JPH06203B2 - Coal liquefaction reaction catalyst and coal liquefaction method using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a catalyst for reaction under coal liquefaction and a coal liquefaction method using the same.

(Prior art and its problems) In 1913, Berkius of Germany attempted a direct liquefaction reaction of coal. At this time, it is known that iron oxide was used as a hydrogenation catalyst that is less likely to be poisoned by organic sulfur contained in coal and inorganic sulfur contained in ash. Since then, many researchers have continued to research iron-sulfur catalysts.

Despite the fact that iron-based catalysts have a very mild hydrogenation activity, coal liquefaction catalysts are still being researched worldwide today due to their advantages of being inexpensive and being available in large quantities everywhere. In many cases, it is often an iron-based catalyst. Iron-based catalysts used for coal liquefaction are red mud,
Iron ore, iron oxide, etc. are generally used with sulfur added as a co-catalyst. On the other hand, instead of using iron oxide and sulfur separately, iron sulfide in coal ash, natural iron sulfide or synthetic iron sulfide may be used as a catalyst. Thus, the reason why coal liquefaction catalyst is more disposable than its activity at the price of the catalyst is that it is extremely difficult to recover it when an expensive catalyst is used because the coal contains ash. It depends on the circumstances. However, since a catalyst such as an iron-based catalyst that has only a mild hydrogenation activity is used, the reaction conditions must be extremely severe. For example, reaction temperature, 400 ℃ or more, hydrogen pressure 200
It is unavoidable to operate under severe reaction conditions that are not seen in ordinary chemical reactions, such as atmospheric pressure or higher and residence time of 40 to 60 minutes. Therefore, the load on the reactor is very large. Therefore, if an effective highly active catalyst is developed and the reaction conditions become mild, not only the coal liquefaction reaction effect will be improved, but also the load on the reactor can be significantly reduced. Therefore, it is expected that a secondary effect that the life of the device will be greatly extended as well as the lightening of the device will be achieved, and the process efficiency will be significantly improved. The present inventor has conducted research and development on a coal liquefaction catalyst from such a point of view. It is an object to provide a coal liquefaction method.

(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by using a ruthenium-containing catalyst, and have completed the present invention. I arrived.

That is, according to the present invention, a coal liquefaction reaction catalyst comprising a ruthenium-containing material is provided.

Further, according to the present invention, there is provided a method for liquefying coal, which comprises reacting coal with hydrogen in the presence of a solvent and in the presence of a ruthenium-containing catalyst.

The method for producing the catalyst of the present invention may be any method as long as it allows ruthenium to be contained in the porous substance, and various conventionally known methods can be used. For example, the catalyst of the present invention can be obtained by impregnating a metal oxide or a metal sulfide with a solution of a ruthenium compound in water or an organic solvent solution and drying. In this case, examples of the metal in the metal oxide or sulfide include iron, zirconium, silicon, aluminum, magnesium and titanium.

Examples of particularly preferable metal oxides and sulfides include iron sulfide, iron oxide, acid-type iron oxide, zirconia-alumina-silica-alumina, alumina, magnesia, titania, and the like. The metal oxide or sulfide may be a synthetic product, or a natural clay mineral or a fired product thereof. Further, the solid substance containing ruthenium may be coal or activated carbon.

The shape of ruthenium contained in the solid substance may be a metal, or various ruthenium compounds such as oxides, sulfides, halides and complexes. The ruthenium content in the catalyst is 0.005 in terms of metallic ruthenium.
Is 0.2% by weight, preferably 0.013 to 0.15% by weight.

As a method of liquefying coal using the catalyst of the present invention,
A conventionally known method is adopted, and for example, coal may be reacted with hydrogen at high temperature and high pressure in the presence of a solvent and a catalyst. In this case, the temperature is 350 to 520 ° C., preferably 400 to 450 ° C. is adopted, and the pressure is 10 to 30 MPa,
Preferably 20 to 30 MPa is adopted. The reaction time is 0 to
It is 90 minutes, preferably 10 to 60 minutes. As the solvent, tetralin, decrystallized anthracene oil, creosote oil, coal-based medium oil, bitumen, shale oil, etc. are used.

