Method of liquefying coal

When low-quality iron ore is used as a coal liquefaction catalyst, in order to improve its catalytic activity it is subjected to one or a combination of reduction, heat-treatment, or washing with or immersion in water for a long period of time so as to remove catalyst poisons before it is used as a catalyst. When high-quality iron ore is used, it is first reduced with carbon monoxide and then used as a catalyst.

BACKGROUND OF THE INVENTION 
FIELD OF THE INVENTION 
The present invention relates to a method of liquefying coal by 
hydrogenation or hydrogenolysis of coal under high temperature and high 
pressure conditions, and in the presence of a coal liquefaction catalyst, 
thereby hydrogenating coal that has been placed in a solvent for the 
specific purpose of liquefaction. 
DESCRIPTION OF THE PRIOR ART 
Coal liquefaction methods include the direct liquefaction method wherein 
hydrogen is added at a high temperature and a high pressure so as to 
perform hydrogenolysis. In this method, a large amount of hydrogen is 
consumed, and the hydrogenation reaction conditions are servere. In order 
to moderate the reaction conditions, various catalysts are conventionally 
used, e.g., oxides or halides or cobalt, molybdenum, tungsten, tin, iron 
or lead, and the reaction is allowed to take place in the presence of a 
catalyst selected from these catalysts. However, none of these catalysts 
satisfies all the properties desired in such an application, i.e., high 
liquefaction activity, low cost, and availability in large amounts. 
For example, in the conventional H-Coal method, 1 to 10 parts by weight of 
a Co-Mo based pellet catalyst are charged in a boiling water reaction 
tower based on 100 parts by weight of coal; coal slurry is passed through 
the tower, and coal is allowed to react with hydrogen at a temperature of 
about 450.degree. C. and a hydrogen pressure of 150 to 220 kg/cm.sup.2. 
However, since this catalyst is expensive, the method is prohibitively 
expensive. 
A known method using iron ore as a ferric catalyst has the advantage of 
availability in large amounts, since iron ore is inexpensive. However, 
this advantage aside, if untreated, such a catalyst has a low liquefaction 
activity. For this reason, sulfur or a compound of sulfur is added as a 
promotor to improve liquefaction activity. Unfortunately, when sulfur or 
its compound is used in a large amount, sulfur or the sulfur compound is 
evident in the liquefied oil, thereby degrading its quality. 
SUMMARY OF THE INVENTION 
It is an object of the present invention to provide a method of converting 
coal into a liquid at a high conversion rate by improving the coal 
liquefaction activity of a catalyst consisting of iron ore so that 
liquefaction can be performed at a lower temperature and a lower pressure 
than in a conventional method using iron ore, without requiring the use of 
a promotor and requiring only a small amount of catalyst. 
In order to achieve the above object of the present invention, low-quality 
iron ore is subjected to one or a combination of a heat-treatment, 
reduction, and washing with or immersion in water for a long period of 
time so as to improve catalyst activity, and treated low-quality iron ore 
is used as a catalyst. (High-quality iron ore reduced by carbon monoxide 
can also be used as a catalyst.) 
According to the present invention, low- or high-quality iron ore is 
treated and then used as a catalyst. Therefore, catalytic activity can be 
increased so that coal liquefaction can be performed at a lower pressure, 
a lower temperature and a higher conversion rate than that of a 
conventional method. Furthermore, since a large amount of a promotor need 
not be used, the quality of the resultant product will not be degraded.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
When Low-Quality Iron ore is Used as the Catalyst Catalyst Activity 
Improvement of Low-quality Iron Ore 
Low-quality iron ore to be used in the method of the present invention is 
preferably that which contains 0.3 to 3% by weight of nickel, 10 to 50% by 
weight of iron and 0.5 to 10% by weight of chromium, and has a ratio of 
Al.sub.2 O.sub.3 /SiO.sub.2 of 3 of 3 or less, and a specific surface area 
of 50 to 100 m.sup.2 /g. An example of such low-quality iron ore is 
laterite ore. Low-quality iron ore having such properties is used as a 
catalyst for the following reasons. As catalysts, iron, nickel and 
chromium have a function of imparting activity to hydrogenation of 
aromatic compounds. As the nickel content of iron ore increases, the iron 
content tends to decrease. When the nickel content is 0.5 to 3% by weight, 
the iron content is 50 to 10% by weight. According to an experiment 
conducted by the present inventors, iron ore having a nickel content 
falling in this range can significantly impart activity to hydrogenation. 
