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Abstract
We have found that adding a proper amount of water can dramatically improve conversion of a sub-bituminous coal in solvent-free
liquefaction under at 3508C using ammonium tetrathiomolybdate (ATTM) as precursor to dispersed MoS2 catalyst H2 pressure. However,
adding water to catalytic reactions at 4008C decreased coal conversion, although water addition to the non-catalytic runs was slightly
beneficial at this temperature. We further examined the effect of water in solvent-mediated runs in addition to “dry” tests and explored a
temperature-programmed liquefaction (TPL) procedure to take advantage of the synergetic effect between water and dispersed Mo catalyst
precursor at low temperatures for more efficient coal conversion. The TPL using ATTM with added water at 3508C, followed by water
removal and subsequent reaction at 4008C gave good coal conversion and oil yield. Model reactions of dinaphthyl ether (DNE) were also
carried out to clarify the effect of water. Addition of water to ATTM substantially enhanced DNE conversion at 3508C. The combination of
data from one-step and two-step tests of DNE and coal at 350–4008C revealed that water results in highly active MoS2 catalyst in situ
generated at 3508C, but water does not promote the catalytic function or reaction once an active catalyst is generated. Using ATTM coupled
with water addition and removal and temperature-programming may be an effective strategy for developing a better coal conversion process
using dispersed catalysts. q 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Coal; Liquefaction; Catalyst; Molybdenum sulfide; Water; Synergetic effect; Temperature-programmed liquefaction
Table 1
Effects of water addition on liquefaction of Wyodak coal at 3508C for 30 min
a
Fresh raw coal was used without predrying in vacuum.
b
The gas yields determined by weighing the micro-reactor before reaction and after releasing the gaseous products.
c
The figures in parenthesis are the gas yields determined by GC analysis.
influence of pre-drying of coal on its catalytic conversion or oven (VD at 1008C for 2 h). The vacuum-dried coal was
pretreatment at low temperatures [30,54]. After we used in the liquefaction tests unless otherwise mentioned.
observed the unusual, synergetic effect between ATTM In selected tests, fresh raw coal and the coal pre-dried in the
and water for coal conversion at low temperatures, we presence of air (AD at 1008C for 2 h) were also used for
conducted liquefaction of several coals using two different comparison.
Mo catalyst precursors, water-soluble ammonium tetrathio- Reagent grade ammonium tetrathiomolybdate (ATTM,
molybdate [53–56] and oil-soluble Molyvan L [57]. from Aldrich with 99.97% purity) was used as the precursor
In the present paper, we report the detailed results on the for the dispersed molybdenum sulfide catalyst. ATTM
effect of water in solvent-mediated runs in addition to [(NH4)2MoS4] was dispersed onto the fresh raw coal or
solvent-free “dry” tests. Using water and dispersed catalyst dried coal (1 wt% Mo on dmmf basis) by incipient wetness
precursor together could dramatically improve coal conver- impregnation (IWI) method from the aqueous solution. In a
sion without any organic solvents at temperatures (325– typical IWI operation, the solution of the precursor ATTM
3758C) that are much lower than those used in conventional was intermittently added dropwise to the coal in a 100 ml
processes (400–4508C). However, adding water to catalytic beaker, in such a fashion that the wet spots over the coal
reactions at 400–4508C range decreased coal conversion, particles do not touch each other, followed by manual stir-
although water addition to the non-catalytic runs was ring with a glass rod until all signs of wetness disappeared.
slightly beneficial in this high temperature range. We also In order to keep the metal loading at a constant level on
explored a temperature-programmed liquefaction procedure different coal samples, we first estimated the incipient
to take advantage of the synergetic effect between water and wetness volume prior to the catalyst impregnation, which
dispersed Mo catalyst precursor at low temperatures for means the total volume of the solvent needed to reach the
more efficient coal conversion. Further, we conducted point of incipient wetness: the point when the solution drops
some model compound reactions for understanding the begin to remain on the external surface of the coal. The
promotional effect of water. impregnated or the raw coal samples were dried in a vacuum
oven at 1008C for 2 h before use.
Liquefaction was carried out using 4 g coal with 4 g
2. Experimental solvent or without any solvent in 25 ml horizontal micro-
autoclave reactors at 350 or 4008C for 30 min (or tempera-
Wyodak sub-bituminous coal from DOE/Penn State Coal ture-programmed) under an initial H2 pressure of 6.9 MPa.
