JP2884050B2 - Selective nuclear hydrogenation over ruthenium-supported metal oxide catalysts. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for selectively subjecting a polycyclic aromatic compound such as coal liquefied oil to a nuclear hydrogenation reaction.
The present invention relates to a method for causing a nuclear hydrogenation reaction of a polycyclic aromatic compound such as coal liquefied oil at a high selectivity using a ruthenium-supported metal oxide having a composite oxide composed of an oxide of zinc and lanthanum as a carrier.

[0002]

2. Description of the Related Art Coal liquefaction is aimed at producing liquid fuel alternative to petroleum such as gasoline and diesel oil. For this purpose, coal is once liquefied, a naphtha fraction and a gas oil fraction are distilled and separated from the produced liquefied oil, and the obtained fraction is secondarily hydrotreated to obtain a liquefied oil fraction. Heterogeneous compounds containing sulfur, nitrogen, oxygen, etc. in them must be hydrocracked and upgraded to liquid fuels. In this case, even if a commercially available desulfurization catalyst is used, the gas consisting of lower hydrocarbons such as methane, ethane, 1-propane, and butane by hydrocracking of the liquefied oil fraction should be used to increase the de-hetero depth. And the liquid yield is significantly reduced. Furthermore, since the chemical structure of liquid fuels such as gasoline and diesel is a straight-chain hydrocarbon, the alicyclic compounds generated by hydrogenation are relatively easy, although the problem of suppressing the gasification reaction still exists. Hydrocracking to produce straight chain hydrocarbons. To date, there have been many studies on secondary hydrogenation catalysts, both in Japan and overseas. For example, Bulletin of Chemical Soc
society of Japan Vol. 62, 3994 (1
989) Sakanishi, K., Ohara, M., Mochida, I. include Rh for tricyclic compounds such as pyrene, fluoranthene, anthracene, fluorene, acridine and carbazole.
When the catalytic activities of Pd, Pt, and Ru and the quantum chemical reaction index were determined and the order of the activities was examined, the order of the activities was that Rh was the highest, followed by Pd and Pt, and that Ru was the lowest. I have. Also, Bulletin of Chemic
al Society of Japan Vol. 61, 3
788 (1988) Song, C., Hanaoka, K., Nomura, M.
Using a nickel-molybdenum catalyst and its sulfide as a catalyst in solvent-extracted coal, hydrogenation of the solvent-extracted coal is performed to evaluate the hetero- and dearomatic reactions. However, the results of these studies are far from over, and further active research is needed in the future.

[0003] The inventors of the present invention have conducted research on the belief that the most important research subject in the coal liquefaction reaction is development of a catalyst regardless of primary liquefaction or secondary liquefaction. For secondary liquefaction,
The main role of the catalyst is its hydrogenation ability. Generally, the high hydrogenation ability of a noble metal such as platinum is known. On the other hand, coal-based feedstocks, even liquefied oils, contain many hetero compounds. For this reason, when these hetero compounds are hydrogenated, they generate water, hydrogen sulfide, and ammonia, causing active site contamination such as neutralizing the surface acidity of noble metal catalysts and carrier compounds such as alumina, and easily occur. It deactivates the catalyst.

[0004]

In order to solve these problems, it is indispensable to select a catalyst having resistance to the hydrode-hetero compound and having a hydrogenation ability. The metal for this purpose is ruthenium, and the carriers include oxides of nickel, manganese, lanthanum, zinc, etc. that do not have surface acidity. As a result, the present invention succeeded.
An object of the present invention is to provide a method for the selective nuclear hydrogenation of polycyclic aromatic compounds such as coal liquefied oil. Another object of the present invention is to provide a method for nucleating a polycyclic aromatic compound such as coal liquefied oil with high selectivity using a ruthenium-supported metal oxide catalyst.

