JP2000328067A - Hydrogenation catalyst for medium-gravity distllate of coal liquefation oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydrogenation catalyst which exhibits an excellent denitrification activity, a high degradation resistance, and a long life by causing a fibrous alumina carrier having a specified average length to carry a metal selected from among metals of the groups VIA and VIII. SOLUTION: The medium-gravity distillate of a coal liquefaction oil is a coal-derived hydrocarbon oil having a b.p. in the range of 100-350 deg.C, and heavy naphtha, kerosene, a gas oil distillate, etc., belong to this category. The fibrous alumina carrier is bundles of fibrous alumina particles having an average length of 5-15 nm, The hydrogenation catalyst is prepared by causing the fibrous alumina carrier to carry a metal selected from among metals of the groups VIA and VIII by a conventional method such as impregnation, immersion or kneading. The metal is e.g. molybdenum, tungsten, cobalt or nickel, tungsten or nickel being especially preferable. The amount of a metal (as an oxide) carried is preferably 20-35 wt.% in the case of a group VIA metal and 3-5 wt.% in the case of a group VIII metal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a hydrotreating catalyst for a middle distillate of coal liquefied oil, and more particularly to a catalyst for denitrification of a middle distillate of coal liquefied oil which is excellent in denitrification activity, has little catalyst deterioration, and has a long service life. For long hydrotreating catalysts.

[0002]

2. Description of the Related Art Coal-based hydrocarbon oils are characterized by high aromaticity, high content of oxygen and nitrogen compounds, and low content of sulfur compounds as compared with petroleum hydrocarbon oils. Such a difference in the properties of the hydrocarbon oil to be hydrotreated requires a slight difference between the coal-based and petroleum-based hydrotreating catalysts and the hydrotreating method.

For example, Japanese Patent Publication No. 3-5435 discloses that
As a method of improving the quality of liquefied coal, liquefied coal is used as a base,
Alternatively, the amount of oxygen compounds contained in the liquefied coal is first reduced by contact with a mixture of N, N'-dimethylformamide and heptane, and then the treated liquefied coal is treated with a hydrogenation catalyst under hydrogenation conditions. An improved method for removing nitrogen compounds contained in liquefied coal by contact has been proposed.

[0004] As described above, coal-based hydrocarbon oil (liquefied coal) contains a large amount of oxygen and nitrogen compounds and a small content of sulfur compounds. In addition to the cause of catalyst deterioration such as metal deposition on active sites, reduction of active sites due to aggregation of active metals can be mentioned.

[0005]

DISCLOSURE OF THE INVENTION The present invention aims to elucidate the cause of the decrease in active sites due to the aggregation of active metals, which is one of the causes of deterioration specific to the above-mentioned hydrotreating catalyst for coal liquefied oil. It is an object of the present invention to provide a hydrotreating catalyst which is excellent in terms of durability, has less catalyst deterioration, and has a long life.

[0006]

Means for Solving the Problems The present inventors have found that the deterioration of the hydrotreating catalyst for the middle distillate of coal liquefied oil is largely attributable to the decrease in active sites due to the aggregation of active metals. Has clarified that the oxygen compound content in the coal liquefied oil medium fraction is high and the sulfur compound content is low, and found a method of physically suppressing the aggregation of active metals,
The present invention has been completed.

That is, the present invention relates to a fibrous alumina carrier comprising a convergent body of fibrous alumina single particles having an average length in the range of 5 to 15 nm, selected from the group consisting of groups VIA and VIII of the periodic table. The present invention relates to a hydrotreating catalyst for a middle distillate of coal liquefied oil, wherein the catalyst carries a metal component.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail.

[0009] The coal liquefied oil medium fraction in the present invention is:
It is a coal-based hydrocarbon oil having a boiling point in the range of 100 to 350 ° C, and corresponds to heavy naphtha, kerosene, gas oil fraction, and the like. The catalyst of the present invention is a catalyst used for hydrotreating the coal liquefied oil middle distillate.

In the catalyst of the present invention, by controlling the average length (L) of the fibrous alumina single particles, the metal component of the obtained catalyst can be used for the hydrogenation treatment of the middle distillate of coal liquefied oil. It is intended to suppress movement and aggregation during growth.