As for the chromium content, when it is less than 0.5% by weight, the 
above-mentioned effect cannot be obtained. Similarly, when the chromium 
conent exceeds 10% by weight, a particularly good effect cannot be 
obtained. However, when the chromium content falls between these limits an 
extremely good effect is realized. For these reasons, nickel, iron and 
chromium are, preferably, contained in the amounts prescribed above. 
Al.sub.2 O.sub.3 and SiO.sub.2 have acidic catalytic activity. However, 
when the content ratio Al.sub.2 O.sub.3 /SiO.sub.2 exceeds 3, catalytic 
activity decreases. In addition, alumina (Al.sub.2 O.sub.3) is converted 
into a compound having a spinel structure with a metal, and its activity, 
likewise decreases. Therefore, the ratio Al.sub.2 O.sub.3 /SiO.sub.2 is, 
preferably, 3 or less. 
The specific surface area is an important factor in physically improving 
the catalytic activity of iron ore. When the specific surface area is less 
than 50 m.sup.2 /g, desired ore activity cannot be obtained. However, when 
the specific surface area exceeds 100 m.sup.2 /g, the catalytic activity 
is, similarly, impaired, according to an experiment conducted by the 
present inventors. Therefore, the specific surface area should fall 
preferably within a range of 50 to 100 m.sup.2 /g. 
However, as described above, if untreated, low-quality iron ore has a low 
liquefaction activity as a catalyst. This is because the iron ore contains 
catalyst poisons such as alkali metal salts or alkaline earth metal salts. 
For example, laterite ore contains 3 to 10% by weight of each of MgO, CaO, 
Na.sub.2 O, K.sub.2 O, and inherent moisture. 
According to the present invention, in order to improve catalytic activity, 
low-quality iron ore is subjected to one or a combination of the following 
treatments. 
(1) Washing with or Immersion in Water for a Long Period of Time, and 
Subsequent Drying 
This treatment removes poisons such as water soluble alkali metal salts or 
alkaline earth metal salts contained in iron ore, and improves the 
catalytic activity of the iron ore. 
Table 1-1 shows an example wherein alkali metal salts contained in iron ore 
are removed by washing in 
TABLE 1-1 
______________________________________ 
Type 
Alkali Metal Salts & Alkaline Earth 
Metal Salts in Iron Ore (%) 
treatment MgO CaO K.sub.2 O 
Na.sub.2 O 
______________________________________ 
Before Washing 
3.4 0.04 0.07 0.05 
with Water 
After Washing 
2.1 0.015 0.02 0.004 
with Water 
______________________________________ 
This treatment also serves to increase the specific surface area of the 
iron ore and thereby to improve the catalytic activity of iron ore. For 
example, a specific surface area (64.0 m.sup.2 /g) of iron ore can be 
increased to about 77 m.sup.2 /g by washing with water. 
The treatment is preferably performed to a degree such that after washing 
or immersion of the iron ore the solution has a pH of 7. This is because 
the pH of 7 indicates that alkali metal salts and alkaline earth metal 
salts have been sufficiently removed. The iron ore must be dried after the 
treatment. 
(2) Reduction 
In the reduction treatment of low-quality iron ore using carbon monoxide or 
hydrogen gas, ferric oxide is reduced and the specific surface area is 
increased so as to increase the catalytic activity of iron ore. Preferable 
treatment conditions are a treatment temperature of 200.degree. to 
500.degree. C. and a treatment time of less than 120 minutes. This 
treatment can be performed in a gas or a solvent. 
(3) Heat Treatment 
In the heat treatment, low-quality iron ore is heated while air is passed 
through it, so as to increase the specific surface area and to improve the 
catalytic activity of the iron ore. (The heating temperature is preferably 
200.degree. to 500.degree. C.) 
Table 1-2 below shows an example of a specific surface area measurement of 
low-quality iron ore samples which were and were not heat treated. 