[0005]

According to the present invention, there is provided a polycyclic hydrocarbon such as coal liquefied oil characterized in that a nuclear hydrogenation reaction is performed at a high selectivity using a ruthenium-supported metal oxide catalyst. A preferred embodiment is a method for the selective nuclear hydrogenation of aromatic compounds, wherein the metal oxide is a composite oxide comprising an oxide of nickel, manganese, zinc or lanthanum.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention,
Polycyclic aromatic compounds such as coal liquefied oil are used, and specific examples thereof include naphthalene, anthracene, and coal liquefied oil fractions. In the above selective nuclear hydrogenation reaction of the polycyclic aromatic compound, a ruthenium-supported metal oxide catalyst is used, and the catalyst comprises nickel, manganese, zinc, ruthenium in a composite oxide formed by combining oxides of lanthanum. What is carried is used. As the metal ruthenium, ruthenium chloride, ruthenium nitrate, etc. are used, lanthanum chloride is used as a carrier for preparing lanthanum oxide, and zinc oxide, manganese oxide, and nitrate are all used as preferable ones for preparing nickel oxide. . Ruthenium-supported metal oxide catalyst in the present invention,
The metal ruthenium is used in the form of being supported on a composite oxide composed of these metal oxides. Specifically, manganese oxide / zinc oxide, manganese oxide / nickel oxide,
It is used as a catalyst for each carrier in which metal ruthenium is carried on a composite oxide carrier comprising an appropriate combination of manganese oxide / lanthanum oxide, lanthanum oxide / zinc oxide and the like. As ruthenium to be supported, 0.2 to 1.0% by weight of the carrier as metal ruthenium is preferred.
In Examples 2 to 6 described below, unless otherwise specified, all the catalysts supported 1% of metal ruthenium. Next, the conditions for the selective hydrogenation reaction of the present invention include a reaction temperature of 230 to 430 ° C and a pressure of 10 to 20M.
Suitable conditions include Pa and 5 to 30 minutes, but these reaction conditions may be appropriately changed according to the type of raw materials and the like, and are not particularly limited.

Hereinafter, the present invention will be described in detail with reference to examples. 1. Experimental Apparatus and Experimental Method A stainless steel autoclave having an inner volume of 70 ml was used as an experimental apparatus, and a predetermined amount of raw materials, a catalyst, and hydrogen gas were charged into the autoclave. The temperature rises at a speed. As soon as the reaction temperature is reached, the autoclave is removed from the electric furnace and quenched with a fan to stop the reaction. During this heating process, a temperature at which the hydrogen pressure drops rapidly is observed. This temperature was the nuclear hydrogenation temperature, which was in the range of 230-430 ° C. in the examples shown.

[0008] 2. Reaction conditions The starting materials were the reagents naphthalene (8 g) and anthracene (5
g) In addition, a medium oil fraction (5 g) having a boiling point of 250-350 ° C. obtained by direct liquefaction of Battle River coal was used. The catalyst is impregnated with a small amount of ruthenium chloride (here, unified as 1% by weight as ruthenium based on the weight of the carrier) in a composite oxide composed of oxides of nickel, manganese, zinc, and lanthanum. The ruthenium chloride-supported metal oxide was reduced at 260 ° C. for 2 hours and used as a catalyst. In addition, a commercially available catalyst, HDS-
3 catalyst (NiO = 3.0-4.0, MoO ₃ = 14.5)
-16.0) was used for comparison. All catalysts are 100
It was pulverized to a mesh size or less, and the amount used was unified to 10% by weight of the raw material. However, even if the amount of the catalyst used is 1% by weight, the object can be sufficiently achieved. Hydrogen gas for reaction was charged into the autoclave at an initial pressure of 10 MPa.

3. Analysis method After the reaction was completed, the gas product was once diffused into a polyethylene bag, and the contents were analyzed by gas chromatography. The contents of the autoclave were then removed and analyzed by capillary gas chromatography and a mass spectrometer. When using coal liquefied oil, it is a mixture, so for the analysis of liquid components following gas analysis, nuclear magnetic resonance analysis of hydrogen was performed,
The distribution of substituted hydrogen was analyzed to evaluate nuclear hydrogenation activity. The catalyst composition was X-ray fluorescence analysis, and the identification of the crystal form was X-ray.
Performed by line diffraction.