The fibrous alumina carrier in the present invention comprises a conglomerate of fibrous alumina single particles having an average length (L) in the range of 5 to 15 nm. In the fibrous alumina carrier catalyst composed of a single-particle convergent body in which the average length (L) of the fibrous alumina single particles is larger than 15 nm, while the fibrous alumina carrier is being used for the hydrotreating of the middle distillate of coal liquefied oil, The metal component moves and aggregates, and aggregates grow according to the length of the fibrous alumina single particles, so that the activity is greatly deteriorated. On the other hand, when the average length (L) of the fibrous alumina single particles is less than 5 nm, a large amount of metal components in a monodispersed state is expressed, and the hydrodenitrogenation function of the catalyst is unpreferably reduced. As the above-mentioned fibrous alumina carrier in the present invention, a desired carrier can be selected from commercially available alumina carriers.

Incidentally, the average length (L) of the fibrous alumina single particles in the present invention is obtained by calculating the average length of the fibrous alumina single particles from a photograph taken with a transmission electron microscope (TEM) by two.
It is obtained as an average value of values measured for 00 or more.

[0013] The hydrotreating catalyst of the present invention is a compound of the Periodic Table VI
It is prepared by supporting a metal component selected from the group consisting of Group A and Group VIII on the above-mentioned fibrous alumina carrier by a usual method such as impregnation, immersion, or kneading. As the metal component, a component usually used for a hydrotreating catalyst, such as molybdenum, tungsten, cobalt, and nickel, is used. Particularly, tungsten and nickel are preferable because of their high denitrification activity.

The amount of the metal component supported is as follows: 20 to 35% by weight of a metal component of Group VIA of the periodic table as an oxide;
It is desirable that the metal component of Group VIII of the periodic table be in the range of 3 to 5% by weight.

The hydrotreating catalyst of the present invention can have any shape, and the above-mentioned hydrotreating of the middle distillate of coal liquefied oil can be carried out under ordinary treating conditions. For example, a reaction temperature of 300 to 450 ° C. and a hydrogen partial pressure of 15 to 350 kg / cm ²
G and the like are adopted. The hydrotreating catalyst is used for the hydrotreating of coal liquefied oil middle distillate, has excellent denitrification activity, has little catalyst deterioration, and has a long service life.

[0016]

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

Example 1 Pseudo-boehmite alumina gel A was kneaded and had a diameter of 1/32
It was extruded into an inch cylindrical shape. Next, the molded product was dried at 110 ° C. for 16 hours and baked at 550 ° C. for 3 hours to prepare a carrier having an average length of alumina fibers of 6.2 nm. 29.0% by weight of WO ₃ was added to 50 g of the carrier.
Of ammonium metatungstate solution of 43.4 g and N
An Ni—W mixed metal salt aqueous solution prepared by dissolving 4.2% by weight of nickel nitrate (12.4 g) as iO in pure water was supported by an impregnation method. After impregnation, dry at 250 ° C for 1 hour,
It was calcined at 50 ° C. for 1 hour to prepare Catalyst A. Table 1 shows the properties of the catalyst.

Example 2 Pseudo-boehmite alumina gel B was kneaded and had a diameter of 1/32
It was extruded into an inch cylindrical shape. Next, the molded product was dried at 110 ° C. for 16 hours and calcined at 550 ° C. for 3 hours to prepare a carrier having an average alumina fiber length of 14.3 nm. Ni-W mixed metal prepared by dissolving 43.4 g of 29.0 wt% ammonium metatungstate solution as WO ₃ and 12.4 g of 4.2 wt% nickel nitrate as pure NiO in 50 g of this carrier in pure water An aqueous salt solution was supported by the impregnation method. After impregnation, dried at 250 ° C for 1 hour,
Calcination was performed at 550 ° C. for 1 hour to prepare Catalyst B. Table 1 shows the properties of the catalyst.

Comparative Example 1 Pseudo-boehmite alumina gel C was kneaded and had a diameter of 1/32.
It was extruded into an inch cylindrical shape. Next, the molded product was dried at 110 ° C. for 16 hours and calcined at 550 ° C. for 3 hours to prepare a carrier having an average alumina fiber length of 26.9 nm. 43.4 g of a 29.0% by weight ammonium metatungstate solution as WO ₃ was added to 50 g of this carrier.
And 12.4 g of 4.2 wt% nickel nitrate as NiO
Was dissolved in pure water and supported by an impregnation method with an aqueous solution of a mixed metal salt of Ni-W. After impregnation, the catalyst was dried at 250 ° C. for 1 hour and calcined at 550 ° C. for 1 hour to prepare Catalyst C. Table 1 shows the properties of the catalyst.