TABLE 1-2 
______________________________________ 
Property 
Specific Area (N.sup.2, 
Treating method BET Method) m.sup.2 /g 
______________________________________ 
Tronto No treatment 64.0 
Palawan Washing with water 
77.2 
Heat treatment 
83.3 
H.sub.2 reduction 
90.2 
CO reduction 94.5 
______________________________________ 
The above-mentioned treatments are performed singly or in combination, and 
preferably as follows: 
(1) Reduction (singly performed) 
(2) Heat treatment (singly performed) 
(3) Washing with or immersion in water for a long period of time, drying 
and subsequent reduction 
(4) Washing with or immersion in water for a long period of time, drying 
and subsequent heat treatment 
(5) Washing with or immersion in water for a long period of time and 
subsequent drying 
(6) Washing with or immersion in water for a long period of time, drying, 
heat treatment, and then reduction. 
(7) Washing with or immersion in water for a long period of time, drying, 
reduction and then heat treatment 
Coal is hydrogenated using a coal liquefaction catalyst from which all 
poisons have been removed and/or which has an increased specific surface 
area. In order to obtain a prescribed catalytic effect, the low-quality 
iron ore can be added in the amount of 1 to 10 parts by weight based on 
100 parts by weight of coal. This addition amount is smaller than that of 
low-quality iron ore in a conventional method using it as a catalyst 
without any treatment. In the present invention, hydrogenation of coal can 
be performed at a high conversion rate even through the use of only 
low-quality iron ore from which poisons have been removed and which has an 
increased specific surface area. However, in order to further improve the 
conversion rate, a promotor selected from sulfur, a sulfur compound or a 
mixture thereof can be added in the amount of 0.1 to 10 parts by weight 
based on 100 parts by weight of coal. 
The coal and the catalyst are mixed with a solvent. The type and amount of 
solvent to be used are the same as in the conventional coal liquefaction 
method. For example, creosote oil is preferably added in the amount of 100 
to 200 parts by weight based on 100 parts by weight of coal. 
Hydrogen is added to the mixture at a high temperature and a high pressure 
so hydrogenate and liquefy the coal. The temperature and pressure for 
hydrogenation can be rendered more moderate than those in the coal 
liquefaction method using a conventional iron ore. For example, whereas 
when the conventional method is performed at a temperature of 450.degree. 
C. and an initial hydrogen pressure of 250 kg/cm.sup.2, the method of the 
present invention can be carried out at a temperature of 400.degree. C. 
and an initial hydrogen pressure of 100 kg/cm.sup.2. 
When High-Quality Iron Ore is Used as the Catalyst 
High-quality iron ore to be used in the method of the present invention is 
preferably one which consists of 50 to 70% by weight of iron, and has a 
ratio Al.sub.2 O.sub.3 /SiO.sub.2 of 0.1 to 2.0, and a specific surface 
area of 1 to 30 m.sup.2 /g. Examples of such high-quality iron ore are 
iron ore having ferric oxide as a main component such as limonite or 
hematite. This is because, as a catalyst, the iron content serves to 
impart activity to hydrogenation of an aromatic compound, and iron ore 
containing a large amount of iron is therefore preferable as a catalyst. 
Wwhen the ratio Al.sub.2 O.sub.3 /SiO.sub.2 is high, the iron ore exhibits 
an acidic catalytic activity. However, when the ratio Al.sub.2 O.sub.3 
/SiO.sub.2 is too high, the catalytic activity is impaired, and alumina 
(Al.sub.2 O.sub.3) is converted into a compound having a spinel structure 
with a metal. For this reason, the ratio Al.sub.2 O.sub.3 /SiO.sub.2 
should, preferably, fall within the above-mentioned range. 
The specific surface area is an important factor in physically improving 
the activity of iron ore as a catalyst. When the specific surface area 
deviates from a prescribed range, coal liquefaction activity is degraded. 
Thus, the specific surface area should, preferably, fall within the 
above-mentioned range. 
According to the present invention, high-quality iron ore is not directly 
used as a catalyst, but is so used only after reduction with carbon 
monoxide. Upon reduction treatment, ferric oxide is reduced to produce FeO 
or metal iron. 
FIG. 1 shows changes in weight over time of Fe.sub.2 O.sub.3 samples 
reduced by carbon monoxide. Production of FeO or metal iron can be 
assessed from the decrease in weight of the samples. The sample weight 
decreases and then increases (most significantly when reduction is 
performed at 450.degree. or 500.degree. C.) since carbon produced in the 
reduction treatment is deposited on the sample. 
