JPH11309372A - Catalyst composition for hydrogenating aromatic hydrocarbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have resistance to sulfur compounds and to reduce the deterioration of activity by supporting a noble metal selected from the group VIII noble metals in the periodic table on an almina-boric carrier. SOLUTION: The component of a noble metal such as ruthenium, rhodium, palladium, osmium, and platinum selected from the group III noble metals in the periodic table is supported on an alumina-boria carrier produced by a method in which alumina or an alumina precursor is mixed with boric acid ammonium borate, or the like as boron compounds, and the mixture is molded, dried, and burned. In this way, its use in the hydrogenation of hydrocarbons contained in catalytic cracking oil, thermal cracking oil, direct distillation light oil, coker gas oil, hydrogenated light oil, desulfurized light oil, and or the like is made possible, resistance to sulfur compounds is exhibited, the activity deterioration is reduced, and the life is extended.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst composition for hydrogenating aromatic hydrocarbons, and more particularly, to hydrogenation of aromatic hydrocarbons and the like, which is resistant to sulfur compounds, has little activity deterioration, and has a long life. The present invention relates to an aromatic hydrocarbon hydrogenation catalyst composition having a long length.

[0002]

2. Description of the Related Art In recent years, when a hydrocarbon containing a polycyclic aromatic compound is used as a fuel, a part of the polycyclic aromatic compound causes incomplete combustion and is discharged into the atmosphere as particulates. There are environmental problems such as concerns about the effects on the human body. In particular, development of catalysts and processes for hydrogenating polycyclic aromatic hydrocarbons in light oil used for diesel engines and the like has become an important issue in enabling production of clean fuels.

[0003] Conventionally, various proposals have been made for aromatic hydrocarbon hydrogenation catalyst compositions in view of the aforementioned situation. For example, JP-A-7-185353 discloses that a refractory oxide carrier and 2 to 15% by weight of a catalytically active metal are used.
A catalyst comprising 5 to 40% by weight of molybdenum and / or tungsten, said molybdenum and / or tungsten being present mainly as its sulfide; Alumina, fluorinated alumina, amorphous silica-alumina, silicon aluminophosphate, zeolites and / or clays are described as oxide carriers.

Japanese Patent Application Laid-Open No. 8-183962 discloses that at least one of catalytic cracking oil, pyrolysis gas oil, straight run gas oil, coker gas oil, hydrotreated oil, and desulfurized gas oil is used as a raw hydrocarbon oil. A carrier containing 80 to 99% by weight of an inorganic oxide and 1 to 20% by weight of a zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 3 to 20; Using a catalyst containing 10 to 30% by weight in terms of oxide, the pressure was 30 to 30%.
A method for hydrotreating an aromatic compound in a hydrocarbon oil, wherein the catalytic reaction is performed at 150 kg / cm ² , a reaction temperature of 200 to 400 ° C., and a liquid hourly space velocity of 0.1 to 5.0 hr ^−1. Is disclosed.

Further, the 26th Petroleum and Petrochemical Symposium Proceedings (1996) sponsored by the Japan Petroleum Institute includes a Pd-P
t / USY zeolite catalyst have been reported for the hydrogenation reaction of the aromatic compound according to the activity, has been studied for the effect of SiO ₂ / Al ₂ O ₃ molar ratio of USY zeolite on sulfidation resistance.

However, the conventional zeolite-based catalyst containing a noble metal component as an active component has a problem that the initial life is high, but the catalyst life is short due to poor sulfuration resistance to sulfur compounds. In addition, a catalyst containing a non-noble metal component such as nickel or tungsten as an active component has a problem that its activity is low although its sulfuration resistance is excellent.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to have a high hydrogenation ability (activity) in hydrogenation of aromatic hydrocarbons and the like in gas oil, and have an activity that is resistant to sulfur compounds. An object of the present invention is to provide an aromatic hydrocarbon hydrogenation catalyst composition which has a small deterioration and a long life.

[0008]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a catalyst composition having a noble metal component supported on an alumina-boria carrier has high activity. The present invention was found to have excellent sulfidation resistance and completed the present invention. That is, the present invention relates to an aromatic hydrocarbon hydrogenation catalyst composition in which at least one noble metal component selected from Group VIII noble metals of the periodic table is supported on an alumina-boria carrier.