COMPARATIVE EXAMPLE 2 800 g of a 5 wt% sodium aluminate aqueous solution was placed in a mixing vessel as alumina, and a 2 wt% aluminum sulfate aqueous solution having a pH of 7 was stirred while the aqueous solution was stirred.
Until a slurry of aluminum hydroxide was formed. The obtained slurry is washed and kneaded, and has a diameter of 1
It was extruded into a / 32 inch cylindrical shape. Next, the molded product was dried at 110 ° C. for 16 hours and calcined at 550 ° C. for 3 hours to prepare a carrier having an average alumina fiber length of 4.6 nm. This carrier 50 g, WO ₃ as 29.
0% by weight ammonium metatungstate solution 43.
11. 4 g and 4.2% by weight of nickel nitrate as NiO
An aqueous Ni-W mixed metal salt solution prepared by dissolving 4 g in pure water was supported by an impregnation method. After impregnation, it was dried at 250 ° C. for 1 hour and calcined at 550 ° C. for 1 hour to prepare Catalyst D. Table 1 shows the properties of the catalyst.

Example 3 The hydrodenitrogenation activities of the catalysts A to D prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated. The catalyst was sulfurized before the reaction. A catalyst is filled in a reaction tube, and 5 vol% H
₂ S / 95 vol% H _{2 in a} stream of air (normal pressure, 100 cm ³ /
min) at 400 ° C. for 2 hours. In the test, the time course of the hydrodenitrogenation activity of coal liquefied petroleum kerosene (139 ° C. to 358 ° C.) was investigated in a high pressure fixed bed flow type reactor. The reaction was carried out in a catalytic amount of 15 ml, hydrogen pressure of 6.9 M.
Pa, reaction temperature; 370 ° C., space velocity (LHSV);
The reaction was performed under the conditions of 2h ⁻¹ , H ₂ / Oil ratio; 1000 Nl / l. The reaction results are shown in FIG.

[0022]

[Table 1]

[0023]

[Effect] From the results of FIG. 1, the initial order of hydrodenitrogenation activity is as follows: Catalyst A = Catalyst B = Catalyst C> Catalyst D, and the deterioration over time indicates the order of Catalyst A = Catalyst B <Catalyst C. . As is clear from the above points, the catalyst of the present invention (catalyst A, catalyst B)
Has the same initial activity as the catalyst C, but has little deterioration over time. Further, the activity is higher than that of the catalyst D.

[Brief description of the drawings]

FIG. 1 shows the catalysts obtained in Examples 1 and 2 and Comparative Example 1.
5 is a graph showing the change over time in the hydrodenitrogenation activity of the catalyst obtained in Examples 1 and 2.

 ──────────────────────────────────────────────────続 き Continuation of the front page (71) Applicant 597126930 Toshio Sato 702-69 Shimohirooka, Tsukuba City, Ibaraki Prefecture (71) Applicant 597126918 Yuji Yoshimura 5-526-201 Matsushiro, Tsukuba City, Ibaraki Prefecture (71) Applicant 599067422 Shimada Hiromichi 4-112-202, Azuma, Tsukuba, Ibaraki Pref. (74) The above five agents 100094466 Patent Attorney Eiji Tomomatsu (one outside) (72) Inventor Akio Nishijima 1-29-11, Hakusan, Abiko, Chiba Inventor Toshio Sato 702-69 Shimohirooka, Tsukuba, Ibaraki Pref. (72) Inventor Yuji Yoshimura 5-526-201, Matsushiro, Tsukuba, Ibaraki Pref. 72) Inventor Takashi Kameoka 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu City, Fukuoka Prefecture Inside the Chemical Industry Co., Ltd.Wakamatsu Plant (72) Inventor Hiroshi Yanase 13-2 Kitaminato-cho, Wakamatsu-ku, Fukuoka Prefecture Kashiwa Kogyo Co., Ltd. (72) Koji Masuda, Inventor 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Catalyst F-term in the Wakamatsu Plant (reference) BC68A BC68B BC69A CC40 DA05 FA01 4H029 CA00 DA00

Claims (1)

[Claims] 1. A fibrous alumina support comprising a convergent body of fibrous alumina single particles having an average length in the range of 5 to 15 nm, comprising a metal component selected from the group consisting of groups VIA and VIII of the periodic table. A hydrotreating catalyst for a middle distillate of coal liquefied oil characterized by being supported.