Rheological behaviour of coal-solvent

slurries

Atsushi Tsutsumi and Kunio Yoshida

Department of Chemical Engineering, University of Tokyo, Bunkyo-ku, Tokyo 113, Japan
(Received 7 October 7985; revised 27 January 7986)

Viscosity and density of coal-recycle solvent slurries for a wide range of shear rates have been measured at
temperatures between 373 and 653 K, at high pressures. The results indicated that solvent-induced swelling
produces an increase in the viscosity of the slurries before extensive coal extraction takes place, and that
agglomeration, due both to bridge formation by colloidal materials and interparticle re-linkage occurring
above 523 K, leads to an increase in viscosity and non-Newtonian behaviour.

(Keywords: rheological properties; coal; slurry)

A knowledge of physical properties, such as the viscosity, pressures. The system consists essentially of a 190ml
density and thermal conductivity of slurries of coal and autoclave, a slurry pump, a preheater, interchangeable
various solvents under process conditions, is essential for capillary tubes, and a differential pressure transducer for
good equipment design for coal liquefaction processes. measuring the pressure drop across the capillary. The
For example, viscosity data are very important because pressure vessel was fitted with a magnetic stirrer which
they are used in the calculation of the pressure drop, heat- maintained the coal-solvent mixture in suspension. The
transfer rate, holdup and flow-pattern. On heating, coal slurry pump had a stainless steel barrel, the bottom of
dissolution and chemical reactions occur resulting in which has been connected to a pipeline.
significant changes in the properties of slurries. There is, Slurries flowing out of the barrel were pushed through
however, little information available on the rheological the preheater and the capillary tube at preselected
properties of coal-solvent slurries, particularly at high constant rates by a plunger which was connected with a
temperatures and pressures. pulse motor through a ball screw. Apparent shear rates
Droege et al. measured viscosities of coal-solvent could be varied from 54.2 to 1084 s-l by the changing
slurries at high temperatures and pressures using a pulse rate with a programmablecontroller. Two taps were
reciprocating concentric-cylinder viscometer and applied connected with the capillary tube at each end for
the Bingham plastic model to analyse the data. They measuring the pressure drop by means of a differential
observed that thickening occurring at 500-550 K causes pressure transducer. The flow behaviour of all samples
high plastic viscosities and high yield stresses. Thurgood was investigated using a capillary, 3.09 mm diam. and
et ~1.~ used a capillary-tube viscometer to study 604 mm length. The internal diameter of the capillary was
rheological properties of coal-solvent slurries under calculated from measurement of the external diameter,
process conditions and reported that the slurry gradually length and density of stainless steel. The autoclave was
becomes pseudoplastic as the temperature is increased surrounded by an electric furnace and the slurry was kept
from 400 to 700 K. Okutani et ~1.~ investigated the at the constant temperature by thermostatic control. Two
viscosity of coal paste using a rotational viscometer and chromel-alumel thermocouples inserted into both ends of
found a peak in the viscosity near 573 K for high-rank the capillary tube accurately indicated the inlet and outlet
bituminous coal slurries. Summarizing some data on slurry temperatures.
viscosity measured at several pilot plants Shah4 stated Slurries were loaded in the autoclave and heated to a
that both swelling and agglomeration cause an increase in designated temperature with stirring. The pressure within
viscosity and non-Newtonian pseudoplastic behaviour. the autoclave was raised to 7.5 MPa with nitrogen. The
The object of this paper is to present the rheological slurry was moved from the autoclave to the barrel of the
data for slurries of coal and recycle solvent obtained from slurry pump by opening a coupling valve and pulling the
a liquefaction plant, and to explain the effect of plunger. After opening valve (2) and shutting valve (l), the
temperature and the type of coal on flow behaviour. The slurry was mechanically driven through the capillary by
viscosity changes with temperature were attributed to the the plunger at a constant rate, and returned to the
structural change occurring in the coal suspensions. autoclave. The pressure drop across the capillary tube and
slurry temperatures at both the inlet and outlet were
EXPERIMENTAL recorded. This procedure was repeated at different slurry
flow rates, maintaining the same temperature. Other
Apparatus and procedure series of experimental runs were further conducted at
The experimental apparatus, shown in Figure 1, was other temperatures. The viscosity of the solvent was
designed to measure both rheological properties and measured in the same way using a 0.766 mm diam.
densities ofcoalsolvent slurries at high temperatures and capillary.
00 16-2361/86/07090644$3.00
9 1986 Butterworth & Co. (Publishers) Ltd.
906 FUEL, 1986, Vol 65, July
 Rheological behaviour of coal-solvent slurries: A. Tsutsumi and K. Yoshida

of temperature on the rheological properties of slurries.

