774 Ind. Eng. Chem. Res.

2001, 40, 774-780

Catalytic Activity of FeMoNi Ternary Sulfide Supported on a

Nanoparticulate Carbon in the Liquefaction of Indonesian Coals
Unggul Priyanto,† Kinya Sakanishi,‡ Osamu Okuma,§ and Isao Mochida*,†
Institute of Material Study, Kyushu University, Kasuga, Fukuoka 816-8580, Japan, National Institute for
Resources and Environment, Tsukuba, Ibaraki 305-8569, Japan, and The New Industry Research
Organization, 1-5-2 Minatojima-minamimachi, Chuo-ku, Kobe 650-0047, Japan

A series of ternary sulfide catalysts of Fe, Mo, and Ni supported on a nanoparticulate carbon,
Ketjen Black (KB), have been shown to be as active as sulfided Mo and Ni catalysts containing
significantly greater quantities of Mo for the liquefaction of some Indonesian coals. Thus, it is
possible to retain a high catalytic activity when replacing some expensive Mo by cheap Fe. Under
the reaction conditions of 450 °C and 15 MPa of H2 pressure at solvent (tetralin)/coal/catalyst
weight ratios of 1/1/0.03, FeMoNi catalyst (10% Fe, 5% Mo, and 2% Ni based on KB) provided
an oil yield (wt %, daf) of 77% from liquefaction of Tanito Harum coal that is comparable to that
obtained with NiMo (2% Ni and 10% Mo) supported on KB. It is found that Fe-based KB catalysts
have the high activity even with a smaller amount of expensive Mo. The activity of the catalyst
for hydrogenation of 1-methylnaphthalene appeared to reflect the Mo content in the combination
of Fe, Mo, and Ni on KB. The activity of FeMoNi/KB catalysts is slightly influenced by the
order of metal impregnation sequences in the catalyst preparation procedure. The repeated use
of the catalyst, recovered as a tetrahydrofuran-insoluble fraction including ash and unconverted
coal, still provided high oil yield, suggesting that bottom recycle may markedly reduce the amount
of catalyst used in the coal liquefaction.

Introduction Table 1. Some Properties of Nanoparticulate Carbon KB

Some developed countries have spent great effort to KB EC600JD
develop the direct coal liquefaction processes; however, surface area (m2/g) 1270
in the free-market economy of the petroleum supply, the volatile matter (%) 0.7
liquefaction has never been commercially viable. A pH 9.0
major key for commercialization of the liquefaction is average particle size (nm) 30
apparent density (g/L) 115
the reduction of the cost of synthesized oil from coal, ash (%) 0.1
that lies on moderating the operating conditions to lower Ni (ppm) 1.5
construction and operation costs of the coal liquefaction V (ppm) 30
plant and developing a better catalyst to produce much Fe (ppm) 100
oil with good quality from the coal.1 In addition, effective Cu (ppm) 1
catalysts can reduce the hydrogen consumption by Mn (ppm) 1
increasing the efficiency of hydrogen for oil production
and can moderate the liquefaction conditions, such as Black (KB), to achieve excellent activity and recovery
temperature, pressure, and residence time. These effects for repeated use in the liquefaction.7,8 The authors also
of the catalyst are also helpful for the reduction of the proposed the FeNi sulfide on KB (FeNi/KB) to reduce
cost. Nevertheless, there is a problem that the cost of the cost of the catalyst, which is superior to NiMo/Al2O3
the catalyst is rather expensive because of the use of but inferior to NiMo/KB when the contents of the active
expensive metals as active species.1 metals are the same.9
In fundamental researches, a number of catalytic In the present study, catalytic activities of ternary
materials have been investigated for coal liquefaction. sulfide FeNiMo/KB were examined by varying the
However, only iron and molybdenum have been exam- contents of Ni, Fe, and Mo on KB to develop the active
ined in commercial-scale developments, and so far the catalyst with the least amount of Mo, being comparable
greatest attention has been given to Fe catalysts to that of the NiMo/KB catalyst. Moreover, some mo-
because of their lower cost and disposability even though lybdenum salts were also tested as sources of Mo to
their activity is not as high as Mo.1-3 The activity of reduce the cost of a catalyst precursor.
iron can be enhanced by combining with more active
metals such as Mo as catalyst promoters for some Experimental Section
synergistic effects.4-6
Catalyst and Materials. Some properties of KB
The present authors have attempted to use the NiMo
carbon nanoparticles are shown in Table 1.
