Carbonization behaviour of pitch in the

presence of inert material

Toshiyuki Obara, Tetsuro Yokono, Yuzo Sanada and Harry Marsh*

Faculty of Engineering, Hokkaido University, Sapporo 060, Japan
* Northern Carbon Research Laboratories, School of Chemistry, University of Newcastle
upon Tyne, Newcastle upon Tyne NE1 7RU UK
(Received 8 February 1984; revised 7 November 7984)

The influence of silica gel (< 45 pm) as an inert additive on the carbonization reactions of A240 pitch was
investigated by optical microscopy, measurements of transferable hydrogen, high-temperature e.s.r. and high-
temperature ‘H n.m.r. Additions of silica gel have the effect of reducing the size of the optical texture of
mesophase which appears in the early stages of carbonization. The higher the concentration of silica gel, the
smaller is the amount of transferable hydrogen. The spin concentration of pitch increases with increasing silica
gel content. Measured values of U,,,, using high-temperature ‘H n.m.r., suggest that the molecular motions
in the pitch become restricted on addition of silica gel. The effect of silica gel on the physical properties and
chemical reactivity of carbonizing pitch is discussed.

(Keywords: pitch carbonization; transferable hydrogen; ear.; n.m.r.; inerts; vkcosity)

It is recognized that the optical texture of mesophase
formed during the carbonization of petroleum and coal-
tar pitches is closely related to the structure and physical
properties of the resulting carbons1q2. The mesophase
texture depends on the chemical composition of the
parent material, heating conditions, presence of organic
or inorganic additives and pressure. Substances showing
catalytic effects in the formation of anisotropic carbons
from co-carbonization systems, such as aluminium
chloride, have been studied in detai13. The influence of
insoluble solid additives such as natural graphite’, mica’,
carbon felt4, carbon black5s6 and silica’ on formation of
mesophase has been investigated phenomenologically.
However, the effect of inert additives on the carbonization
reaction is still obscure chemically and physically.
The authors have previously reporteds*9 that hydrogen
transfer reactions in pitches and coals play an important
role in determining the size and shape of the optical
texture of mesophase during the early stages of carbon-
ization. The hydrogen transfer can be monitored by
determining the extent of formation of 9,10-dihydro-
anthracene (9,10-DHA) from anthracene as an acceptor.
It was suggested that pitches which form carbon with
larger units of optical texture exhibit pronounced
hydrogen donor ability. This Paper reports a study of the
effect of an inert additive on hydrogen transfer in the early
stages of carbonization of petroleum pitch and, using
high-temperature e.s.r. and ‘H n.m.r., of the carbonization
behaviour of pitch in the presence of inert material.
EXPERIMENTAL
Sample preparation and carbonization
The Ashland A240 petroleum pitch used had the
composition (wt%): C, 91.9; H, 5.4; S, 2.6; 0, 0.1 (by
difference); it was virtually ash-free. Silica gel (< 45 pm)
from Wakojunyaku was used as the inert additive. The
pitch was mixed with the silica gel by grinding in a mortar,
intheweightratios100:1,20:1,10:1,2:1and1:1.Samples
were carbonized under nitrogen in a vertical infrared
image furnace. The heating rates, soak temperatures and
soak times were 5 and 10K min-‘, 673 and 723 K and 0
and 30min, respectively. The solid residues were mounted
in resin, polished and examined by optical microscopy.
Determination of extent of hydrogen transfer
Anthracene and sample (anthracene-pitch weight ratio
1: 1) were mixed, sealed in a Pyrex glass tube and heated to
673 or 723 K. The CDCl,-soluble fraction of the products
was examined by ‘H n.m.r. using a Varian XL-200
200MHz spectrometer. The amount of hydrogen
transferred was evaluated from the peak intensity of the
9,10-protons (3.87 ppm) in 9,10-DHA sv9.
High-temperature e.s.r.
A specimen mounted in a 4mm diameter quartz tube
was inserted directly into a cavity preheated to 723K
under nitrogen. The e.s.r. spectra were measured using a
Varian E-109 spectrometer (microwave power 30dB,
scanning time 7.5 s) and converted to spin concentrations
using a Varian E-900 data system and programs.
High-temperature ‘H n.m.r.
A specimen in an 8mm diameter quartz tube was
inserted into the high-temperature probe and heated at
5K min-’ under nitrogen. Spectra were observed at
selected reaction temperatures using a Bruker SXP 4-100
pulsed FT spectrometer with an improved JEOL 3H
electromagnet, operating at 36.4 MHz, sweeping over
6 kHz”.

