Fuel Processing Technology 90 (2009) 1047–1051

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Effect of pre-swelling of coal at mild temperatures on its hydro-liquefaction properties

Hengfu Shui a,⁎, Jianlong Liu a, Zhicai Wang a, Meixia Cao a, Xianyong Wei b
a
School of Chemistry & Chemical Engineering, Anhui Key laboratory of Coal Clean Conversion & Utilization, Anhui University of Technology, Ma'anshan 243002, Anhui Province, China
b
China University of Mining & Technology, Xuzhou 221008, Jiangsu Province, China

a r t i c l e i n f o a b s t r a c t

Article history: The effects of pre-swelling treatment of Shenhua coal at mild temperatures (less than 160 °C) on its hydro-
Received 8 August 2008 liquefaction properties were determined in this paper. It was found that with the increase of pre-swelling
Received in revised form 27 March 2009 temperature in tetralin (THN) up to 120 °C, the liquefaction conversions of swollen coals increased. However,
Accepted 30 March 2009
when N-methyl-2-pyrrolidinone (NMP) was used as swelling solvent, the liquefaction conversion decreased
with the increase of pre-swelling temperature. The liquefied product distributions were very much
Keywords:
dependent on the pre-swelling pretreatment conditions, and the mechanism was discussed. Based on the
Pre-swelling treatment
Mild temperature
results obtained, a new swelling-liquefaction combining technology (SLCT) was advanced, in which the
Liquefaction liquefaction conversion and oil + gas yield were enhanced.
Coal © 2009 Published by Elsevier B.V.

1. Introduction swelling solvents at room temperature enhanced coal porosity and

The cost-effective use of coal for transportation fuels in an
environment-friendly manner becomes more and more important
due to the rapid increases in crude oil price and oil consumption. Coal
liquefaction processes have been designed to achieve the desired
levels of dissolution and molecular weight reduction [1]. In order to
assuage coal liquefaction conditions and increase liquefaction con-
version and oil yield, thus increasing the utilization efficiency of coal, a
series of basic research about coal pre-treatment before liquefaction
has been carried out. Hydrothermal treatment is one of important pre-
treatment processes [2–7]. We [6,7] have reported that hydrothermal
treatment above 200 °C increases the hydrogen content of treated
coal, disrupts the weak covalent bond, and changes the distribution of
hydrogen bonding in the coal. The conversion of liquefaction and the
yield of extraction with a carbon disulfide/N-methyl-2-pyrrolidinone
(CS2/NMP) mixed solvent (1:1 by volume) at ambient temperature
were enhanced by hydrothermal treatment. Another effective pre-
treatment of coal is swelling in organic solvents [8,9]. Coals pre-
swollen with organic solvents at room temperature were liquefied
after removal of swelling solvents, and it was found that the pre-
swelling treatment improved coal conversion [10–16]. Hu et al. [8]
believed that pre-swelling of coal could facilitate internal hydrogen
self-donation reactions, thus suppressed initial regressive reactions
and enhanced reactivity of coal and increased coal liquefaction
conversion. Pinto et al. [9] found that pre-treatment of coal with
⁎ Corresponding author. Tel.: +86 5552311552; fax: +86 5552311822.
E-mail address: shhf@ahut.edu.cn (H. Shui).
thus facilitated catalyst activity. The yields of products obtained by
coal liquefaction were very much dependent on the type of swelling
solvents used.
Pre-swelling treatments really facilitate coal liquefaction. In our
previous work [17] it was found that pre-swelling treatments of coal in
three solvents, i.e. toluene, N-methyl-2-pyrrolidinone (NMP) and
tetralin (THN) at room temperature increased its liquefaction
conversion. Swelling ratio of coal is affected by temperature; therefore
pre-swelling of coal at mild temperature should affect its liquefaction
properties. However few works have been done to investigate
systematically the effect of pre-swelling at mild temperatures (less
than 160 °C) on coal liquefaction. In the present study, we examined
the effects of pre-swelling of coal at mild temperatures on its hydro-
liquefaction properties by pre-swelling of coal up to 160 °C in NMP and
THN before hydro-liquefaction, and a new swelling-liquefaction
combining technology (SLCT) was advanced. Our results show that
the SLCT has great advantages with higher liquefaction conversion and
oil + gas yield compared to the traditional single-stage liquefaction.
The pre-swelling temperature of the SLCT is less than 160 °C, which is
different from the multi-liquefaction reported before [18–21].
Priyanto et al. [20] reported that when the total reaction time was
fixed to 120 min, the oil yield of two-stage liquefaction at the best
conditions increased from 77% of single-stage liquefaction to 80%. The
first stage of the multi-stage liquefaction was carried out at higher
temperature of 360–390 °C, where pyrolysis of coal was taken place.
Inukai et al. [21] found that the two-stage liquefaction with in situ
preheat treatment at more than 250 °C gave higher yields of toluene
solubles and hexane solubles than the one-stage liquefaction without
in situ preheat treatment. However the effects of preheat treatment of