sulfide supported on a nanoparticulate carbon, Ketjen
Fe, Ni, and Mo salts were impregnated onto KB by
* Corresponding authors. Tel.: +81-92-583-7797. Fax: +81- several impregnating methods using iron(II) fumarate
92-583-7798. E-mail: mochida@cm.kyushu-u.ac.jp. (FeC4H2O4), Ni(NO3)2, or nickel acetate (Ni(OAc)2) and
† Kyushu University. MoO2-acetylacetonate (AA) or (NH4)6Mo7O24 in metha-
‡ National Institute for Resources and Environment. nol or water depending on the solubility of the salts.9-11
§ The New Industry Research Organization. The catalysts prepared in the present study are listed
10.1021/ie000432i CCC: $20.00 © 2001 American Chemical Society
Published on Web 01/09/2001
 Ind. Eng. Chem. Res., Vol. 40, No. 3, 2001 775

Table 2. Catalysts and Salts Table 4. Elemental Analysis of Coals Used in the Present
Study
catalysta Fe salt Ni salt Mo salt
Ca Ha Na Oa Sa ashb H/Cc O/Cc
1. Fe(10) FeC4H2O4
2. Fe(20) FeC4H2O4 Tanito Harum 71.2 5.5 1.6 21.7 0.16 3.9 0.93 0.23
3. Fe(10)Ni(10) FeC4H2O4 Ni(NO3)2 coal
4. Fe(10)Ni(15) FeC4H2O4 Ni(NO3)2 Adaro coal 70.2 5.2 1.0 23.5 0.05 1.3 0.89 0.25
5. Fe(10)Mo(2) FeC4H2O4 MoO2-AAb South Banko 65.8 5.4 1.2 27.2 0.44 1.8 0.99 0.31
6. Fe(10)Mo(3) FeC4H2O4 MoO2-AA coal
7. Fe(10)Mo(2)Ni(2) FeC4H2O4 Ni(NO3)2 MoO2-AA a In wt % (daf: dry ash free). b In wt % (d.b.: dry base). c Atomic
8. Fe(10)Mo(2)Ni(5) FeC4H2O4 Ni(NO3)2 MoO2-AA
9. Fe(10)Mo(3)Ni(3) FeC4H2O4 Ni(NO3)2 MoO2-AA ratio.
10. Fe(10)Mo(3)Ni(5) FeC4H2O4 Ni(NO3)2 MoO2-AA
11. Fe(10)Mo(5)Ni(2) FeC4H2O4 Ni(NO3)2 MoO2-AA The liquid and solid products of coal liquefaction were
12. Fe(10)Mo(5)Ni(4) FeC4H2O4 Ni(NO3)2 MoO2-AA recovered from the autoclave by washing out with
13. Fe(16)Mo(3)Ni(3) FeC4H2O4 Ni(NO3)2 MoO2-AA
tetrahydrofuran (THF). After THF was removed by
14. Fe(14)Mo(3)Ni(3) FeC4H2O4 Ni(NO3)2 MoO2-AA
15. Fe(8)Mo(3)Ni(3) FeC4H2O4 Ni(NO3)2 MoO2-AA evaporation, the product was extracted in sequence with
16. Fe(6)Mo(3)Ni(3) FeC4H2O4 Ni(NO3)2 MoO2-AA n-hexane, acetone, and THF. The n-hexane-soluble (HS),
17. Fe(10)Mo(3)Ni(3) FeC4H2O4 Ni(NO3)2 (NH4)6Mo7O24 n-hexane-insoluble but acetone-soluble (HI-ACS), acetone-
18. Fe(10)Mo(5)Ni(2) FeC4H2O4 Ni(NO3)2 (NH4)6Mo7O24 insoluble but THF-soluble (ACI-THFS), and THF-
19. Ni(2)Mo(10) Ni(OAc)2c MoO2-AA insoluble (THFI) substances were defined as oil (O) and
20. Ni(2)Mo(10) Ni(NO3)2 (NH4)6Mo7O24
solvent, asphaltene (A), preasphaltene (PA), and residue
a Numbers in parentheses indicate the weigh percent of metals.