0016-2361/85/070995-04%3.00
0 1985 Butterworth & Co. (Publishers) Ltd FUEL, 1985, Vol 64, July 995
Carbonization behaviour of pitch: T. Obara et al.
RESULTS AND DISCUSSION 1O:l. This increase of spin concentration is correlated
with the reduction in transferable hydrogen at 723 K. The
Figure 1 shows optical micrographs of polished surfaces
observed free radical concentration depends on the
of carbonization products from A240 petroleum pitch
competing effects of free radical formation and
with and without additions of silica gel. The carbon-
quenching; the latter would depend on hydrogen transfer
ization product from pitch alone produced typically
and radical recombination. It is conceivable that addition
spherical units of mesophase, as shown in Figure la. With
of silica gel would reduce radical recombination in pitch
increasing silica gel content, the mesophase spheres
by acting as a diluent; the population of measured
became smaller: Figure lb-d. At a pitch-silica gel ratio of
radicals should consequently increase, but in fact it does
1: 1, an isotropic carbon was obtained at 723 K; in other
not.
words, the silica gel totally suppressed the formation and
Although silica gel is said to be catalytically inert for the
growth of mesophase. The presence of silica gel did not
hydrogenation of coal”, these results show that silica gel
affect the yield of carbon residue from the pitch, nor was
has an influence on hydrogen transfer and spin con-
sedimentation of the gel observed.
centration during pyrolysis. High-temperature ‘H n.m.r.
Figure2 shows the variation in the amount of H,,,
is an excellent technique for directly measuring changes in
formed in the pitch-silica gel system with the silica gel
molecular motion relating to fluidity of the system during
content. Here, H,,,A is the transferable hydrogen, defined
as the hydrogen transferred from pitch to anthracene
under the given carbonization conditions. HDH,,decreases
by a factor of up to two with increasing silica gel content*.
It has been shown”p9 that pitch which forms carbon with a
large optical texture possesses considerable amounts of
transferable hydrogen. The suppression of mesophase
growth shown in Figure I can then be associated with a
reduction in the amount of transferable hydrogen
(Figure 2). Transferable hydrogen could contribute to the
c
stabilization of radicals created during pyrolysis. The Y
addition of silica gel, by increasing the viscosity of the a
- l
'i
system, prevents convection within the fluid matrix and
yo.2 -
consequently restricts hydrogen transfer reactions in the
carbonization system. This results in a reduction in the
size of the mesophase spheres and eventually prevents the
formation of mesophase.
Recently, several in situ pyrolysis experiments with coal
in e.s.r. cavities have provided information on the free
radical chemistry of coal liquefaction”-14 and the
carbonization behaviour of model compounds’ 5 and
pitches16. Figure3 shows the change in spin con-
0
centration with reaction time at 723 K in A240 pitch alone
and the pitch-silica systems. It can be seen that the higher L I I I
0 10 30 50
the percentage of silica gel, the higher is the spin
Content of silica gel (wt%)
concentration in the pitch. The spin concentration in I I I I I
pitch at a weight ratio of 1: 1 was nearly the same as at 1OO:l 2O:l 1O:l 7:3 1 :l
Ratlo pitch I s111ca gel

* Approximately the same values of HDHA were obtained with ~425 as Figure 2 Transferable hydrogen (H DHA) in pitch as a function of silica
with ~45 pm silica gel at weight ratios of 1O:l and 1:l gel content. 0, 723 K, no soak; 0,673 K, no soak

Fiie 1 Photomicrographs ofmesophase texture in pitch with silica gel (HTT 723 K, 30min soak, 10 K mm -‘):(a)pitchalone; (b) pitchsilica(lOO:l);
(c) pitch-silica (2O:l); (d) pitch-silica (1O:l)

996 FUEL, 1985, Vol 64, July

 Carbonization behaviour of pitch: T. Obara et al.

carbonization”. The carbonization reaction of pitch can

also be monitored in terms of the increase in the hydrogen
aromaticity (fHa) in well-resolved, high-temperature ‘H
n.m.r. spectra lo . The temperature dependence of the
hydrogen aromaticity thus obtained for pitch-silica gel
systems is shown in Figure 4. Hydrogen aromaticity was
derived from the integral intensity ratio H,,/(H,, + H,,).
With increasing proportion of silica gel, the curve of fna
against temperature is displaced to the left and the
temperature of signal loss falls.
The viscosity of the system may be considered in terms
of the line widths of half height (AH1,2), which reflect the
viscosity”. The temperature dependence of AH,,, in
pitch alone and pitch-silica systems is shown in Figure 5.
For both H,, and H,,, AH,,, remains small over a wide
temperature range for A240 pitch but increases with
increasing silica gel content. The contribution of the
increase in radical concentration, as shown in Figure 3, to
the n.m.r. line width may be not as important as that of the
00
proton dipole+lipole interaction”. It is suggested that 473 573 673 773
the molecular motion in pitch is suppressed by the Temperature (K )
presence of silica gel.
The above results lead to the conclusion that the Figure 5 Temperature dependence of half-height width (AH, r2) of ‘H
presence of silica gel in the early stages of carbonization of n.m.r. signal: 0. pitch alone; A, pitch-silica (1O:l); 0. pitch-silica (1: 1)

pitch has an influence on transferable hydrogen, free

l l
radicals and also viscosity, resulting in a change in the
. A optical texture of the solid residue. The chemical reactivity
.
. A and physical properties of pitch may be affected by silica
A
0 gel’. It is possible that modification of the silica gel surface
. ’ A A 0 q may cause an alteration in the carbonization behaviour of
A 0
.
A 0
0
0
0 pitch.
A 0 0 00
00
0 0
00
0 0
ACKNOWLEDGEMENTS
The authors wish to thank Messrs S. Shimokawa and E.
Yamada for their assistance in utilizing the Bruker pulsed
FT n.m.r. spectrometer. The assistance of Miss B. A. Clow
in the preparation of the manuscript is acknowledged.
0 10 20 30 40 50 60
Time (mln)

Figure 3 Spin concentration (arbitrary units) as a function of time at REFERENCES

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998 FUEL, 1985, Vol 64, July