0378-3820/$ – see front matter © 2009 Published by Elsevier B.V.

doi:10.1016/j.fuproc.2009.03.022
1048 H. Shui et al. / Fuel Processing Technology 90 (2009) 1047–1051
coal at mild temperatures (less than 160 °C) on its liquefaction have
not been reported.
2. Experimental
2.1. Coal and solvents
Shenhua coal (a Chinese sub-bituminous coal) used in this study
was provided by Shenhua Group. The coal as received was ground to
particles of a size less than 100 μm, stored under nitrogen atmosphere
and dried under vacuum at 80 °C overnight before use. The ultimate
and proximate analyses of the coal are shown in Table 1. All solvents
used were commercial pure chemical reagents (Purity higher than
99.5%) and used as received without further purification.
2.2. Swelling and solubility measurements
The volumetric swelling ratios of coal at different temperatures
were measured in NMP, THN. 0.1 g of coal particles was placed in a
Pyrex tube (3 mm i.d.) and centrifuged for 5 min at 6000 rpm. The
height of the coal layer was measured as h0. About 0.6 mL solvent was
then added and mixed thoroughly using a spatula. The sample with
the solvent absorbed was set at a measurement temperature for 4 h,
then centrifuged again for 5 min at 6000 rpm and the height of the
coal layer was measured as h1. The swelling ratio (Q) at the
temperature was obtained as Q = h1/ho.
Solubilities of raw coal at different temperatures were measured.
About 1.5 g of coal sample and 45 ml of solvent (NMP or THN) were
charged into a centrifuge tube to be extracted for 5 min under
ultrasonic (38 kHz) irradiation at room temperature. The mixture was
set in an oil bath at a measurement temperature for 4 h, and then
filtered through a filter membrane (0.8 μm) after centrifugation for
50 min at 14000 rpm. The residue was washed with acetone for three
times, and dried in vacuum at 353 K overnight. The solubility was
determined from the weight of the residue.
2.3. Pre-swelling treatments
Pre-swelling treatments at different temperatures were carried out
in a centrifuge tube. About 20 g of coal sample with the swelling
solvent of a weight 3 times that of the coal sample were loaded into
the centrifuge tube, and mixed thoroughly, then set at a measurement
temperature for 4 h. After 4 h swelling at the temperature the
centrifuge tube was centrifuged for 30 min at 1500 rpm to obtain
centrifugate of the swollen coal. The swollen coals were used for
further hydro-liquefaction experiments.
2.4. Liquefaction and fractionation
Hydro-liquefaction operations were carried out in a 100 ml batch
autoclave reactor. In each run, about 20 g of swollen coal (20 g of raw
coal after pre-swelling treatment) and 40 ml tetralin with 1 g FeS
(catalyst, 200 mesh, chemical reagent) were charged into the reactor.
The autoclave was pressurized with hydrogen to 4.0 MPa at room
temperature, and heated to 400 °C (salt bath which had been set at
400 °C) with stirring. After 5 min to let the autoclave get to heat
Table 1
Ultimate and proximate analyses of Shenhua coal.
Sample Ultimate analysis wt.%, daf Proximate analysisb
(wt.%)
C H N S Oa Ad Vdaf Mad
Shenhua Coal 80.13 4.88 1.06 0.42 13.51 5.5 38.2 9.3
a
By difference.
b
Ad: ash content in dry base; Vdaf: volatile yield in dry and ash-free base; Mad:
moisture content in atmosphere dry base.
Fig. 1. Fractionation procedure of liquefaction mixture.
balance, the autoclave was soaked at 400 °C for 30 min, and cooled
rapidly to room temperature by cooling water. Considering the
remaining of solvent in the swollen coal, the weight of raw coal
before swelling was used as the liquefaction conversion calculation
basis in the case of swollen coal liquefaction.
In a SLCT run, 20 g of raw coal and 40 ml tetralin with 1 g FeS were
charged into the reactor with 4.0 MPa H2 pressure. The autoclave was
kept at 120 °C or 160 °C for 4 h without stirring. Then the autoclave
was quickly heated to 400 °C at stirring and maintained at 400 °C for
30 min.
The liquefaction mixture was separated by Soxlet solvent extrac-
tion with tetrahydrofuran (THF), toluene and n-hexane in turn. The n-
hexane insoluble but toluene soluble fraction and the toluene
insoluble but THF soluble fraction were defined as asphaltene (AS)
and preasphaltene (PS), respectively. The conversion of coal was
defined as the THF solubles calculated from the THF insoluble residue.
Considering the weight loss of the liquefaction product during
transferring from the autoclave, the gas and oil products were lumped