[0009]

Embodiments of the present invention will be described below in detail. Alumina in the present invention - boria carrier, it is preferable that boria content is in the range of 97 / 3-70 / 30 _{Al 2 O 3 / B 2 O} 3 weight ratio. The boria content is Al ₂ O ₃ /
If the B ₂ O ₃ weight ratio is less than 97/3, the improvement in the resistance of the catalyst composition to sulfur compounds may decrease. If the B ₂ O ₃ weight ratio is more than 70/30, the pore volume of the catalyst composition may be reduced. It tends to be small, and the diffusion of the polycyclic aromatic hydrocarbon into the catalyst composition becomes poor, so that the activity may be reduced. A more preferred boria content of the alumina-boria support is from 95/5 to 80/20 in terms of Al ₂ O ₃ / B ₂ O ₃ weight ratio.
Range.

The above-mentioned alumina-boria carrier can be produced by a known method in which, for example, alumina or an alumina precursor is mixed with a boron compound, for example, boric acid or ammonium borate, and then molded, dried and calcined. Alternatively, it can be produced by a method of impregnating an alumina carrier with a solution of a boron compound, drying and firing.

The above-mentioned alumina can be obtained by a known preparation method. For example, a sodium aluminate aqueous solution is neutralized with an aluminum sulfate aqueous solution to produce pseudo-boehmite alumina hydrate, and the produced alumina hydrate is washed, aged, kneaded, molded into a desired shape, and dried. And calcined. It is also possible to use alumina hydrate during the preparation process as an alumina precursor.

The catalyst composition of the present invention comprises the alumina
The boria support carries at least one noble metal component selected from Group VIII noble metals of the periodic table. As the noble metal component, ruthenium, rhodium, palladium,
Examples include osmium, iridium, and platinum components.
In the present invention, the amount of the noble metal component described above is preferably in the range of 0.1 to 10% by weight as a metal. If the amount of the metal component is less than 0.1% by weight, the desired hydrogenation ability may not be obtained.
Even if the amount is increased, the increase in the hydrogenation capacity tends to be small and the cost tends to be high. More preferred amount of the noble metal component is,
It is in the range of 0.5 to 5% by weight as a metal.

In the present invention, it is particularly preferable to use a combination of palladium and platinum as the above-mentioned noble metal component. The use of a combination of palladium and platinum maintains high hydrogenation capacity and increases resistance to sulfur compounds. This is presumably because palladium has a high affinity for sulfur and thus protects against sulfur poisoning of platinum. The combination of palladium and platinum preferably has a Pd / Pt atomic ratio in the range of 0.1 / 1 to 10/1.

The catalyst composition of the present invention comprises the alumina
It can be produced by supporting the above-mentioned noble metal component on a boria carrier by an ordinary method. For example, the above-mentioned alumina-boria carrier is impregnated with an aqueous solution of a noble metal component such as palladium chloride, palladium nitrate or an amine complex thereof, platinum amine hydroxide or a platinum amine complex, dried and calcined to obtain a catalyst composition. Further, it can be prepared by a method of kneading an aqueous solution of a noble metal component in the above-mentioned kneading step of alumina-boria.

The catalyst composition of the present invention has a specific surface area (SA)
Is from 100 to 400 m ² / g and the pore volume is from 0.30 to 0.
80 ml / g, average pore diameter in the range of 5 to 30 nm, and has a sharp pore distribution. Further, the catalyst composition of the present invention can contain other active metal components in addition to the above-mentioned noble metal components.

The catalyst composition of the present invention is used for hydrogenating aromatic hydrocarbons contained in catalytic cracking oil, pyrolysis oil, straight run gas oil, coker gas oil, hydrotreated gas oil, desulfurized gas oil and the like. It is suitable. The catalyst composition of the present invention can employ ordinary hydrogenation reaction conditions. Specific hydrogenation conditions include a hydrogen partial pressure of 30 to 150 kg / c.
m ² , the reaction temperature is 200 to 400 ° C., and the liquid hourly space velocity is 0.
For example, ^{1 to} 5.0 hr ^-1 .