The present invention will now be described by way of its Examples. The 
types of iron ore and treatments before using the iron ore in the 
respective examples to be described below, are shown in Table 2 below. 
TABLE 2 
______________________________________ 
Washing 
with or Heat Sulfur 
Type of Immersion Treat- Reduc- 
Addi- 
Iron Ore in water ment tion tion 
______________________________________ 
Example 1 
Low-quality 
o x o (CO) 
o 
iron ore 
Example 2 
Low-quality 
o x o (CO) 
x 
iron ore 
Example 3 
Low-quality 
x x o (CO) 
o 
iron ore 
Example 4 
Low-quality 
o o o (CO) 
o 
iron ore 
Example 5 
Low-quality 
o o o (CO) 
x 
iron ore 
Example 6 
Low-quality 
x o x o 
iron ore 
Example 7 
Low-quality 
x o x x 
iron ore 
Example 8 
Low-quality 
o x o (H.sub.2) 
o 
iron ore 
Example 9 
Low-quality 
o x o (H.sub.2) 
x 
iron ore 
Example 10 
Low-quality 
x x o (H.sub.2) 
o 
iron ore 
Example 11 
Low-quality 
o x x o 
iron ore 
Example 12 
Low-quality 
o x x x 
iron ore 
Compara- 
Low-quality 
x x x o 
tive iron ore 
Example 1 
Example 13 
High-quality 
x x o (CO) 
o 
iron ore 
Example 14 
High-quality 
x x o (CO) 
x 
iron ore 
Example 15 
High-quality 
x x o (CO) 
o 
iron ore 
Compara- 
High-quality 
x x x o 
tive iron ore 
Example 2 
______________________________________ 
o: Performed 
x: Not performed 
Example 1 
Coal used had 60 mesh (250 .mu.m or less) and the properties shown in Table 
3 below. A low-quality iron ore catalyst was one which was obtained by 
immersing low-quality iron ore, having the composition and specific 
surface area shown in Table 4, L in distilled water for 100 hours, washing 
it with water, drying it under a reduced pressure, and reducing it at 
350.degree. C. for 2 hours under carbon monoxide flow. Fifty grams of the 
coal, 1.5 g of the low-quality iron ore and 0.3 g of sulfur were mixed 
with 75 g of creosote oil, and the resultant mixture was charged into a 1 
l-rocking autoclave. The mixture was allowed to react at an initial 
hydrogen pressure of 100 kg/cm.sup.2 G, and a temperature of 400.degree. 
C. for a reaction time of 30 minutes. An extraction test and gas analysis 
of the obtained content was performed. As shown in Table 3, the test 
revealed that the conversion rate after tetrahydrofuran (THF) extraction 
was 91.8%. The conversion rate herein indicates the ratio of the total 
content of gas and THF soluble substance (e.g., oil, asphaltene, or 
preasphaltene) in the hydrogenation product (dry base; ash free base). The 
conversion rate used hereinafter is also the same. 
TABLE 3 
______________________________________ 
(Drumhellar) 
Total Water 
Industrial Analysis 
Element Analysis 
Content (d.b %) (d.a.f %) 
(%) Ash VM FC C H S H Odiff 
______________________________________ 
13.4 9.7 46.8 43.5 74.1 4.9 0.4 1.7 18.9 
______________________________________ 
d.b: dry base 
d.a.f: dry ash free 
Ash: ash 
VM: volatile material 
FC: fixed carbon 
TABLE 4 
__________________________________________________________________________ 
Composition (wt %) Specific 
Na.sub.2 O Surface Area 
Type T.Fe 
SiO.sub.2 
Al.sub.2 O.sub.3 
MgO 
CaO 
K.sub.2 O 
Ni 
Al.sub.2 O.sub.3 /SiO.sub.2 
(m.sup.2 /g) 
__________________________________________________________________________ 
Toronto 
42.0 
10.5 
9.6 3.4 
0.04 
0.12 
0.8 
0.92 64 
Palawan 
__________________________________________________________________________ 
TABLE 5 
______________________________________ 
Hydrogenation Product (%) Conversion 
Type Gas THF Soluble Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
8.2 83.6 8.2 91.8 
Palawan 
______________________________________ 
Example 2 
Coal liquefaction was performed using the same coal and low-quality iron 
ore catalyst as in Example 1, and under the same conditions as in 
Eexample 1 l except that sulfur was not added. The obtained results are 
shown in Table 6. 