as one fraction. The yield of the oil + gas was calculated from the
difference between the conversion of coal and the total yields of AS
and PS so as to rule out the effect of swelling solvent existed in the
swollen coal on the yield of oil. The fractionation procedures in detail
were shown in Fig. 1. The liquefaction conversions and product yields
including the liquefaction of swollen coals were on a raw coal basis. All
the liquefaction yields presented in this paper were the average values
from two experimental runs, and the error in the liquefaction yields
between the two runs was within ±3%.
2.5. Characterization of the swollen coal
The raw coal and the dried swollen coals were characterized by IR
spectra using a PE-Spectrum One IR spectrometer at ambient
temperature. In the IR measurement, the sample was mixed with
KBr and the mixture was pressed into a pellet. In order to eliminate the
effect of remaining solvent, the swollen coal was washed with acetone
and vacuum dried before measurement. The element analysis was
carried out with an Elementar Vario EL III.
3. Results and discussion
3.1. Swelling and solubility of Shenhua raw coal at different temperatures
Swelling ratios of Shenhua coal in NMP and THN at different
temperatures are shown in Table 2. Swelling of coal is determined by
the balance of the elasticity of the cross-linked network and the
permeability of the solvent into the network. Swelling of coal in non-
polar solvent may display the cross-linking density of coal macro-
structure. Solvents which have greater affinity to coal molecules
 H. Shui et al. / Fuel Processing Technology 90 (2009) 1047–1051
Table 2
Swelling ratios of Shenhua coal in THN and NMP at different temperatures.
Solvent 40 °C 80 °C 120 °C
THN 1.36 1.45 1.69
NMP 2.10 2.38 2.41
normally give a greater permeability, resulting in a larger swelling
ratio [15]. Table 2 shows that the swelling ratio of Shenhua coal in
NMP is much higher than that in THN at the same temperature. This is
because NMP, a stronger polar solvent with greater affinity to coal
molecules, can disrupt the stronger non-covalent interactions in coal;
therefore it has greater permeability than the non-polar solvent THN.
Shenhua coal has higher oxygen content and therefore higher
hydroxyl groups compared to some other bituminous coals as
shown in Table 1. NMP can strongly interact with these oxygen
functional groups such as hydroxyl groups to form new hydrogen
bonding and break some stronger interactions originally present in
coal molecules, resulting in a larger swelling ratio for the coal. With
the temperature increasing the swelling ratios in the two solvents
have an increased tendency. This is consistent with Lucht's result [16]
because of the thermal disruption of some weaker non-covalent
interactions. However several works noted that the variation of coal
swelling with temperature was small or negligible [17,18]. It is very
interesting that the swelling ratio in THN gets to maximum of 1.69 at
120 °C, and then decreases to 1.56 at 160 °C as shown in Table 2. The
decrease of swelling ratio in non-polar solvent THN may suggest the
increase of cross-linking density of coal macromolecular structure.
The change of property of solvent may also be one of the reasons.
Some solubles may be extracted out of the coal and dissolve in the
solvent during the swelling operation, thus change the property of
swelling solvent especially at higher temperatures. Table 3 shows the
solubilities of Shenhua coal in the two swelling solvents at different
temperatures. With temperature increasing the solubilities of Shen-
hua coal in the two solvents increase. The amount of coal fractions
dissolving in a solvent depends on the type of solvent. The solubility of
Shenhua coal in NMP is higher than that in THN at the same
temperature as shown in Table 3. This is consistent with their swelling
ratio difference because of the stronger solvent of NMP. However, the
difference of the solubility between the two solvents decreases with
the increase of temperature. For example, the difference of the
solubility between the two solvents decreased from 5.3% at 40 °C to
1.4% at 160 °C. A large amount of lighter constituents extracted from
coal will cause further aggregation of the heavier constituents left in
the coal [19], resulting in the increase of the cross-linking density of
the coal macromolecular structure. The solubles dissolving in solvent
may also decrease the swelling ability of solvent. These may lead to
the decrease of swelling ratio of THN at higher temperature 160 °C.