[0010]

Hereinafter, the present invention will be described in more detail with reference to specific examples. Example 1 (Catalyst preparation method and catalyst pretreatment method) For the preparation of lanthanum oxide as a carrier, lanthanum chloride was added to zinc oxide, manganese oxide,
Nitrate was used in all preparations of nickel oxide. Specifically, a predetermined amount of salts are mixed and dissolved in ion-exchanged water,
A 2.5N aqueous solution of caustic soda was added to neutralize the salts, and stirring was continued for 4 hours while maintaining the pH at 10.4, and then left overnight to confirm that there was no change in pH. Thereafter, the resulting cake was filtered and thoroughly washed with ion-exchanged water, and the obtained cake was once dried at 110 ° C. overnight and further calcined at 500 ° C. for 3 hours in an electric furnace. This was pulverized to 100 mesh or less to obtain a carrier. To carry ruthenium,
After measuring ruthenium trichloride so as to be 1% by weight of the carrier as metal ruthenium, this is dissolved in ion-exchanged water corresponding to the water content, and the carrier is added thereto in a predetermined manner. I waited for the spread. After that, it was dried at 100 ° C. overnight, filled in a cylindrical glass tube, fired and dried at 260 ° C. for 2 hours in an air stream, switched to a hydrogen stream, reduced at 260 ° C. for 2 hours, and reacted. It was used for. A commercially available Cyanamid desulfurization catalyst (H
DS-3) In the case of a catalyst, it was preliminarily sulfurized with a hydrogen gas containing 5.6% by volume of hydrogen sulfide at an initial pressure of 6 MPa at 360 ° C. for 2 hours, and then used for the reaction.

Example 2 A naphthalene nuclear hydrogenation reaction was carried out using a manganese oxide / zinc oxide carrier system catalyst. Table 1 shows the results. However, the selectivity of decalin is shown for both trans and cis (3/1) isomers. Cyclohexane indicates ethylcyclohexane.

[0012]

[Table 1] * Results when ruthenium was not supported. ** Selectivity of high boiling products was 4%.

From these results, it can be understood that the remarkable nuclear hydrogenation activity of ruthenium. In addition, no gas product was detected other than unreacted hydrogen, and the liquid yield was almost 100%. However, in the case of the HDS-3 catalyst, a high boiling point product having a selectivity of 4% was obtained, so that the nuclear hydrogenation selectivity was only 96%.

Example 3 A nuclear hydrogenation reaction of naphthalene was carried out using a manganese oxide / nickel oxide carrier system catalyst. Table 2 shows the results.
However, the selectivity of decalin was trans and cis (3 /
1) is also shown. Cyclohexacin refers to ethylcyclohexane.

[0015]

[Table 2] * Results when ruthenium was not supported. ** Selectivity of high boiling products was 4%.

In this catalyst system, high nuclear hydrogenation activity can be obtained without the coexistence of ruthenium. In addition, no gas product was detected other than unreacted hydrogen, and the liquid yield was almost 100%. However, in the case of the HDS-3 catalyst, a high boiling point product having a selectivity of 4% was obtained, so that the nuclear hydrogenation selectivity was only 96%.

Example 4 A naphthalene nuclear hydrogenation reaction was carried out using a manganese oxide / lanthanum oxide carrier system catalyst. Table 3 shows the results.
However, the selectivity of decalin was in the trans and cis form (2 /
1) is also shown. Cyclohexane indicates ethylcyclohexane.

[0018]

[Table 3] ** Selectivity of high boiling products was 4%.

In this catalyst system, it can be judged that the activity of sequentially synthesizing decalin from tetralin and further promoting hydrogenolysis is poor. In addition, no gas product was detected other than unreacted hydrogen, and the liquid yield was almost 100%. However, in the case of the HDS-3 catalyst, a high boiling point product having a selectivity of 4% was obtained, so that the nuclear hydrogenation selectivity was only 96%.