(R), respectively. The gas yield was calculated by the
b AA: acetylacetonate. c OAc: acetate. weight difference between the initial coal and the
recovered product. The oil yield was calculated by
Table 3. Some Properties of Commercial NiMo Catalysts
and Synthetic Pyrite subtracting the solvent weight from the total weight of
HS.9,11,18-20 The reaction under the same conditions was
NiMo/Al2O3 FeS2 repeated at least three times to make sure the experi-
surface area (m2/g) 400 12 mental deviation was within 1 wt % daf coal base.
average particle size (µm) <250 10 Hydrogenation of 1-Methylnaphththalene (1-
apparent density
Ni (wt %) 2.4 MN). 1-MN (6 g) and catalyst (1.5% based on 1-MN)
Mo (wt %) 10 were charged into the 50 mL autoclave. Standard
Fe (wt %) conditions for hydrogenation were 60 min at 360 °C
under 15 MPa of H2 reaction pressure. 1-Methyl- and
in Table 2. For preparation of the FeNi/KB catalyst, a 5-methyltetralin and traces of tetralin were identified
prescribed amount of KB was dispersed in methanol by gas chromatography (GC)-mass spectrometry (MS)
under ultrasonic irradiation for 15 min, and a mixture and quantified by GC to calculate their conversion in
of FeC4H2O4 and Ni(NO3)2 dissolved in methanol was hydrogenation.9,10
added to the KB-methanol slurry with a small amount
of nitric acid (1 vol %) as an additive. The slurry was Analysis of Oil. The analyses of oil products from
heated at 40 °C for 2 h under ultrasonic irradiation. solvent-free liquefaction were carried out by 1H and 13C
Then, the solid in the slurry was recovered by evapora- NMR. For 1H NMR measurements using CDCl3 solvent
tion and dried at 120 °C for 12 h in vacuo. In the case (ca. 0.5 mL), the spectra were separated into four
of successive impregnation, nickel was first impregnated regions: Hγ, 0.5-1.0 ppm; Hβ, 1.0-1.9 ppm; HR, 1.9-
followed by iron. Other combinations of metal precur- 4.5 ppm; Har (aromatic hydrogen), 6.0-9.0 ppm.21 For
13C NMR measurements using CDCl solvent (ca. 0.5
3
sors, Mo/Ni, Fe/Mo, and Fe/Mo/Ni were also impreg-
nated on KB in the same manner.9,10 These metal orders mL) with 5 mg of Cr(AA)3 (acetylacetonate) as a
of the catalysts indicate the impregnation order in the relaxation-enhancing agent, the spectra were separated
successive impregnation method. Commercial catalysts into two regions: Cal (aliphatic carbon), 0-51 ppm; Car
of Ni(2)Mo(10)/Al2O3 and synthetic pyrite supplied by (aromatic carbon), 93-160 ppm.22
New Energy and Industrial Technology Development
Organization (NEDO) were examined for comparison. Results
Their properties are summarized in Table 3. All of these
catalysts except pyrite were presulfided by flowing 5% Effects of Ni or Mo Addition on the Catalytic
by volume H2S/H2 at 360 °C for 2 h prior to the Activities of Iron Supported on KB. Figure 1 il-
reaction.7-15 lustrates the yields of Tanito Harum coal liquefaction
The elemental analyses of Indonesian sub-bituminous using Fe-based binary sulfide on KB. Fe(10)/KB and
coals used, namely, Tanito Harum, Adaro, and South Fe(20)/KB catalysts gave oil yields (wt %, daf) of 60 and
Banko coals, are summarized in Table 4. Commercially 63%, respectively. While the Fe(10)Ni(10)/KB catalyst
guaranteed grade tetralin (TL) and 1-methylnaphtha- provided an excellent oil yield as high as 68%, being
lene were used as a liquefaction solvent and a reactant higher than that (63%) of Fe(20)/KB. Fe(10)Mo/KB
in the hydrogenation, respectively.9,11,16,17 catalysts with Mo contents of 2 and 3% also improved
Liquefaction Procedure. Coal liquefaction was the oil yield to 67 and 68%, respectively, which were
performed in an electromagnetic-driven autoclave of 50 inferior to those of Fe(10)Ni/KB with a large Ni content
mL capacity. A total of 3 g of coal, 3 or 0 (solvent free) of 15%.