However, when NMP is used as solvent, with the temperature increase
the permeability of NMP increases because of the decrease of viscosity
of solvent at higher temperature, thus the swelling ratios increase.
Although the viscosity of THN at higher temperature also decreases,
but this decrease has little effects on the penetrability of THN
compared to that of NMP because of the lower viscosity of THN at
room temperature.
Table 3
Solubility of Shenhua Coal in THN and NMP at different temperatures (wt.%).
Solvent 40 °C 80 °C 120 °C
THN 9.2 13.4 14.1
NMP 14.5 15.6 16.5
1049
160 °C
1.56
2.55
Fig. 2. Effect of pre-swelling treatments in THN at different temperatures on the
liquefaction conversion of Shenhua coal.
3.2. Effect of pre-swelling at mild temperatures on the liquefaction of coal
Shenhua coal was pre-swelling treated in NMP and THN firstly at
mild temperatures, and then the swollen coals with a small amount of
swelling solvent (after centrifugation) were liquefied. The results are
shown in Figs. 2 and 3. Fig. 2 shows that after pre-swelling treatment
in THN at room temperature, the liquefaction conversion of Shenhua
coal increases from 55.5% of raw coal to 59.0% of the swollen coal.
With the pre-swelling temperature increasing up to 120 °C, the
liquefaction conversions of the swollen coals increase, then decrease
with the further increasing of temperature to 160 °C. The maximal
conversion of 70.0% was obtained at 120 °C pre-swelling treatment.
The effects of pre-swelling temperature on the liquefaction conversion
are similar as that on the swelling ratio discussed above. The higher
swelling ratio in THN results in higher liquefaction conversion for the
swollen coal. The swelling ratio of coal got to maximum of 1.69 in THN
at 120 °C, meanwhile pre-swelling treatment at this temperature in
THN gave a maximal liquefaction conversion of 70.0% for the swollen
coal. The results may demonstrate that one of important factors effect
of coal liquefaction is the diffusing of the hydrogen donating solvent
into coal macromolecular network, thus ferrying active H to stabilize
radicals formed from pyrolysis [20,21]. Swelling pre-treatment makes
the relaxation of coal macromolecular network, and creates macro-
pores [22] or increases the porosity of swollen coal, therefore
decreases the diffusion resistant of hydrogen donating solvent into
coal macromolecular network. It may also enhance the internal
hydrogen donation ability of coal hydrogen-rich species themselves
[8], thus increases the liquefaction conversion. The decrease of
liquefaction conversion after pre-swelling treatment at 160 °C in
THN may be related to the higher solubility of THN at the temperature
and the increase of cross-linking density of the swollen coal, which
was also reflected in the decrease of swelling ratio in THN at the
temperature. However, quite different observation was obtained for
NMP used as pre-swelling solvent. The maximal liquefaction conver-
sion of 61.2% was obtained for the swollen coal pre-swelling at room
temperature in NMP and then the liquefaction conversion decreased
with the increasing of pre-swelling temperature as shown in Fig. 3.
160 °C
15.8
17.2 Fig. 3. Effect of pre-swelling treatments in NMP at different temperatures on the
liquefaction conversion of Shenhua coal.
1050 H. Shui et al. / Fuel Processing Technology 90 (2009) 1047–1051
The CS2/NMP mixed solvent (1:1 by volume) was found to give higher
extraction yield for some bituminous coals and the synergistic effect
was attributed to the lowered viscosity of the system [23,24]. The
viscosity of NMP obviously decreases with the increase of tempera-
ture; therefore the solubility of coal in NMP will be greatly increased
during pre-swelling treatment at higher temperatures. This will cause
a stronger aggregation among swollen coal molecules [25,26],
resulting in the decrease in liquefaction conversions. Fig. 4 shows
the FTIR spectra of swollen coals pre-swelling treated at 120 °C in THN
and NMP respectively, comparing with that of raw coal. An increase in
intensity of band near 2920 cm− 1 assigned to CH3 stretch vibration for
the swollen coal pre-swelling treated in THN at 120 °C was observed.
The increase in intensity of band near 2920 cm− 1 shows the increase
in the aliphatic hydrogen content of the pre-swelling treated coal. This
may suggest that hydrogen transfer from swelling solvent THN to coal
occurs during the pre-swelling process due to the good hydrogen
donating ability of THN. That is to say another mechanism of pre-