TABLE 6 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Type Gas THF Soluble Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
8.4 75.4 14.2 85.8 
Palawan 
______________________________________ 
Example 3 
Coal used had 60 mesh or less and the properties shown in Table 3. A 
low-quality iron ore catalyst was prepared from iron one ground to 200 
mesh or less (74 .mu.m or less), and having the composition and specific 
surface area shown in Table 4. The catalyst was prepared by reducing this 
iron ore with carbon monoxide (pressure: 30 kg/cm.sup.2 G; temperature: 
400.degree. C.) for 2 hours, substituting the residual gas with Ar gas, 
and decreasing the temperature. Fifty grams of the coal, 1.5 g of the 
treated iron ore and 0.3 g of sulfur were mixed with 75 g of creosote oil, 
and the resultant mixture was charged into a 1 l-rocking autoclave. The 
mixture was allowed to react at an initial hydrogen pressure of 100 
kg/cm.sup.2 G and a temperature of 400.degree. C. for a reaction time of 
30 minutes. An extraction test and gas analysis of the obtained content 
was performed. The obtained results are shown in Table 7 below. 
TABLE 7 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Type Gas THF Soluble Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
8.2 82.6 9.2 90.8 
Palawan 
______________________________________ 
Example 4 
Coal used had 60 mesh or less and properties as shown in Table 3. A 
low-quality iron ore catalyst was prepared from low-quality iron ore 
having the composition and specific surface area shown in Table 4. The 
catalyst was prepared by immersing the low-quality iron ore in distilled 
water for 100 hours, heat-treating it at 500.degree. C. for 2 hours under 
air flow, and reducing it with carbon monoxide at 350.degree. C. for 2 
hours. Fifty grams of the coal, 1.5 g of the low-quality iron ore 
catalyst, and 0.3 g of sulfur were mixed with 75 g of creosote oil, and 
the resultant mixture was charged into a 1 l-rocking autoclave. The 
mixture was allowed to react at an initial hydrogen pressure of 100 
kg/cm.sup.2 G and a temperature of 400.degree. C. for a reaction time of 
30 minutes. An extraction test and gas analysis of the obtained content 
was performed. According to the results obtained, as shown in Table 8, 
the conversion rate after tetrahydrofuran (THF) extraction was 92%. 
TABLE 8 
______________________________________ 
Hydrogenation Product (%) Conversion 
Type Gas THF Soluble Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
8.2 83.8 8.0 92.0 
Palawan 
______________________________________ 
Example 5 
Coal liquefaction was performed using the same coal and low-quality iron 
ore catalyst as in Example 4, and under the same conditions as in Example 
4 except that sulfur was not added. The obtained results are shown in 
Table 9 below. 
TABLE 9 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Type Gas THF Soluble Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
8.0 77.0 15.0 85.0 
Palawan 
______________________________________ 
Example 6 
Coal used had 60 mesh or less and the properties shown in Table 3. A 
low-quality iron ore catalyst was prepared by immersing low-quality iron 
ore, having the composition and specific surface area shown in Table 4, in 
distilled water for 100 hours, and heattreating it at 500.degree. C. under 
air flow for 2 hours. Fifty grams of the coal, 1.5 g of the low-quality 
iron ore catalyst and 0.3 g of sulfur were well mixed with 75 g of 
creosote oil, and the resultant mixture was charged into a 1 l-rocking 
autoclave. The mixture was then allowed to react at an initial hydrogen 
pressure of 100 kg/cm.sup.2 G and a temperature of 400.degree. C. for 30 
minutes. An extraction test and gas analysis of the obtained content was 
performed. As shown in Table 10, the conversion rate after tetrahydrofuran 
(THF) extraction was 83.7%. 
TABLE 10 
______________________________________ 
Hydrogenation Product (%) Conversion 
Type Gas THF Soluble Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
9.7 74.0 16.3 83.7 
Palawan 
______________________________________ 
Example 7 
Coal liquefaction was performed using the same coal and low-quality iron 
ore catalyst as in Example 6, and under the same conditions in Example 6 
except that sulfur was not added. The obtained results are shown in Table 
11. 