g of solvent, and 0.09 g of catalyst were charged to the Effects of Mo Content on the Catalytic Activities
autoclave. The liquefaction was performed under 15 of the NiMo/KB Catalyst. Figure 2 compares the
MPa of hydrogen pressure at 450 °C for 60 min. The activities of the NiMo/KB catalyst with different Mo
heating rate up to the reaction temperature was 20 °C/ loadings on the liquefaction of Tanito Harum coal. Ni(3)-
min, and the stirring speed was 1300 rpm. Mo(3)/KB and Ni(2)Mo(5)/KB gave oil yields of 69 and
776 Ind. Eng. Chem. Res., Vol. 40, No. 3, 2001
Figure 1. Effect of Ni or Mo addition to Fe(10)/KB on the
liquefaction of Tanito Harum coal: (a) Fe(10)/KB; (b) Fe(20)/KB;
(c) Fe(10)Ni(10)/KB; (d) Fe(10)Ni(15)/KB; (e) Fe(10)Mo(2)/KB; (f)
Fe(10)Mo(3)/KB. Reaction condition: 450 °C, 60 min; reaction H2
pressure ) 15 Mpa. The impregnation process was done with
simultaneous impregnation.
Figure 2. Effects of Mo content on the catalytic activities of NiMo/
KB catalysts in the liquefaction of Tanito Harum coal. Reaction
conditions are the same as Figure 1. (a) Ni(3)Mo(3)/KB; (b)
Ni(2)Mo(5)/KB, (c) Ni(2)Mo(10)/KB [successive impregnation (Mo
first, Ni second); others are simultaneous impregnation].
Figure 3. Effect of addition of Ni to the FeMo/KB catalysts on
the liquefaction of Tanito Harum coal. Reaction conditions are the
same as Figure 1. (a) Fe(10)Mo(2)Ni(2)/KB; (b) Fe(10)Mo(2)Ni(5)/
KB; (c) Fe(10)Mo(3)Ni(3)/KB; (d) Fe(10)Mo(3)Ni(5)/KB; (e) Fe(10)-
Mo(5)Ni(2)/KB [successive impregnation (Mo first, Ni second);
others are simultaneous impregnation]; (f) Fe(10)Mo(5)Ni(4)/KB
[successive impregnation (Mo first, Ni second); others are simul-
taneous impregnation].
72%, respectively. The Ni(2)Mo(10)/KB catalyst provided
the highest oil yield of 78%. A larger Mo content
increased significantly the activity of the catalysts
supported on KB.
Effects of Ni Addition to the FeMo/KB Catalyst.
Figure 3 shows the effect of Ni addition to the FeMo/
KB catalyst on the liquefaction of Tanito Harum coal.
The activities of the catalysts were basically governed
by the Mo content because the oil yield improved from
Figure 4. Effect of Fe addition to the MoNi/KB catalysts on the
liquefaction of Tanito Harum coal. Reaction conditions are the
same as Figure 1. (a) Fe(6)Mo(3)Ni(3)/KB; (b) Fe(8)Mo(3)Ni(3)/
KB; (c) Fe(10)Mo(3)Ni(3)/KB; (d) Fe(14)Mo(3)Ni(3)/KB, (e) Fe(16)-
Mo(3)Ni(3)/KB. The impregnation process was done by simulta-
neous impregnation.
70 to 77% with its increase from 2 to 5%. The Ni content
was optimized at 2-3%. This optimum content of Ni was
the same as that was found with NiMo/KB catalysts,
which showed the best catalytic activity when Ni loading
was increased up to 2-3%.7,10 It must be noted that 5%
Mo in FeMoNi/KB provided an oil yield comparable to
that of Ni(2)Mo(10)/KB under the same reaction condi-
tions. Moreover, 3 and 5% Mo in FeMoNi/KB (Fe(10)-
Mo(3)Ni(3) and Fe(10)Mo(5)Ni(2)) gave oil yields of 5%
higher than those of NiMo/KB with the same Mo
contents (see Figure 2a,b).
Effects of Fe Addition to the MoNi/KB Catalyst.
Figure 4 summarizes the effects of the iron content on
the activity of FeMoNi/KB catalysts. The oil yield
increased from 71 to 74% by increasing the Fe content
from 6 to 10% when the Mo and Ni contents on KB were
fixed to 3%. However, the activity of the catalyst was
saturated with the iron loading by more than 10%.
