JP2609301B2 - Method for producing hydrotreating catalyst - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a hydrotreating catalyst, particularly a catalyst suitable for hydrotreating a hydrocarbon oil.

[Conventional technology]

BACKGROUND ART Conventionally, in a hydrotreating step of a hydrocarbon oil such as an oily fraction obtained from crude oil or coal, a catalyst in which an active metal such as nickel or molybdenum is supported on an alumina carrier has been used. These catalysts usually form alumina hydrate,
Impregnated with a salt aqueous solution of these active metals into a γ-alumina carrier fired at about 300 to 600 ° C, again at 300 to 600 ° C
It is manufactured by firing at a degree.

In the catalyst thus obtained, nickel, molybdenum and the like are supported in an oxidized state, so that the catalyst does not show activity as it is. Therefore, usually, when subjected to the hydrotreating, the supported nickel and molybdenum are converted into a sulfide state by flowing a sulfide agent together with hydrogen through the catalyst layer after filling the catalyst into the reactor for the hydrotreatment. A pre-sulfurization treatment is performed, followed by a hydrogenation treatment.

[Problems to be solved by the invention]

By the way, in the above-mentioned production method, at the stage of baking the γ-alumina carrier after impregnating with an aqueous salt solution such as nickel and molybdenum, the supported active metal component, particularly nickel, reacts with γ-alumina to form nickel aluminate. Form. However, nickel aluminate does not contribute to the catalytic activity because it is not converted to the sulfide form in the pre-sulfurization step. Therefore, there is a problem that the catalyst obtained by the above-described method cannot bring out the catalytic activity corresponding to the amount of supported nickel. In particular, in nickel-molybdenum-based catalysts, it is considered that the optimal combination of nickel sulfide and molybdenum sulfide, or the interaction between both, is indispensable for improving catalytic activity and selectivity. When a nate is formed, the activity expression by the combination of the two is inhibited.

[Means for solving the problem]

Therefore, an object of the present invention is to solve the problems of the conventional hydrotreating catalyst, and to fully exploit the potential catalytic activity of the supported active metal component. It is to provide a manufacturing method of.

The present inventors have found that, in a conventional production method, by firing a γ-alumina support at a constant temperature before nickel or molybdenum is supported on the support, aluminate conversion of these active metal components can be suppressed, and catalytic activity can be reduced. It has been found that improvement can be achieved.

That is, according to the present invention, as a means for achieving the above object, a γ-alumina carrier is calcined at 800 to 1,100 ° C. (excluding 1050 ° C.), and then the carrier is provided with at least a nickel salt and a molybdenum salt. An object of the present invention is to provide a method for producing a hydrotreating catalyst, which comprises calcining at 300 to 600 ° C. after supporting one type.

The γ-alumina carrier used in the method of the present invention is the same as that conventionally used, and is not particularly limited.For example, those obtained by firing alumina hydrate at about 300 to 600 ° C. after molding. And commercially available ones.

In the method of the present invention, first, the γ-alumina support is
Fired at 800-1,100 ° C (excluding 1050 ° C).
The atmosphere is an oxygen-containing gas, typically in a stream of air or the like. The time depends on the temperature, but may be about 1 to 4 hours. By this calcination treatment, the crystal form of alumina progresses from the γ-phase to the δ-phase, further to the θ-phase at a high temperature, and further to the α-phase in some cases.
Therefore, although it depends on the firing temperature and time, generally, it is a hybrid state of several crystal forms. However, under the conditions of the present invention, an alumina support in which a δ-phase and a θ-phase, which are particularly difficult to form nickel and aluminate, are usually formed in an amount of about 10% by weight or more is obtained. If the firing temperature is less than 800 ° C, it is difficult to form a δ-phase and a θ-phase,
When the temperature exceeds δ-phase and θ-phase, α-phase having a small specific surface area is generated in large quantities and deteriorates the function as a catalyst carrier, so it is necessary to calcine at 800 to 1,100 ° C. .