swelling of coal in THN is H transferring from THN to coal, thus
offering advantages for the further liquefaction of the swollen coal,
resulting in a great enhancement of liquefaction conversion for the
pre-swelling treated coal in THN at this temperature.
3.3. Effect of pre-swelling at mild temperatures on the liquefaction
product distribution
The effects of pre-swelling treatment at different temperatures on
the hydro-liquefaction product distribution are shown in Figs. 5 and 6.
Oil is of the most economically valuable fraction and more beneficial
for coal liquefaction. The yields of oil + gas decreased for all THN
swollen coals except for 80 °C pre-swelling treated one compared to
that of raw coal. Pre-swelling in THN at 80 °C gave the highest yield of
oil + gas 23.8%. It is interesting that the oil + gas yields of NMP
swollen coals pre-swelling treated from 40 °C to 120 °C are similar
with that of raw coal. However it dramatically decreased for the pre-
swelling in NMP at 160 °C. This is probably due to the worse catalyst
dispersion [9,20] owing to the strong aggregation of swollen coal after
much of solubles dissolving in NMP during pre-swelling at this
temperature.
The dispersion of catalyst on the pore surface of coal may influence
the liquefaction product distribution. Pinto et al. [9] believed that
catalyst action on coal surface would lead to higher yield of lighter
fractions, while a more internal catalyst action might lead to higher
yield of asphaltene or preasphaltene. The effect of pre-swelling of coal
on the dispersion of catalyst may include two sides. On the one hand it
is beneficial for the dispersion of catalyst on coal pore surface due to
Fig. 4. FTIR spectra of raw coal and its swollen coals pre-swelling in NMP and THN at
120 °C.
Fig. 5. Effect of swelling pre-treatment in THN at different temperatures on the
liquefaction product distributions of Shenhua coal.
the relaxing structure or expanded pore structure of swollen coal by
pre-swelling treatment. On the other hand, higher solubility of coal in
the swelling solvent at higher temperature may lead to strong
aggregates formed in the swollen coal [19], thus decreases the
porosity resulting in worse catalyst dispersion. In addition, the
swelling solvent permeating the pores of swollen coal may also lead
to a worse dispersion of catalyst on the surface of coal pores. Further
related research work about catalyst dispersion is being carried out in
our group.
It is very interesting that pre-swelling of coal in THN at 120 °C
greatly increases the liquefaction conversion mentioned above. Based
on this result, a swelling-liquefaction combining technology (SLCT)
was designed to check the pre-swelling effects again. The autoclave
with coal, catalyst, hydrogen donation solvent THN and 4.0 MPa H2
pressure charged was kept at 120 °C or 160 °C for 4 h. Then the
autoclave was heated to 400 °C at stirring and maintained at 400 °C for
30 min. The SLCT liquefaction result was compared with those of pre-
swelling treatment in THN at 120 °C or 160 °C and raw coal as shown in
Table 4. Table 4 shows that the SLCT at 120 °C gives 67.6% of
conversion, which is a little lower than that of pre-swelling treatment
at the temperature 70.0%, but is much higher than that of raw coal
55.5%. In addition, SLCT also gives much higher of oil + gas yield 26.8%.
This is probably due to the better catalyst dispersion on the pore
surface of coal promoted by the first stage of swelling, which is
different from the case of pre-swelling in THN at 120 °C, where
catalyst was not added. Table 4 also shows that the SLCT at 160 °C gives
63.6% of conversion, which is a little higher than that of pre-swelling
treatment at the temperature 57.6%, but is a little lower than that of
SLCT at 120 °C. The oil + gas yields for the SLCTs at 120 °C and 160 °C
are similar. The result further supports that the SLCT at 120 °C is an
optimal pre-swelling condition, and it has great advantages compared
to the traditional single-stage liquefaction. It can also be speculated
that the operation cost of the SLCT is lower than that of the multi-
liquefaction mentioned above because of the lower pre-swelling
temperature in the SLCT. Therefore, this SLCT is a new and a very
Fig. 6. Effect of swelling pre-treatment in NMP at different temperatures on the
liquefaction product distributions of Shenhua coal.
 H. Shui et al. / Fuel Processing Technology 90 (2009) 1047–1051 1051

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