The relative viscosity of slurry is defined by the ratio of
apparent viscosity to solvent viscosity and depends on the
degree of agglomeration resulting from the dynamic
equilibrium caused by the hydrodynamic force and
particle-particle interactions. The hydrodynamic force is
proportional to the term (viscosity of solvent pO) x (shear
rate $). As the particle-particle interaction does not
depend on temperature, only one master curve can be
given at various temperatures by plotting the rheograms
between the shear stress t and pOj. This method can
determine the effect of temperature on particle-particle
interactions from the change in the solvent viscosity with
temperature. In the case of coal slurries the viscosity of the
liquid phase is subject to change due to the dissolution of
extractable materials, particularly at higher temperatures.
Nevertheless, some useful information can be obtained, as
Figure 1 Schematic diagram of the experimental system: 1 and 2, described below.
valves; 3, autoclave: 4. magnetic stirrer; 5, slurry pump; 6, preheater; 7,
capillary: 8, differential pressure transducer; 9, pulse motor; 10, pulse
motor driver; 11,controller; 12, sampling tap RESULTS
Viscosity of recycle solvent
The viscosity of recycle solvent was measured up to
Materials 623 K, as shown in Figure 2. The recycle solvent is
Two Japanese coals, Horonai and Taiheiyo, were used. Newtonian and the viscosity decreases exponentially with
They were crushed to 5-175 pm (average = 70 pm). temperature increase.
Analytical data are shown in Table 1. The solvent was
obtained from a 2.4 tonne day- direct coal 1iquefaFtion Density measurements
plant, operated under MITIs Sunshine project. The Figure 3 shows the density change with temperature for
recycle solvent was taken from a mixture of bottom oil the recycle solvent and two kinds of coal-solvent slurries,
and heavy oil in a distillation tower after a 380 h run5. The 33.3 wt% Horonai coal and 40 wt% Taiheiyo coal. The
concentrations of Horonai and Taiheiyo coal slurries density decreases as the temperature increases for all
were 33.3 and 40 wt%, respectively. The different slurry cases.
concentrations for the two coals allowed a comparison of
the rheological behaviour in the same viscosity range. Rheological behaviour of slyrries
The rheograms of r against pO$ at various temperatures
Analysis for two kinds of slurries are shown in Figures 4 and 5.
For fully developing flow in a capillary tube the wall Figure 6 shows the effect of temperature on the apparent
shear stress 5 is given by: viscosity for these coal-solvent slurries; the viscosity of
Horonai-coal slurries was found to increase rapidly above
r = DAP /4L (1)
423 K. In the region between 473 and 523 K only a single
where: D= the diameter and L= the length of the master curve was obtained between t and ,+j (Figure 4),
capillary tube; and AP= the pressure drop across the indicating that the rheological property remains
capillary. unchanged in this region.
Assuming that no slippage occurs on the walls, the true It may be suggested that there was no variation in
wall shear rate $ is given by6.: interactive forces between the coal particles, and also no
physical changes such as swelling and expansion in this
(2) region. Furthermore, the viscosity of the liquid phase was
found to be the same as that of the solvent, i.e. extensive
where: V= the mean velocity of slurry; and n= the slope coal extraction which produces an increase in the
of the relationship between log z and log 8V/D. It is not viscosity of the liquid phase did not occur below 523 K.
necessary to give one unique value of II in a wide range of
apparent shear rates 81//D unless the power-law model is Table 1 Analyses of coals
applied a priori. Coal Horonai Taiheiyo
When the pressure taps joined to the capillary tube are
filled at each end with toluene, the differential pressure Proximate analysis (wt%)
transducer indicates the head difference AP between the Moisture (as received) 2.9 2.3
Volatile matter (dry) 47.5 46.6
slurry and flowing toluene. Hence, the density of slurry p
Fixed carbon (dry) 45.2 37.5
is given by Ash (dry) 7.3 15.9
Ultimate analysis (wt?;, daf)
p=pt+~ (3) Carbon 80.9 77.5
CJL Hydrogen 6.3 6.9
where: 9 =gravity; and y, = the density of toluene. Nitrogen 1.4 1.0
Sulphur 0.4 0.3
The authors previously proposed the shear rate- Oxygen 10.9 14.3
temperature superposition method to elucidate the effect