Figures 5 and 6 show the transmission electron micro-
graphs (TEM) of Fe(10)Mo(3)Ni(3)/KB and Fe(14)Mo-
(3)Ni(3)/KB, respectively. The iron sulfide of 14% load-
ing is not well dispersed compared to that of 10% Fe.
For the loading of 14%, there are some cluster crystal-
lites of 3-4 nm (see Figure 6), while almost no cluster
was found for 10% Fe that was well dispersed.
Effects of the Catalyst Preparation Procedure
on the Activity of NiMo and FeMoNi/KB Catalysts.
The effects of the catalyst preparation procedure are
shown in Figure 7. For the NiMo/KB catalyst, the
successive impregnation method appeared definitely to
be much better than the simultaneous impregnation
when Mo was first impregnated.10 However, the im-
pregnating order of Mo/Fe/Ni in the successive method
gave the same oil yield as that in simultaneous impreg-
nation (see Figure 7c,d), while the order of Fe/Mo/Ni
provided a slightly higher oil yield (see Figure 7e). The
effect of the impregnation process on the dispersion of
the metal is measured by using X-ray diffraction (XRD)
and TEM. The crystallites could not be determined by
XRD because their low crystallization. TEM images of
the Fe(10)Mo(3)Ni(3)/KB catalysts are shown in Figures
5, 8a, and 8b. The images revealed that the successive
impregnation of Fe/Mo/Ni in this order showed a better
dispersion than the simultaneous impregnation. In the
simultaneous impregnation, some cluster crystallites of
Fe were found on some surfaces of KB particles (see
Figure 8b) although other surfaces showed good disper-
sion (see Figure 8a). However, in the successive impreg-
nation, cluster crystallites were hardly found on the

Figure 5. TEM of the Fe(10)Mo(3)Ni(3)/KB catalyst with a
successive impregnation process.
Figure 6. TEM of the Fe(14)Mo(3)Ni(3)/KB catalyst with a
successive impregnation process.
surfaces of particles as shown in Figure 5, indicating
that Fe/Mo/Ni metals were dispersed very well on KB.
Figure 9 shows the catalytic activities of Mo-based
catalysts prepared from the different salts of metal
precursors and solvents in the successive impregnation
procedure. The NiMo/KB catalyst from (NH4)6Mo7O24
salt gave a lower oil yield than that from MoO2-AA
(Figure 2c), indicating that MoO2-AA, which is soluble
in organic solvent, can be dispersed better over a
hydrophobic KB support. However, the activities of Fe-
(10)Mo(5)Ni(2)/KB and Fe(10)Mo(3)Ni(3)/KB catalysts
were not so influenced by the kinds of Mo salts (see
Figure 3c,e).
Ind. Eng. Chem. Res., Vol. 40, No. 3, 2001 777
Figure 7. Effect of the preparation method on the catalytic
activity of Mo-based catalysts in the liquefaction of Tanito Harum
coal. Reaction conditions are the same as Figure 1. (a) Ni(2)Mo(10)
simultaneous impregnation process; (b) Ni(2)Mo(10) successive
impregnation process; (c) Fe(10)Mo(3)Ni(3) simultaneous impreg-
nation; (d) Fe(10)Mo(3)Ni(3) successive impregnation process I [Mo
was firstly impregnated]; (e) Fe(10)Mo(3)Ni(3) successive impreg-
nation process II [Fe was firstly impregnated].
Comparison of Various Catalysts in the Lique-
faction of Sub-bituminous Coals. Figure 10 il-
lustrates the product slates from South Banko and
Adaro coals in the liquefaction with the FeMoNi/KB
catalyst at 450 °C and 15 MPa of H2 pressure. Both
South Banko and Adaro coals with the FeMoNi/KB
catalyst provided 75% oil (Figure 10a,c), reflecting its
high catalytic activity. The liquefaction of Adaro coal
with FeS2 and without catalyst gave much lower oil
yields of 58 and 43%, respectively, while pyrite in the
liquefaction of South Banko coal produced an oil yield
of 63%, which was much lower than that produced by
the FeMoNi/KB catalyst. The catalyst recovered from
Adaro coal liquefaction (Figure 10c) as the THFI fraction
of 0.1726 g including ash and unconverted coal could
still provide a high oil yield of 71% (see Figure 10f) in
the repeated run. The amount of the catalyst reused was
assumed to be 0.09 g, which was the same as the fresh
catalyst in the first run, because all of the recovered
THFI was used. A better recovery procedure such as
gravimetric floating separation can reproduce the cata-
lyst having the same activity by recovering completely
the used catalyst without contamination of residues
such as ash and unconverted coal.7
Figure 11 compares the activities of KB-supported
binary and ternary catalysts with those of commercial
Ni(2)Mo(10)/Al2O3 and FeS2 catalysts in the liquefaction
of Tanito Harum coal. The oil yields with all of the KB-
supported catalysts were above 70% even without Mo
(FeNi/KB; Figure 11d), while NiMo/Al2O3 and FeS2
catalysts gave lower oil yields of 69 and 63%, respec-
tively. The oil yield without catalyst was the lowest. It
is noted that the FeMoNi/KB catalyst with less Mo
content provided an oil yield at the same level as the
NiMo/KB catalyst with a high Mo content of 10%. The
high oil yield was compensated by low yields of gas,
asphaltene, and preasphaltene, suggesting the high
selectivity of the ternary FeMoNi/KB catalyst.