Example 5 A nuclear hydrogenation reaction of naphthalene was carried out using a lanthanum oxide / zinc oxide carrier system catalyst. Table 4 shows the results. However, the selectivity of decalin is shown for both trans and cis (2/1) isomers. Cyclohexane indicates ethylcyclohexane.

[0021]

[Table 4] ** Selectivity of high boiling products was 4%.

In this case, no gaseous product was detected other than unreacted hydrogen, and the liquid yield was almost 100%. However, in the case of the HDS-3 catalyst, a high boiling point product having a selectivity of 4% was obtained, so that the nuclear hydrogenation selectivity was only 96%.

Example 6 A nuclear hydrogenation reaction of anthracene was carried out using various catalysts. Table 5 shows the results.

[0024]

[Table 5]

In the nuclear hydrogenation of anthracene, no gaseous products were produced other than unreacted hydrogen. But HD
In the case of the S-3 catalyst, a high-boiling compound was produced with a selectivity of 11.4%, so that the selectivity of nuclear hydrogen was kept at 90% or less.

Example 7 Hydrogenation of a liquefied oil nucleus was performed using various catalysts, and the distribution of hydrogen in the product was examined. Table 6 shows the results.

[0027]

[Table 6]

In the above Table 6, Arom, α-H, β
-H and γ-H indicate the content of aromatic nuclear hydrogen, α-position hydrogen, β-position hydrogen, and γ-position hydrogen, respectively. As is evident from the results in Table 6, the amount of aromatic hydrogen in the liquefied oil was greatly reduced by any of the catalysts, and the nuclear hydrogenation reaction proceeded remarkably. Among them, the Mn ₂ O ₃ / NiO catalyst shows much higher nuclear hydrogenation activity than the commercially available catalyst (HDS-3).

As described above, the present invention has been described in detail with reference to Examples. As is clear from these results, the various ruthenium-supported metal oxide catalysts according to the present invention show excellent nuclear hydrogenation activity and are commercially available. It has been shown to exhibit highly selective nuclear hydrogenation activity comparable to or well beyond the nickel / molybdenum catalyst of US Pat. Among them, the activity of the manganese oxide / nickel oxide catalyst was remarkably high, and it was clarified that this catalyst was an epoch-making catalyst that showed extremely high nuclear hydrogenation activity without gasification even to liquefied oil.

[0030]

As described above in detail, the present invention relates to a method for producing a polycyclic aromatic compound such as coal liquefied oil, which comprises subjecting a nuclear hydrogenation reaction with a high selectivity using a ruthenium-supported metal oxide catalyst. The present invention relates to a selective nuclear hydrogenation method, and according to the present invention, the following effects can be obtained. (1) A selective nuclear hydrogenation reaction of a polycyclic aromatic compound such as coal liquefied oil can be performed at a high selectivity. (2) By using a ruthenium-supported metal oxide catalyst, nuclear hydrogenation can be performed with a high selectivity close to 100%. (3) A ruthenium-supported metal oxide catalyst having high selective nuclear hydrogenation activity can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 13/48 C07C 13/58 13/58 C07B 61/00 300 // C07B 61/00 300 B01J 23/64 104X (56) Reference Document JP-A-3-242243 (JP, A) JP-A-1-176451 (JP, A) JP-B-52-3933 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C10G 45/52 C07C 5/10 C10G 1/06 C10G 35/085 C10G 49/06 C10G 65/08 C10G 67/02 C10G 69/02

Claims (2)

(57) [Claims] 1. A ruthenium-supported metal oxide catalyst, wherein the metal oxide carrier comprises nickel, manganese, zinc ,
Or characterized in that the nuclear hydrogenation reaction at a high selectivity at a reaction temperature range two hundred thirty to four hundred thirty ° C. using ruthenium supported metal oxide catalyst which is a composite oxide support comprising at least two components of the oxides of lanthanum For the selective nuclear hydrogenation of polycyclic aromatic compounds. 2. The selective nuclear hydrogenation method according to claim 1, wherein the metal oxide is a composite oxide containing two components of nickel, manganese, zinc and lanthanum oxide.