FUEL, 1986, Vol 65, July 907

 Rheological behaviour of coal-solvent slurries: A. Tsutsumi and K. Yoshida

coal slurries above 423 K and the superposition of

rheograms of r against ,uo$ in the temperature range 4733
523 K. These results indicate that the rheological
behaviour of Taiheiyo-coal slurry is similar to that of
Horonai-coal slurry except that the degree of increase in
viscosity is different. The real increase in slurry viscosity
might be hidden by the decrease of solvent viscosity with
temperature.
The viscosities above 523 K were found to be
dependent on time. This dependence turned to time-
thinning from time-thickening at the peak ofviscosity and
became stronger at higher temperatures.

DISCUSSION
When the temperature rises above 523 K, the mobile
phase content increases and molecular fragments
detached from the macromolecular coal network are
progressively dispersed into solvent*. Although much
1O'L
1

lo'=
1.5 2.0 2.5 30
l/T (@K-')
Figure 2 Viscosity of recycle solvent measured r?
0 373K
E
0 423K
z
A 473K
P A 523 K
T
1O0r q 553 K
W
n 573 K
V 623 K

7
E lOOO-

,
Figure 4 Rheograms for 33.3 wt% Horonai coal-solvent slurries. n 1,
x
r after 0 h; W2, after 0.5 h; vl, after 0 h; 772, after 3 h
2
$ 900-
1
o 373K
l 423K R
A 473K
A 523K
800- 0 553K
n 593K
v 623K
v 653K

300 400 500 600 70

Temperature (K)
Figure 3 Density of solvent and slurries measured. A, Recycle solvent;
0, 33.3 wt% Horonai coal-solvent slurry; 0, 40 wt% Taiheiyo coal-
solvent slurry

It was found that above 523 K the slurry became non-

Newtonian and the viscosity increased with temperature
to reach a maximum at 573 K and subsequently
decreased. However, the viscosity of Taiheiyocoal t
10.'I I I1111111 I II111111 I I ,,,,I,

slurries did not increase between 423 and 473 K, and there 10-2 10-l loo 1(
was no viscosity peak at about 573 K. However, Figure 5 po?(N.rn-')
shows an increase in the relatively viscosity of Taiheiyo- Figure 5 Rheograms for 40 wt% Taiheiyo coal-solvent slurries

908 FUEL, 1986, Vol 65, July

 Rheological behaviour of coal-solvent slurries: A. Tsutsumi and K. Yoshida

473 K the solvent-induced swelling was already

completed. In addition, this result also indicates that no
extensive coal extraction occurs below 523 K, because the
viscosity of the solvent and the liquid phase is similar.
In hydrogenolysis, Taiheiyo coal gives higher yields of
oil, gas and water but lower yields of asphaltenei4 than
Horonai coal. The liquid products obtained from
Taiheiyo coal contain a high percentage of low boiling
point fraction, while Horonai coal produces more heavy
liquids. So, Taiheiyo coal is considered to consist of
structural units having low molecular weight. These
facts suggest that Taiheiyo coal contains few extractable
and colloidal materials with highmolecular weight, giving
rise to the difference in rheological properties between
Taiheiyo and Horonai coal slurries.