Table 5 shows the activities of the catalysts for the
hydrogenation of 1-methylnaphthalene at 360 °C, 15
MPa of H2, and 60 min. The Mo content basically
governed the hydrogenation activity of the catalyst. The
Mo content of 2 and 3% on the Fe-based catalysts on
KB and 10% Mo on the NiMo/KB catalyst impregnated
simultaneously provided conversions of 16, 24, and 94%,
respectively. The catalysts prepared by the successive
778 Ind. Eng. Chem. Res., Vol. 40, No. 3, 2001
Figure 8. (a) TEM of the Fe(10)Mo(3)Ni(3)/KB catalyst with a
simultaneous impregnation process. (b) TEM of the Fe(10)Mo(3)-
Ni(3)/KB catalyst with a simultaneous impregnation process on
different surfaces.
impregnation showed a little higher activity than those
by the simultaneous impregnation regardless of the
metal components.
Table 6 summarizes the hydrogen and carbon distri-
bution by 1H and 13C NMR analyses of the oil product
(from solvent-free liquefaction) Tanito Harum coal with
various catalysts. Har and Car of oil produced by the Fe-
(10)Mo(3)Ni(3)/KB catalyst were slightly higher than
those of the Ni(2)Mo(10)/KB catalyst, but they were
similar to those of Ni(2.5)Mo(10)/Al2O3, indicating that
the oil may be slightly more aromatic compared to that
of Ni(2)Mo(10)/KB but similar to that of Ni(2.5)Mo(10)/
Al2O3.
Discussion
The greatest attention has been given to sulfided Fe-
based catalysts in the coal liquefaction because of their
Figure 9. Activities of Mo-based catalysts from (NH4)6Mo7O24 salt
in the liquefaction of Tanito Harum coal with tetralin solvent.
Reaction conditions are the same as Figure 1. (a) Ni(2)Mo(10)
[successive impregnation]; (b) Fe(10)Mo(5)Ni(2) [successive im-
pregnation]; (c) Fe(10)Mo(3)Ni(3) [successive impregnation].
Figure 10. Activities of Fe(10)Mo(3)Ni(3)/KB and FeS2 catalysts
in the liquefaction of South Banko and Adaro coals with tetralin
solvent. Reaction conditions are the same as Figure 1. (a) and (b)
South Banko coal; (c), (d), (e), and (f) Adaro coal; (a) and (c)
Fe(10)Mo(3)Ni(3)/KB catalyst, (b) and (d) FeS2 catalyst, (e) no
catalyst, (f) Adaro coal liquefied with the reused Fe(10)Mo(3)Ni(3)/
KB catalyst recovered as THF-Insoluble.
Figure 11. Comparison of the activities of KB-supported catalysts
with those of NiMo/Al2O3 and FeS2 catalysts in the liquefaction
of Tanito Harum coal with tetralin solvent. Reaction conditions
are the same as Figure 1. Catalysts: (a) Ni(2)Mo(10)/KB [succes-
sive impregnation]; (b) Fe(10)Mo(5)Ni(2)/KB [successive impregna-
tion]; (c) Fe(10)Mo(3)Ni(3)/KB [successive impregnation]; (d)
Fe(10)Ni(10) [successive impregnation]; (e) NiMo/Al2O3; (f) FeS2;
(g) no catalyst.
