
Vol. 8, March 200 I, pp. 149-152
Note
Effect of heating rate on the char yield and
pore structure of chars prepared from viscose
rayon cloth
K Kumar, R K Saxena & A K Sarkar*
Material Characterisation Division, National Physical Laboratory,
Dr K.S. Kri shnan Road, New Delhi I 10012, Indi a
Received 24 Ma rch 1999; accepted 1 December 2000
Characteristics of the char prepared from viscose rayon cloth
has been studied. Effect of heatin g rate in different tempe rature
zones has been investi gated. Rate of weight loss of the pretreated
viscose rayon cloth varies with time throughout the temperature
zone.
An attractive means for converting an organic
substance into its char, is the pyrolysis process which
involves the heating of the material under inert
atmosphere. The heating rate during the pyrolysis
process greatly influences the char yield and textural
properties of char'- 3 . Brunner and Roberts' carbonized
powdered cellulose at different heat treatment
temperatures with different heating rates ranging from
0.03 -70°C/min. The heating rate was kept constant
(slow or fast) throughout the temperature range. It
was found that for a fixed max imum heat treatment
temperature (MHTT), the char yield and micropore
volume increase at slower heating rates. Marcilla et
al. 2 activated the chars obtained by the carbonization
of sub-bituminous coal at different heating rates. They
observed that the chars, prepared with slow heating
rates showed an increased value of BET surface area
than those produced at high heating rates on
subsequent activation.
In the present study the effect of heating rate, in
different temperature zones, on characteristics of the
char prepared from pretreated viscose rayon cloth, has
been investigated. These studies show some
interesting results, contrary to expectations. These are
discussed in the following sections.
Experimental Procedure
Thermogravimetric analysis was conducted in
order to locate the most sensitive temperature range
*Forcorrespondance
which affects the degradation (weight loss) during
pyrolysis of viscose rayon cloth. Thermogram of
phosphoric acid pretreated viscose rayon cloth was
taken up to 800°C under nitrogen flow of 5 cc/min. A
constant heating rate of 10°C/min was maintained
throughout the experiment on 10 mg of the sample.
Rigaku-8150 TG-DT instrument was used for thi s
experiment and the thermogram is shown in Fig. 1.
From Fig. 1 it is seen that the rate of weight loss of
the pretreated viscose rayon cloth varies with time
throughout the temperature range. Maximum weight
loss occurs in the temperature range of 330-350°C. As
the samples showed different weight losses in different
temperature ranges, the authors were motivated to
investigate the effect of heating rate in the different
temperature zones. The pyrolysis of cellulose may be
divided into two stages: first, the degradation and
decomposition below 400°C and second, the
repolymerisation above 400°C. On account of this view
together with T.G.A. results, the entire temperature
range was divided into two zones-1st zone, from room
temperature to 450°C and lind zone, from 450 to
850°C. In order to detect significant changes in the
char yields, a minimum heating rate of 2°C/min and a
maximum heating rate of 14°C/min were chosen.
Viscose rayon cloth was pretreated with a 4% (vlv)
solution of phosphoric acid prior to heat treatment.
Conditions of sample preparation are summarised in
Table 1 alongwith char yield, BET surface area and
micropore volume. Most of the samples have been
prepared under nitrogen atmosphere. A few samples
were also prepared under carbon dioxide atmosphere
for comparison. Samples A and B were prepared at a
MHTT of 450°C with constant heating rates of 2 and
14°C/min respectively. In the case of samples C and
D the MHTT was increased from 450°C to 850°C
with same heating rates in order to observe the effect
of heating rate in the lind zone (450-850°C). Samples
E and F were prepared by using different heating rates
in the two zones. For sample E the heating rates were
kept as 2 and l4°C/min in zones 1st and lind
respectively while in the case of sample F, the
corresponding heating rates in the zones Ist and lind,
were kept as 14 and 2°C/min. Samples G and H were
prepared under carbon dioxide atmosphere up to a
150 INDIAN J. CHEM . TECHNOL., MARCH 2001