Sample Bank (DECS-8) was used. It was collected in June Agitation was provided by vertical shaking at about
1990, ground to # 60 mesh (sieve opening: # 250 mm) 240 strokes/min. Selected tests were conducted at other
and stored under argon atmosphere in heat-sealed, argon- temperatures in the range of 325–4508C. For the experi-
filled laminated foil bags consisting of three layers. This ments with added water, the weight ratio of water to
coal contains 32.4% volatile matter, 29.3% fixed carbon, dmmf coal was kept at 0.46. The gaseous products were
9.9% ash and 28.4% moisture, on as-received basis; collected for analysis by GC with FID and TCD. The liquid
75.8% C, 5.2% H, 1.0% N, 0.5% S and 17.5% O, on and solid contents of the reactor were placed into a tared
dmmf basis. Drying of the coal was done in a vacuum ceramic thimble and separated into oil, asphaltene and
252 C. Song et al. / Fuel 79 (2000) 249–261
Fig. 2. Effect of water addition on liquefaction of DECS-8 Wyodak coal at 3508C for 30 min using ATTM loaded on the fresh raw coal (Raw), vacuum-dried
coal (VD) and air-dried coal (AD) without any organic solvent. Cat means catalyst precursor ATTM.
C. Song et al. / Fuel 79 (2000) 249–261 253
RCOR 0 1 H2 O RH 1 CO2 1 R 0 H
Fig. 3. Effect of water addition on liquefaction of DECS-8 Wyodak coal at
3
3508C for 30 min in the presence of 1-methylnaphthalene (non-donor) R; R 0 aryl or alkyl
solvent.
Fig. 4. Effect of water addition on liquefaction of DECS-8 Wyodak coal at Fig. 5. Effect of water addition on gas formation during liquefaction of
3508C for 30 min in the presence of tetrahydronaphthalene (H-donor) DECS-8 Wyodak coal at 3508C for 30 min without any organic solvent
solvent. (vacuum-dried coal was used for both non-catalytic and catalytic runs).
254 C. Song et al. / Fuel 79 (2000) 249–261
Fig. 6. Effect of water addition on gas formation during liquefaction of DECS-8 Wyodak coal at 3508C for 30 min using ATTM loaded on the fresh raw coal
(Raw), vacuum-dried coal (VD) and air-dried coal (AD) without any organic solvent. Cat means catalyst precursor ATTM.
To clarify the effects of dispersed catalyst and water 3.2. Effect of water addition on runs at 4008C
on chemical composition of products, we have
performed two-dimensional HPLC analysis of the oils Table 2 shows the results for non-catalytic and catalytic
from various liquefaction reactions using a normal- runs using ATTM with and without added water at 4008C
phase column [65]. The HPLC results revealed that and Fig. 7 illustrates the effect of water and ATTM. In the
the oils from catalytic liquefaction with added water absence of added water, use of ATTM improved coal
contain more phenolic compounds [66]. This suggests conversion substantially, which is manifested by enhanced
that water participates in the reaction leading to phenols oil and asphaltene formation. These increases are also
(Eq. (4)). Supporting evidence for Eq. (4). can also be accompanied by enhanced H2 gas consumption. Compared
found in previous studies by Townsend and Klein [67] to the runs at 3508C, the positive effect of water addition to
on hydrothermal reactions of dibenzylether with water the non-catalytic run becomes much less, but the positive
at 3748C and by Siskin and Katritzky [59] on diary- impact of using ATTM becomes much more remarkable.
lether with water at 3158C. The use of ATTM for reaction at 4008C afforded a high
Table 2
Effect of water addition on catalytic liquefaction of Wyodak coal at 4008C for 30 min
a
The gas yields determined by weighing the microreactor before reaction and after releasing the gaseous products.
b
The figures in parenthesis are the gas yields determined by GC and volumetric analyses.