CONCLUSIONS
It was found that the viscosity of Horonai coal-recycle
solvent slurries increased initially with temperature and
caused gelation above 523 K, leading to non-Newtonian
behaviour and a peak in the viscosity at z 573 K. The
300 400 500 600 700
viscosity of Taiheiyo-coal slurry was not found to increase
Temperature (K 1
between 423 and 473 K. However, by plotting the relation
Figure 6 Variation of apparent viscosity with temperature
(i = 542 s )_A, Recycle solvent; O,O, 33.3 wtp(, Horonai coal-solvent between T and poj, it was found that the slurries of both
slurry; 0. n . 40 wt% Taiheiyo coal-solvent slurry. Open and solid coals have very similar rheograms. It was considered that
symbols show heating and cooling process. respectively the increase in viscosity between 423 and 473 K is
attributable to solvent-induced swelling while above
of the coal extract forms a true solution, some may 523 K it is due to the agglomeration of coal particles by
aggregate to form high molecular weight colloidal liquid bridging with colloidal materials produced or by
material. interaction of mobile units on the surface of coal particles.
Agglomerates of coal particles are considered to be
formed by bridging of colloidal materials produced or
ACKNOWLEDGEMENT
by interparticle re-linkage between mobile units due to
hydrogen bonding and van der Waals forces. As the The authors wish to thank the New Energy Development
solvent is trapped in agglomerates this reduces the Organization (NEDO) for the kind supply of recycle
effective volume concentration and the apparent viscosity solvent used in this study.
of the slurry increases. The increase of viscosity above
523 K (Figure 6) can probably be attributed to this
phenomenon. The reason that the slurry behaves in anon- REFERENCES
Newtonian way above 523 K, as shown in Figures 4 and 5, 1 Droege, J. W., Stickford, G. H., Longanbach, J. R., Venkateswar,
is similarly explained because the coagulated suspensions R. and Cauhan, S. P. Thermophysical Properties of Coal
are of a non-Newtonian nature12,13. The rate of Liquids, Final Report. submitted to US Department of Energy
under Contract No. DE-AC22-79ET14941. 1982
coagulation, however, is considered to be very slow,
Thorgood, J. R., Hanks, R. W., Oswald, G. E. and Youngblood,
because the collision probability among coal particles E. L. AIChE. J. 1982, 28, 111
should be small in the viscous flow. The thickening of Okutani, T., Yokoyama, S. and Maekawa, Y. Fuel 1984,63, 164
slurry with time between 523 K and the temperature at Shah, Y. T. Reaction Engineering in Direct Coal Liquefaction,
viscosity peak presumably depends on this slow rate of Addison-Wesley Pub. Co., USA,-1981
5 Sakai. N. Direct Coal Liauefaction Process: 2.4t/d PDU
coagulation. Operation, PETC-NED0 Joint Technical Meeting, 11-13
Above 573 K colloidal materials forming the liquid December 1984
bridge between coal particles tend to decompose and 6 Mooney, M. J. Rheol. 1931, 2, 210
disperse into the solvent as its solubility is increased. 7 Robinowitsch, B. Z. Phys. Chem. 1929, I, 145A
8 Tsutsumi, A. and Yoshida, K. J. Non-Newtonian Fluid
Hence, it is reasonable to consider that the structure of
Mechanics, submitted for publication
aggregates is progressively broken, so that the viscosity of 9 Barton, W. A., Lunch, L. J. and Webster, D. S. Fuel 1984,63,1262
slurry decreases rapidly. 10 Jurkiewicz, A., Marzec, A. and Pislewski, N. Fuel 1982,61, 647
Above 623 K, coal particles disintegrate and disperse 11 Kao,S. V., Nielsen, L. E. and Hil1,C. T.J. Co/l. InretfbceSci. 1975,
into thesolvent due to thecleavage ofcovalent bonds. The 53, 367
I2 Michaels, A. S. and Bolger, J. C. Ind. Eng. Chem. Fundam. 1962, I,
solute has a high molecular weight at the initial stage, but 153
changes into lower weight material with the progress of 13 Firth, B. A. and Hunter, R. J. J. Coil. Inre$uce Sci. 1976,57, 248
depolymerization. Thus, the viscosity of the slurry 14 Yoshida, R., Maekawa, Y., Ishii, T. and Takeya, G. Nippon
decreases, showing time-thinning nature. Kaguku Kaishi (J. Chem. Sot. Japun Chem. Ind. Chem.) 1972, No.
10, 1885
The increase of relative viscosities observed between
15 Nagai, H. and Akama, A. Kogyo Kagaku Zusshi 1964,67, 1260,
423 and 473 K may be considered to result from solvent- 1266
induced swelling. The superposition of rheograms 16 Yoshida, R., Maekawa, Y. and Takeya, G. Nenr?;o Kyokaishi (J.
between 473 and 523 K (Figures 4 and 5) suggests that at Fuel sot. Japan) 1974, 53, 1011

FUEL, 1986, Vol 65, July 909