MHIT of 850°C with constant heating rates of 2 and constant heating rate of 2 and 14°C/min respectively .
l4°C/min respectively. Fig. 2 shows the adsorption- Although the heating rates of sample C and D differ
desorption isotherms of nitrogen at 77K for samples C significantly, their yields of char are the same
and F. Isotherms of samples D and E could not be (Table 1). These results appear to be contrary to those
obtained due to very long equilibrium time. Samples obtained by Brunner and Roberts 1, that is the char
A and B were prepared only to have an idea about the yield should be higher at slower heating. If one looks
char yield at 450°C and were not subjected to at the values of yield of char obtained separately
adsorption measurements. during two temperature ranges i.e. from room
temperature to 450°C and from 450 to 850°C one
Samples-C and D finds a proper explanation. Char yields of samples A
Samples C and D have been prepared under and B can be looked upon as the yields of samples C
nitrogen atmosphere at a MHIT of 850°C with a and D at an intermediate stage up to 450°C. Thus the
char yields of samples C and D at 450°C can be
( mgl TG -DTA (m icro• )
10 r - - - - , - - - - . - - -....15:-;
.3.,23"'%...--- . . . - - - - , 200
considered as 41.3 and 39.3 % respectively. These
329 .4
values of char yield for samples C and D follow the
352.5
observation of Brunner and Roberts. When the MHIT
of sample C is increased from 450 to 850°C (zone
lind) with a heating rate of 2°C/min, the char yield
0 0
decreases from 41.3 % to 30.8 %. The decrease in
98.3 char yield is 10.5%. In the case of sample D char
yield decreases from 39.3 % to 30.8 % with a
decrease of 8.5%, when the MHTT was increased
from 450 to 850°C with a heating rate of 14°C/min. It
- I 0 .____ __,__ ___.__ _....L....__ _,__--..1._ __, -20()
0 100 200 300 400 500 600 is clear that in lind zone faster heating (14°C/min)
RIGAKU8150
Temp~ro ture ('C) results in the decrease of char yield by a Jesser
amount. It is this observation which is actually
Fig. 1-Thermogram of phosphoric acid pretreated viscose rayon
cloth under nitrogen flow . contrary to the finding of Brunner and Roberts 1•

0
c
:J
0
E
<!

0 .1 0.2 0.3 0.4 0.5 0.6

Fig. 2-Adsorption-desorption isotherms of nitrogen at 77K for samples C and F. (open symbols-adsorption, closed symbols-desorption)
 NOTE 151

In order to explain the char yields of samples C and
D, a mechanism has been proposed which is
somewhat different from the one proposed by Brunner
and Roberts', in lind temperature zone (450-850°C).
Brunner and Roberts considered the effect of constant
rate of heating throughout the temperature range and
reported the overall effect of rate of heating on the
yield of char whereas in the present study the
contributions of heating rates on the yield of char in
the two distinct temperature zones have been
investigated. In the opinion of the author the effect of
heating rate on the pyrolysis of viscose rayon cloth
changes with temperature in a particular temperature
range investigated. In the temperature range of 450-
8500C (zone II) the effect of heating rate seems to be
opposite to the effect observed by Brunner and
Roberts possibly due to two reasons.
One reason for this behaviour may be that in the
case of sample C (2°C/min) the volatile products
produced per unit time are less than those produced in
the case of sample D (14°C/min). The total time
required for the pyrolysis of sample C, in lind
temperature zone, is more than that for sample D
because of difference in the heating rates. As the rate
of gas flow during pyrolysis has been kept identical
for both the samples, the complete removal of
volatiles might take place in the case of sample C
where as this removal may be partial in case of
sample D, leading to the partial deposition of volatiles
on the char surface, thereby increasing its yield of
char. The restricted entry for nitrogen molecules in
the case of sample D (Table 1) may be a consequence
of the deposition of volatile products on the pore
entrances. The complete removal of volatiles in the
case of sample C makes its pores accessible for
nitrogen adsorption. Moreover the lower value of DR-
micropore volume (COr273K) for sample D
compared to that for sample C (Table 1), may also be
due to the partial deposition of volatiles leading to
blockage of some pores/pore entrances.
Another reason for the discrepancy in the effect of
heating rate in the lind temperature zone (450-850°C)
may be that the complete degradation of a material
requires sufficient time. In the case of sample C, when
heated slowly (2°C/min) from 450 to 850°C, complete
degradation occurs leading to a greater weight loss. A
higher heating rate (l4°C/min) in case of sample D
may result in 'skipping' over the degradation stage in
the temperature range of 450-850°C. In other words,
due to faster rate of heating sample D could not
degrade completely leading to a lesser decrease in the
yield of char.
From the values of char yields obtained in
experimental conditions, it is conclude that the effect
of heating rate seems to be different in different
temperature zones. At lower temperatures below
450°C the slow heating increases the yield of char
while at higher temperatures (above 450°C) the yield
of char decreases at slow heating rates. Faster heating
is accompanied by an increase in char yield at higher
temperatures while at lower temperatures faster
heating decreases the yield of char.
Samples-E and F
The yields of char of samples E and F follows the
mechanism proposed for the samples C and D. In the
case of sample E heating rates in both the temperature
zones (lower rate of heating upto 450°C and higher
rate of heating above 450°C) tends to increase the
yield of char while in the case of sample F both the
heating rates (higher upto 450°C and lower above
450°C) decrease the char yield. Therefore the yield of