(Example) Next, the present invention will be described in more detail with reference to examples.

Example 1 Various ruthenium-containing catalysts shown below were prepared.

(A) Ru / Y catalyst After impregnating FeS ₂ of the reagent with ruthenium trichloride, 120 ° C
And dried over to obtain a Ru / Y catalyst. The metal Ru content of this catalyst is 0.013 wt%.

(B) Ru / K catalyst Dissolve about 2 to 3 times the stoichiometric amount of urea in the aqueous solution of ferric sulfate as a reagent, and dissolve the mixed aqueous solution at 90 ° C or higher, preferably at 93 ° C.
Ruthenium trichloride is impregnated into acid-type iron oxide obtained by firing ferric hydroxide obtained by heating at ~ 95 ° C for 2-3 hours in an electric furnace, and then dried at 120 ° C to form Ru / A K catalyst was obtained.
The metal Ru content of this catalyst is 0.013 wt%.

(C) Ru / ZA catalyst 14% ammonia water was added to a mixed aqueous solution of zirconium oxychloride and aluminum nitrate, which were weighed so that the molar ratio was 9: 1, to obtain hydroxide coprecipitation. Ruthenium trichloride is impregnated into the composite oxide of zirconia and alumina obtained by calcining, and once dried at 120 ° C, this is hydrogen-reduced at 250 ° C to obtain a Ru / ZA catalyst. It was The metal Ru content of this catalyst is 0.013 wt%.

(D) Ru / SA catalyst Ruthenium trichloride is impregnated into commercially available silica alumina, and the same reduction treatment as the Ru / ZA catalyst shown in (c) is performed to obtain Ru / SA catalyst.
A / SA catalyst was obtained. The metal Ru content of this catalyst is 0.013 wt%.

(E) Ru / Al catalyst Commercially available gamma-alumina is impregnated with ruthenium trichloride, and reduction treatment similar to that of the Ru / ZA catalyst shown in (C) is performed.
/ Al catalyst was obtained. The metal ruthenium content of this catalyst is 0.0
It is 13 wt%.

(F) Ruthenium / coal catalyst 120 ° C by directly impregnating coal with aqueous ruthenium trichloride solution
And dried to prepare Ru / Cl, Ru / C2 and Ru / C3 catalysts. The respective metal Ru contents are 0.013 wt%, 0.076 wt% and 0.15 wt%
wt%.

Next, a liquefaction reaction of coal was performed using each of the catalysts obtained above.

The liquefaction reaction of coal was carried out by filling a predetermined amount of coal, a solvent, a catalyst, and hydrogen gas into a stainless steel autoclave having an internal volume of 70 ml, and raising the temperature from room temperature to 450 ° C at a heating rate of 2.5 ° C per minute. . Immediately after the reaction temperature reached 450 ° C., the oclave was taken out of the furnace and rapidly cooled with a fan to stop the reaction.

In a normal autoclave experiment, when the temperature reaches the reaction temperature, the temperature is maintained for a certain period of time to set the reaction time. However, even if the reaction temperature is low, the activity increases if the reaction time is sufficiently long. Therefore, in this example, the reaction time was not deliberately set in order to clearly distinguish the catalytic activities.

As coal, vacuum dried Pacific charcoal (carbon; 76.6%
(Weight), hydrogen: 6.2%, nitrogen: 1.2%, sulfur: 0.1%, oxygen: 15.9%) were crushed to 100 mesh or less and used in each experiment in an amount of 3 g.

Tetralin, which was the reagent, was used as the solvent, and 10 g was used for each experiment.

Hydrogen gas was filled in the autoclave at an initial pressure of 10 MPa. The maximum pressure during the reaction was about 23 MPa.