[0017]

EXAMPLES The present invention will be described in detail with reference to Examples, but the present invention is not limited by these Examples.

Example 1 1700 g (dry basis) of 85% by weight of pseudo-boehmite alumina hydrate as Al ₂ O _{3 and} 533 g of 15% by weight of boric acid as B ₂ O ₃ were mixed and kneaded, and the diameter was 1/16. It was extruded into an inch cylindrical shape. Next, the molded product is
After drying at 550 ° C. for 16 hours and calcining at 550 ° C. for 3 hours, it was pulverized (particle size: 22 to 48 mesh) to prepare an alumina-boria carrier. This alumina-boria carrier 49.35
g in 0.9 g by weight of [Pd (NH ₃ ) ₄ ]
The Cl ₂ and 1.04 g, was impregnated with 0.40 wt% of [Pt (NH _{3) 4]} The Cl ₂ was prepared by dissolving and 0.34g of pure water Pd-Pt mixed metal salt solution as Pt .
The impregnated product is then dried in a vacuum at 60 ° C. for 6 hours,
300 ° C. in an oxygen stream (2 dm ³ / min · g)
For 3 hours (temperature rise; 0.5 ° C./min) to prepare Catalyst A. Table 1 shows the properties of the catalyst A.

Comparative Example 1 ₂ g of 80 g of a faujasite-type aluminosilicate zeolite (hereinafter referred to as USY zeolite) having a SiO ₂ / Al ₂ O ₃ molar ratio of 15.0 and a unit cell constant of 24.29 ° was measured.
ol / dm ³ in 4000 ml of hydrochloric acid solution, and subjected to a dealumination treatment at 100 ° C. for 2 hours with stirring.
Next, after washing the zeolite, it is dried at 110 ° C. overnight and calcined at 500 ° C. for 1 hour to obtain SiO ₂ / Al ₂ O ₃
A USY zeolite having a molar ratio of 680 was obtained. This USY
0.90% by weight as Pd in 49.35 g of zeolite
1.04 g of [Pd (NH ₃ ) ₄ ] Cl ₂ and 0.30 wt% of [Pt (NH ₃ ) ₄ ] Cl ₂ as Pt
4 g of Pd-Pt mixed metal salt aqueous solution prepared by dissolving 4 g in pure water. Next, the impregnated product was dried in a vacuum at 60 ° C. for 6 hours, disc-shaped and pulverized to a particle size of 2 μm.
2 to 48 mesh. Then, in an oxygen stream (2d
m ³ / min · g) at 300 ° C. for 3 hours (temperature rise;
The mixture was calcined at 0.5 ° C./min to prepare Catalyst B. Table 1 shows the properties of the catalyst B.

Comparative Example 2 Commercially available δ-alumina (49.35 g) was added with Pd of 0.1.
1.04 g of 90% by weight of [Pd (NH ₃ ) ₄ ] Cl ₂
And 0.40% by weight of Pt [Pt (NH ₃ ) ₄ ] C
Pd-P a l ₂ was prepared by dissolving and 0.34g of pure water
t impregnated with a mixed metal salt aqueous solution. Next, the impregnated product was dried in a vacuum at 60 ° C. for 6 hours and then pulverized to a particle size of
2 to 48 mesh. Then, in an oxygen stream (2d
m ³ / min · g) at 300 ° C. for 3 hours (temperature rise;
The catalyst C was prepared by calcining at 0.5 ° C./min). Table 1 shows the properties of the catalyst C.

Example 2 The hydrogenation activity of aromatic hydrocarbons was evaluated using the catalysts A to C prepared in Example 1 and Comparative Examples 1 and 2. The catalyst was reduced before the reaction. The catalyst was filled in a reaction tube, and reduced at 300 ° C. for 3 hours (heating rate: 0.5 ° C./min) in a hydrogen stream (normal pressure, 100 cm ³ / min). The exam is
30wt% as feed oil in high pressure fixed bed flow type reactor
Tetralin-0.3 wt% dibenzothiophene-69.
The change over time in the nuclear hydrogenation activity (conversion rate from tetralin to decalin) of 7 wt% hexadecane (corresponding to a sulfur concentration of 500 wt ppm) was examined. The reaction conditions were as follows.
g, a hydrogen partial pressure of 3.9 MPa, a reaction temperature of 280 ° C., a space velocity (WHSV) of 16 h ⁻¹ , and a H ₂ / Oil ratio of 500 normal liter / liter (NL / L). The reaction results are shown in FIG. The catalyst A of the present invention comprises the catalysts B and C of the comparative examples.
It can be seen from FIG. 1 that the catalyst is less deteriorated and maintains high activity for a long period of time.