TABLE 11 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Type Gas THF Soluble Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
8.2 59.4 32.4 67.6 
Palawan 
______________________________________ 
Example 8 
Coal used had 60 mesh or less and the properties shown in Table 3. A 
low-quality iron ore catalyst was prepared by immersing low-quality iron 
ore, having the composition and specific surface area shown in Table 4, in 
distilled water for 100 hours, washing it with water and drying it under a 
reduced pressure. After this treatment, the iron ore was reduced at 
350.degree. C. for 2 hours under hydrogen flow. Fifty grams of the coal, 
1.5 g of the low-quality iron ore catalyst and 0.3 g of sulfur were well 
mixed with 75 g of creosote oil, and the resultant mixture was charged 
into a 1 l-rocking autoclave. The mixture was allowed to react at an 
initial hydrogen pressure of 100 kg/cm.sup.2 G and a temperature of 
400.degree. C. for 30 minutes. An extraction test and gas analysis of the 
obtained content was performed. As a result, as shown in table 12, the 
conversion rate after tetrahydrofuran (THF) extraction was 92.3%. 
TABLE 12 
______________________________________ 
Hydrogenation Product (%) Conversion 
Type Gas THF Soluble Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
8.6 83.7 7.7 92.3 
Palawan 
______________________________________ 
Example 9 
Coal liquefaction was performed using the same coal and low-quality iron 
ore catalyst as in Example 8, and under the same conditions as in Example 
8 except that sulfur was not added. The obtained results are shown in 
Table 13. 
TABLE 13 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Type Gas THF Soluble Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
8.2 79.4 12.4 87.6 
Palawan 
______________________________________ 
Example 10 
Coal used had 60 mesh or less and the properties shown in Table 3. A 
low-quality iron ore catalyst was prepared by reducing a low-quality iron 
ore having 200 mesh or less and the composition and specific surface area 
shown in Table 4 at 350.degree. C. for 2 hours under hydrogen flow, 
substituting the residual gas with Ar gas and then decreasing the 
temperature. Fifty grams of the coal, 1.5 g of the iron ore, and 0.3 g of 
sulfur were well mixed with 75 g of creosote oil, and the resultant 
mixture was charged into a 1 l-rocking autoclave. The mixture was allowed 
to react at an initial hydrogen pressure of 100 kg/cm.sup.2 G and a 
temperature of 400.degree. C. for 30 minutes. An extraction test and gas 
analysis of the obtained content was performed. The obtained results are 
shown in Table 14. 
TABLE 14 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Type Gas THF Soluble Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
8.6 82.7 8.7 9l.3 
Palawan 
______________________________________ 
Example 11 
Coal having 60 mesh or less and the properties as in Table 3 was used. A 
low-quality iron ore catalyst was prepared by immersing low-quality iron 
ore, having a mesh of 200 or less and the composition and properties shown 
in Table 4, in distilled water for 100 hours, washing it with water and 
drying it under a reduced pressure. 
Fifty grams of the coal, 1.5 g of the low-quality iron ore catalyst and 0.3 
g of sulfur were well mixed with 75 g of creosote oil, and the resultant 
mixture was charged into a 1 l-rocking autoclave. After the mixture was 
allowed to react at an initial hydrogen pressure of 100 kg/cm.sup.2 G and 
a temperature of 400.degree. C. for 30 minutes, the content was subjected 
to an extraction test and gas analysis. 
As shown in Table 15, the conversion rate after tetrahydrofuran (THF) 
extraction was 79.7%. 
TABLE 15 
______________________________________ 
Hydrogenation Product (%) Conversion 
Type Gas THF Soluble Content 
Residue 
Rate (%) 
______________________________________ 
Toronto 
9.7 70.0 20.3 79.7 
Palawan 
______________________________________ 
Example 12 
Coal liquefaction was performed using the same coal and low-quality iron 
ore catalyst as in Example 11, and under the same conditions as in Example 
11 except that sulfur was not added. The obtained results are shown in 
Table 16. 
TABLE 16 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Type Gas THF Soluble Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
8.5 65.9 25.6 74.4 
Palawan 
______________________________________ 
Comparative Example 1 
Coal as shown in Table 3 was used. The low-quality iron ore catalyst used 
was one having the composition and properties as in Table 4, and was not 
treated before use. Coal liquefaction was performed under the same 
conditions as in Example 1. The obtained results are shown in Table 17. 