After the reaction was completed, the content of the autoclave was extracted with benzene using a Soxhlet extractor, and the benzene-soluble content was defined as the conversion rate (% by weight) of coal. Furthermore, the elemental analysis of the benzene-soluble component and the structural analysis using ¹³ C-NMR were also performed to evaluate the reaction product. In addition, hydrogen consumption during the reaction was also determined. This hydrogen consumption is the sum of the hydrogen consumption from both the solvents of hydrogen gas. However, the amount of hydrogen consumed as hydrogen sulfide is excluded from the calculation of hydrogen consumption, and the amount of consumption (weight
%).

Table 1 shows the results of experiments conducted using the above-mentioned catalysts. The coal conversion rates shown in Table 1 are expressed in terms of benzene-soluble matter.

In addition, Ru / Cl, Ru / C and R in which ruthenium was impregnated in coal
u / C3 used 3 g of each as it was as a coal raw material.

It is known that coal contains organic and inorganic sulfur. Therefore, in order to investigate the sulfur resistance of each catalyst,
The same experiment was conducted by adding about 0.05 g of sulfur to the catalyst used in Table-1, and the results are shown in Table-2.

Table 3 shows the results of elemental analysis (C, H, N and O) of the benzene-soluble matter obtained in the above-mentioned experiment in order to investigate the hydrogenation depth.

From the results shown in Table 3, it is clear that the catalyst of the present invention is rich in sulfur resistance and has excellent hydrogenation activity.

Table 4 shows the structure index (fa: ratio of aromatic carbon in total carbon, S3: ratio of methylene carbon in total carbon number) and S4: terminal methyl in total carbon obtained in the above experiment. The ratio of base carbon) is shown.

From the results of Table-4, by using the catalyst of the present invention,
Promotes the hydrogenation of aromatic rings, methyl groups and, in particular,
It can be seen that the carbon of the methylene group can be increased significantly. In addition, the fa value was smaller in the presence of sulfur. This indicates that sulfur does not poison ruthenium in this catalyst system, but rather acts as a promoter.

Table 5 shows hydrogen gas consumption (wt%) during the reaction when the catalyst of the present invention was used, that is, consumed hydrogen gas (g) / dry, ashless base coal (g).

It is clear from Table-5 that the catalyst of the present invention has excellent hydrogenation ability.

Comparative Example An experiment was conducted in the same manner as in the above-mentioned example except that a known red mud-sulfur catalyst and a commercially available iron sulfide catalyst were used. The results are shown in Table-6.

[Effects of the Invention] The embodiments have been described in detail above with reference to the embodiments.

The purpose of coal liquefaction is to hydrolyze the coal structure to lower its molecular weight, and at the same time, to obtain a liquefaction product with a high hydrogenation depth. This is because it is possible to reduce the process load for secondary hydrogenation and uploading.

Therefore, when the catalyst according to the present invention is used, it is possible to achieve a high hydrogenation depth which cannot be obtained by the conventional catalyst system under mild reaction conditions and with a very small amount of catalyst, so that the coal liquefaction efficiency can be significantly increased. It became clear.

Front page continuation (72) Inventor Wakunori Maekawa 172-12-1 Tsukikanto, Toyohira-ku, Sapporo-shi, Hokkaido Inside the Hokkaido Industrial Development Laboratory, Industrial Technology Institute (72) Ryoichi Yoshida Nijo, Tsukikanto, Toyohira-ku, Sapporo-shi, Hokkaido 17-2-1, Hokkaido Institute of Industrial Technology (72) Inventor Tadashi Yoshida 2-1-1 Tsukikanto, Toyohira-ku, Sapporo-shi, Hokkaido (2-1) Institute of Industrial Technology, Hokkaido Industrial Development Laboratory (72) Inventor Hiroshi Nagaishi Hokkaido Industrial Development Laboratory, Industrial Technology Institute

Claims (2)

[Claims] 1. A catalyst for coal liquefaction reaction, which comprises a ruthenium-containing material. 2. A method for liquefying coal, which comprises reacting coal with hydrogen in the presence of a solvent and a ruthenium-containing catalyst.