[0022]

[Table 1]

The embodiments of the present invention will be listed below. (1) An aromatic hydrocarbon hydrogenation catalyst composition comprising at least one noble metal component selected from Group VIII noble metals of the periodic table supported on an alumina-boria carrier. (2) The alumina-boria carrier has a boria content of A
_{l 2 O 3 / B 2 O} 3 weight ratio at 97/3 to 70/30 preceding the range of (1) an aromatic hydrogenation catalyst composition of hydrocarbons according. (3) The loading amount of the noble metal component is 0.1 to
The aromatic hydrocarbon hydrogenation catalyst composition according to the above (1) or (2), which is in a range of 10% by weight. (4) The aromatic hydrocarbon according to the above (1), (2) or (3), wherein the noble metal component comprises palladium and platinum, and has a Pd / Pt atomic ratio in a range of 0.1 / 1 to 10/1. Hydrogenation catalyst composition. (5) The specific surface area (SA) of the catalyst composition is from 100 to
400 m ² / g, pore volume 0.30 to 0.80 ml /
g, wherein the average pore diameter is 5 to 30 nm (1) to
(4) The aromatic hydrocarbon hydrogenation catalyst composition according to any of (4). (6) Using the catalyst composition according to any one of (1) to (5) above, a hydrogen partial pressure of 30 to 150 kg / cm ² , a reaction temperature of 200 to 400 ° C, and a liquid hourly space velocity of 0.1 to 5.0 hr ^-1. A method for hydrogenating aromatic hydrocarbons, comprising hydrogenating aromatic hydrocarbons contained in oil under the reaction conditions described in (1).

[0024]

The hydrogenation catalyst composition of the present invention is a catalyst in which a noble metal component is supported on an alumina-boria carrier, and therefore has a high hydrogenation ability and is resistant to sulfur compounds in the hydrogenation of aromatic hydrocarbons. And the life is long with little degradation of activity.

[Brief description of the drawings]

FIG. 1 shows the results of the change over time in the conversion of tetralin to decalin in Example 2.

 ──────────────────────────────────────────────────続 き Continued on the front page (71) Applicant 597126929 Hiroyuki Yasuda 1-408-101, Azuma, Tsukuba, Ibaraki (71) Applicant 597126930 Toshio Sato 702-69, Shimohirooka, Tsukuba, Ibaraki (74) Representation of the above four persons Attorney Eiji Tomomatsu (one outsider) (72) Inventor Yuji Yoshimura 5-526-201 Matsushiro, Tsukuba, Ibaraki Prefecture (72) Inventor Hiroyuki Yasuda 1-408-101, Azuma, Tsukuba City, Ibaraki Prefecture (72) Invention Toshio Sato 702-69 Shimohirooka, Tsukuba City, Ibaraki Prefecture (72) Inventor Takashi Kameoka 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Catalyst Wakamatsu Plant

Claims (4)

[Claims] 1. An alumina-boria support having a periodic table VIII
A catalyst composition for hydrogenating aromatic hydrocarbons, comprising at least one noble metal component selected from group noble metals. 2. The hydrogenation of an aromatic hydrocarbon according to claim 1, wherein the alumina-boria carrier has a boria content in the range of 97/3 to 70/30 by weight of Al ₂ O ₃ / B ₂ O ₃ . Catalyst composition. 3. The hydrogenation catalyst composition for an aromatic hydrocarbon according to claim 1, wherein the amount of the noble metal component carried is 0.1 to 10% by weight as a metal. 4. The hydrogenation of an aromatic hydrocarbon according to claim 1, wherein the noble metal component comprises palladium and platinum, and a Pd / Pt atomic ratio is in a range of 0.1 / 1 to 10/1. Catalyst composition.