TABLE 17 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Type Gas THF Solub1e Substance 
Residue 
Rate (%) 
______________________________________ 
Toronto 
8.2 67.4 24.4 75.6 
Palawan 
______________________________________ 
Example 13 
The coal used had 60 mesh or less and the properties shown in Table 13. A 
high-quality iron ore catalyst was prepared by reducing iron ore having 
the composition and specific surface area shown in Table 18 with carbon 
monoxide (pressure: 30 kg/cm.sup.2 G; temperature: 350.degree. C.) for 2 
hours, substituting the residual gas with Ag gas, and decreasing the 
temperature. Fifty grams of the coal, 5 g of the iron ore and 1 g of 
sulfur were well mixed with 75 g of creosote oil, and the resultant 
mixture was charged into a 1 l-rocking autoclave. The mixture was allowed 
to react at an initial hydrogen pressure of 100 kg/cm.sup.2 G and a 
temperature of 400.degree. C. for 30 minutes. The obtained content was 
subjected to an extraction test and gas analysis. As shown in Table 19, 
the conversion rate after tetrahydrofuran (THF) extraction was 93.4% for 
iron ore A and 99.6% for iron ore B. 
TABLE 18 
______________________________________ 
Specific 
Iron Major Composition (wt %) 
Al.sub.2 O.sub.3 / 
Surface Area 
Ore T.Fe SiO.sub.2 
Al.sub.2 O.sub.3 
CaO SiO.sub.2 
(m.sup.2 /g) 
______________________________________ 
A 59.2 4.38 2.60 2.60 0.59 10 
(Hamersley) 
B 60.0 0.56 3.01 3.01 1.18 13 
(Timblo Goa) 
______________________________________ 
TABLE 19 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Iron THF Soluble Rate 
Ore Gas Substance Residue (%) 
______________________________________ 
A 8.4 85.0 6.6 93.4 
(Hamersley) 
B 8.8 90.9 0.3 99.6 
(Timblo Goa) 
______________________________________ 
Example 14 
Coal liquefaction was performed using the same coal and high-quality iron 
ore as in Example 13, and under the same conditions as in Example 13 
except that sulfur was not added. The obtained results are shown in Table 
20. 
TABLE 20 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Iron THF Soluble Rate 
Ore Gas Substance Residue (%) 
______________________________________ 
A 8.8 76.5 14.7 85.3 
(Hamersley) 
B 8.1 85.9 9.6 90.4 
(Timblo Goa) 
______________________________________ 
Example 15 
Coal having 60 mesh or less and the properties shown in Table 3 was used. A 
high-quality iron ore catalyst was prepared by mixing 5 g of an iron ore 
having the composition and specific surface area shown in Table 18 with 75 
g of creosote oil, reducing the mixture with carbon monoxide (pressure: 30 
kg/cm.sup.2 G; temperature: 350.degree. C.) for 2 hours, substituting the 
residual gas with Ar gas, and decreasing the temperature. After mixing 50 
g of the coal, 5 g of the iron ore and 1 g of sulfur in the reduce 
creosote soil, the mixture was charged into a 1 l-rocking autoclave. The 
mixture was allowed to react at an initial hydrogen pressure of 100 
kg/cm.sup.2 G and a temperature of 400.degree. C. for 30 minutes. The 
obtained content was subjected to an extraction test and gas analysis. The 
obtained results are shown in Table 21. 
TABLE 21 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Iron THF Soluble Rate 
Ore Gas Substance Residue (%) 
______________________________________ 
A 8.4 84.0 7.6 92.4 
(Hamersley) 
B 8.8 88.2 3.0 97.0 
(Timblo Goa) 
______________________________________ 
Comparative Example 2 
Coal as shown in Example 13 was used. The high-quality iron ore used was 
one having the composition and specific surface area as shown in Table 18 
and was not treated before use. Coal liquefaction was performed using the 
same conditions as in Example 13. The obtained results are shown in Table 
22. 
TABLE 22 
______________________________________ 
Hydrogenation Product (Wt %) 
Conversion 
Iron THF Soluble Rate 
Ore Gas Substance Residue (%) 
______________________________________ 
A 9.2 62.4 28.4 71.6 
(Hamersley) 
B 8.8 70.3 20.9 79.1 
(Timblo Goa) 
______________________________________