Table !-Conditions of sample preparation, char yield, BET surface area (S8 ET). and DR-micropore volume of the samples prepared
Sample Code Heating rate (0 C) Atmosphere Char yield SsET DR-micropore volume (c.c./g)
1st zone lind zone during pyrolysis (%) (N 2-77K) m2g· 1 N2-77K C0 2-273K
(R.T. to (450 to
450°C) 850°C)
A 2 N2 41.3
B 14 N2 39 .. 3
c 2 2 N2 30.8 757 0.30 0.31
D 14 14 N2 30.8 * * 0.26
E 2 14 N2 33.2 * * 0.27
F 14 2 N2 29.3 705 0.28 0.31
G 2 2 C02 27.3 912 0.35 0.35
H 14 14 C02 30. 1 642 0.26 0.28
*The parameter could not be calculated due to restricted entry to nitrogen molecules.
152 INDIAN J. CHEM. TECHNOL., MARCH 2001

Table 2-Char yie lds of the samples prepared at different
MHTT's, having other processing conditions same
Sample MHTT Atmosphere Char Yield(%)
No. (OC) Soaking Soaking
time
30 min 60 min
800 N2 29.1
2 750 N2 33 .2
3 700 N2 34.1
4 650 N2 37.5
5 600 N2 37.8
char for sample E is higher than that for sample F
(Table 1). The restricted entry to nitrogen molecules
and lower value of micropore volume (C0 2-273K) for
sample E as compared to those for sample F can be
explained in the same manner as explained in the case
of samples C and D.
Table 1 shows that the heating scheme has a
significant effect on the pore structure of the chars.
Under the experimental conditions of preparation of
samples C and F, the entrances of the pores are
accessib le for both the nitrogen and carbon dioxide
molecules. In the case of samples D and E, the
conditions of preparation are such that the nitrogen
molecules at liquid nitrogen temperature find it
difficult to enter the pore system (evident from the
very long equilibration time) while carbon dioxide
molecules at 273K can be easily adsorbed. These
results indicate that by selecting a suitable heating
scheme, it is possible to obtain the chars with
molecular sieve properties.
Samples-G and H
Samples G and H have bee n prepared under carbon
dioxide atmosphere upto a MHTT of 850°C with a
constant heating rate of 2 and 14°C/min respectively.
The char yield of sample H, prepared at high heating
rate, is higher than that of sample G, prepared at slow
heating rate. This result seems to be contrary to the
result obtained by Brunner and Roberts' who
pyrolysed powdered cellulose under nitrogen
atmosphere. Nitrogen being an inert gas does not react
with the char. In the present study the carbon dioxide
being reactive gas reacts with the char, thus reduces
the yield. The values of char yield for the samples
time given in Table 2 indicates that the reaction of C0 2
with the char begins at about 650°C. The total time
27.3 taken from 650 to 850°C is longer in the case of
32.0 sample G as compared to that for the sample H,
32.9
because of the difference in heating rates. As the
37.0
37.9 atmosphere is reactive and the time of reaction is
rather long, more char is gasified ir. the case of
sample G as compared to that of sample H, leading to
a lower value of the yield of char for sample G.
Consequently the values of BET surface area and
micropore volume for sample G are higher as
compared to those of sample H, as shown in Table 1.
Suitability of nitrogen and carbon dioxide
adsorption for the characterisation of the pore
structure
Table 1 shows that the values of DR-micropore
volume (C0 2-273K) for all the samples are some what
higher than those calculated from nitrogen adsorption
at 77K. Moreover the samples D and E which show
restricted entry towards nitrogen molecules, when
characterized by C0 2 adsorption at 273K, showed a
significant micropore volume. These results indicate
that the C02 adsorption is most suitable to
characterize the porosity of chars having molecular
size pores or narrow entrances to the pores. If
nitrogen adsorption does not occur significantly on a
particular char, one should not conclude that the char
is non porous. In such cases, the material must be
characterized by C0 2 adsorption at 273K to confirm
the pore structure.
References
I Brunner Paul H & Roberts Paul V, Carbon, 18 (1980) 217.
2 Marc illa A, Asensio M & Martin-Gullon I, Carbon, 34
(1996) 449.
3 Mahajan 0 P & Walker P L, Analytical Meth ods for Coal
and Coal Products, Vol II, edited by Karr C Jr (Academic
Press, New York), 1978, 465.