lower cost and disposability. However, their inferior
catalytic activity requires a large amount of Fe and
severe reaction conditions which increase the total cost
of coal liquefaction. Therefore, the methods enhancing
the activity of iron, for example, the addition of other
active metallic species and the use of a catalyst support
with a larger surface area, are required. KB was
selected as the support because it has an extremely
small particle size with a hollow structure and a large

Table 5. Hydrogenation of 1-MNa
catalyst
Fe(10)Ni(10)/KB (simultaneous impregnation)
Fe(10)Ni(10)/KB (successive impregnation)
Fe(10)Mo(2)Ni(2)/KB (simultaneous impregnation)
Fe(10)Mo(3)Ni(3)/KB (simultaneous impregnation)
Fe(10)Mo(3)Ni(3)/KB (successive impregnation)
Fe(10)Mo(5)Ni(2)/KB (successive impregnation)
Ni(2)Mo(10)/KB (simultaneous impregnation)
Ni(2)Mo(10)/KB (successive impregnation)
a Catalyst, 0.09 g; 1-MN, 6 g. b Reaction conditions: 360 °C; 15
MPa; 60 min; 1300 rpm stirring speed.
Table 6. 1H and 13C NMR Analyses of Oil Product from
Tanito Harum Coal
catalyst Hara HR Hβ Hγ Halb
Ni(2)Mo(10)/KB 0.23 0.25 0.38 0.14 0.77
Fe(10)Ni(10)/KB 0.24 0.28 0.37 0.10 0.76
Fe(10)Mo(3)Ni(3)/KB 0.27 0.24 0.35 0.14 0.73
Ni(2.5)Mo(10)/Al2O3 0.28 0.22 0.38 0.12 0.72
a Aromatic. b Aliphatic.
surface area, as shown in Table 1.9,23 The previous study
proved that an Fe-based catalyst supported on KB gave
very high oil yield, and the addition of a small amount
of Mo to the Fe/KB catalyst further increased the oil
yield in the coal liquefaction.9
The present study revealed that the combination of
Fe, Mo, and Ni supported on KB provided significantly
high oil yields in the liquefaction of Indonesian coals,
which seems to reflect its high hydrogenation activity
for the coals although that for 1-MN is not as high as
that for the NiMo/KB catalyst. The active sites of NiMo
sulfide for hydrogenation and desulfurization have been
discussed for many years. There is still much discussion
on the details about the structure and location of the
sites. Nevertheless, the site located on the edges of the
MoS2 crystallites, which are occupied by Ni2+ ions, is
basically accepted as one of the active sites.24 Such an
active site is unique to the combination of Mo and Ni
or Co in their mixed sulfides, where a higher activity
has occurred.24 The ternary combination of Fe, Mo, and
Ni may carry active sites of NiMo as well as sulfided
FeNiMo sites for hydrogenation of coals depending on
the amount of Mo, as suggested by the hydrogenation
of 1-MN. Such a combination may allow us to minimize
the content of expensive molybdenum by using cheap
iron for coal liquefaction even though the hydrogenation
activity for the aromatic ring is limited.25
For the binary or ternary sulfide catalysts supported
on KB, it has been proved that the order of metal
impregnation influences the activity of the catalyst.
Successive impregnation appears to give the higher
activity when the most dominant metal component is
first loaded. The metal component can be better dis-
persed in the first impregnation than that in the second
one because it occupies more effective sites on the
support. Thus, Mo had better be first impregnated for
the preparation of the more active NiMo catalyst.
However, the effect of the impregnation for an inferior
metal such as Fe on the activity may not be as strong
as Mo.
The other point in the discussion concerns the re-
peated use of the catalyst. In the present study, the
catalyst recovered as the THFI fraction still provided a
high oil yield in the second run of the liquefaction. The
bottom recycle of a used catalyst together with heavy
Ind. Eng. Chem. Res., Vol. 40, No. 3, 2001 779
residual products is a promising way to minimize the
conv use of a fresh catalyst with higher oil yield.26 Such
(%)b repeated uses of the present catalyst in the bottom
14 recycle process will be reported in the next paper.
16
16 Acknowledgment
24
28 We gratefully acknowledge the contributions of Dr.
47 Xavier Bourrat for the TEM work and Ms. Rie Sugimoto
94 for NMR analysis.
98
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Received for review April 27, 2000
Revised manuscript received October 19, 2000
Accepted October 20, 2000
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