C. Song et al. / Fuel 79 (2000) 249–261 255
Fig. 9. Effect of water addition on liquefaction of DECS-8 Wyodak coal at 4008C for 30 min in the presence of tetrahydronaphthalene (H-donor) solvent.
efficiency by utilizing the strong-promoting effect of water single-stage 4008C runs shown in Table 2 without added
on ATTM-loaded coal at low temperatures. Therefore, we water. This is likely due to the negative effect of water on
conducted several exploratory experiments of temperature- the catalytic reactions or negative effect of water on in situ
programmed liquefaction (TPL). Table 3 shows the results. generated Mo sulfide catalyst.
The TPL runs shown in the first five columns of Table 3 Consequently, we examined the effect of hot water
involve rapid heat up to 3508C, holding at 3508C for 30 min, removal as the inter-stage separation. No solvent was used
followed by heat up to 4008C and a final holding time of in this batch process. The sixth and seventh columns of
30 min at 4008C. In the presence of added water throughout Table 3 give the results. It is clear that hot water removal
the reaction process, it appears to be beneficial to use ATTM
and the H-donor solvent together. However, the overall
conversion levels and oil yields are not more than the
Table 3
Temperature-programmed liquefaction using ATTM and water with and without inter-stage hot water removal
Fig. 14. System time–pressure profiles for catalytic and non-catalytic reactions of DECS-8 Wyodak coal at 3508C in the absence and presence of added water
without organic solvent.
products, even when the oils yields are similar between runs DNE using ATTM with and without added water in n-C13
under different conditions. solvent at 3508C.) presents the results of DNE tests using
catalyst in situ generated from ATTM with and without
3.5. Role of water in catalytic liquefaction by model tests added water. DNE shows little or no conversion with
added H2O alone. The strong-promoting effect of water on
To clarify the origin of the observed strong synergetic the tests using ATTM in one-step reaction is clearly seen
effect between water and ATTM for coal conversion at from high degree of C–O bond cleavage, high DNE conver-
3508C, we conducted model compound reactions using sion and tetralin yield. To see if water is involved in ATTM
dinaphthyl ether (DNE). Scheme 2 (Model reactions of activation or catalytic reaction of DNE, we performed
Fig. 15. System time–pressure profiles for catalytic and non-catalytic reactions of DECS-8 Wyodak coal at 4008C in the absence and presence of added water
without organic solvent.
C. Song et al. / Fuel 79 (2000) 249–261 259
Scheme 2.
two-step reactions, where water was added before or after temperatures. The use of water also leads to enhanced
ATTM decomposition (1st step) and water was left or CO2 formation at either low or high temperatures, regardless
removed before the reaction of DNE (2nd step). of its impact on coal conversion.
The combination of the one-step and two-step tests of On the basis of coal conversion under different conditions
DNE revealed that at a low temperature of 3508C, the coupled with one-step and two-step tests of model
main role of water is to promote the formation of highly compounds, we propose a new process concept character-
active Mo sulfide catalyst. BET measurements showed that ized by temperature-programmed liquefaction using
the Mo sulfide generated with added water at 3508C has dispersed Mo catalyst precursor together with a proper
much higher surface area, 335 m 2/g, and much higher poros- amount of water in the first stage at 325–3758C, inter-
ity, 0.85 ml/g, than the Mo sulfide from ATTM alone stage hot removal of water and other gases, followed by
(54 m 2/g, 0.17 ml/g). second stage reaction at 400–4408C under H2 pressure
We also performed more detailed model compound tests [73,74]. The results from this work point to a promising
using dinaphthyl ether [69] and 4-(1-naphthylmethyl)biben- new direction for further research in catalytic conversion
zyl at different temperatures [70,71] and an unexpected of coal to liquid fuels and chemical feedstocks.
outcome of clarifying the unusual observation in coal lique- While the trends observed in this study have been found
faction led us to finding a new method for preparing highly to be reproducible, it must be noted that the present results
active MoS2 catalyst [72]. It was also found that in the were obtained in 25 ml micro-reactors. They should not be
model compound tests that the catalysts in situ generated compared on absolute yield basis with the data from large-
at 3758C appear to be more active than those generated at scale tests. Mass transfer conditions are different between
either a lower (3508C) or a higher (4008C) temperature [69– the micro-tubing reactors and in stirred-tank autoclave reac-
71]. tors and the amount of coal sample used in a given reactor
system can also be influential. Care must be taken when one
tries to compare liquefaction data from different sources.
4. Summary and conclusions
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