After this firing treatment, a step of supporting at least one of nickel and molybdenum and firing at 300 to 600 ° C.
This is performed in the same manner as in the related art. These metals are supported, for example,
The carrier after the calcination treatment may be immersed in an aqueous solution of nickel nitrate, ammonium molybdate or the like, dried, and then calcined at 300 to 600 ° C. in air. Firing temperature is 300 ℃
If it is less than this, nickel or molybdenum is not easily converted to an oxide state, and if it exceeds 600 ° C., a composite oxide is formed with the carrier, which is not preferable. The amount of nickel or molybdenum supported in the active metal supporting step is preferably 2% by weight or more, particularly preferably 2 to 20% by weight, based on the catalyst. 2% by weight
If it is less than 30, the obtained catalyst activity is insufficient.

The supported metal is either nickel or molybdenum.
Although it may be a seed, it is preferably a combination of nickel and molybdenum. Each supported amount is NiO 2 in terms of oxide.
10 wt%, selected by the target from M ₀ O ₃ 5 to 25 wt% range.

In the firing step, the alumina carrier is usually
10% by weight or more of the δ-
Since it is converted to alumina and θ-alumina, very little nickel or the like is converted to aluminate in the step of supporting nickel or the like, and most of nickel and molybdenum are supported in an oxide state.

 Next, the present invention will be specifically described with reference to examples.

〔Example〕

Example 1 A commercially available γ-alumina cylindrical extruded product was prepared at 1,000 ° C. for 2 minutes.
After impregnating 84 ml of an impregnating liquid prepared by dissolving 45.6 g of nickel nitrate (11.1 g in terms of nickel oxide) in water, 100 g of an alumina carrier obtained by calcining for an hour, and drying at 100 ° C. for 16 hours, By calcining at 500 ° C. for 2 hours, a catalyst having a composition of nickel oxide 10% by weight in terms of oxide and the remainder being alumina was obtained.

When the alumina content of the obtained catalyst was analyzed by X-ray diffraction, it was found that the catalyst had the following composition.

δ-alumina 10% by weight θ-alumina 80% by weight Comparative Example 1 100 g of a commercially available γ-alumina cylindrical extruded product was
A catalyst comprising 10% by weight of nickel oxide and the balance being alumina was obtained in exactly the same manner as in the above example, except that the impregnation solution was not impregnated with 84 ml of the impregnating solution without being calcined.

Example 2 Into 100 g of an alumina carrier obtained in the same manner as in Example 1, 4.0 g of nickel carbonate (1.8 g in terms of nickel oxide) and 84 ml of an impregnation liquid prepared by dissolving 7.7 g of molybdenum oxide in water were impregnated. After drying at 100 ° C. for 16 hours, it is calcined at 500 ° C. for 2 hours, and is 2% by weight of nickel oxide and 7% of molybdenum oxide in terms of oxide.
A catalyst having a composition of weight%, the balance being alumina was obtained.

Comparative Example 2 100 g of a commercially available γ-alumina cylindrical extruded product was subjected to 1,000 ° C.
A catalyst having a composition of 2% by weight of nickel oxide, 7% by weight of molybdenum oxide in terms of oxide and the balance being alumina was obtained in exactly the same manner as in Example 2 except that the impregnation solution was impregnated with 84 ml of the impregnating solution without being subjected to the calcination.

Evaluation of hydrogenation activity After the catalysts prepared in Examples and Comparative Examples were subjected to preliminary sulfurization under the following conditions, the hydrogenation activity was evaluated.

(1) Preliminary sulfurization A reaction tube having a capacity of 10 ml was filled with 1.5 g of the catalyst, and a mixed gas of H ₂ S / H ₂ containing 5% by volume of H ₂ S was supplied at a flow rate of 100 ml / min and a temperature of 400.
The mixture was allowed to flow for 2 hours at a temperature of 70 ° C and a pressure of 70 kg / cm ² .

(2) Measurement of hydrogenation activity In a micro autoclave having a content of 50 ml, 0.5 g of a pre-sulfurized catalyst and 10 ml of 1-methylnaphthalene were charged, and hydrogen gas was further introduced at an initial pressure of 70 kg / cm ² . Example 1 and Comparative Example 1 at 400 ° C., Example 2 and Comparative Example 2 at 350 ° C.
For one hour. Thereafter, the production amounts of 1-methyltetralin and 5-methyltetralin were measured by gas chromatography, and the hydrogenation activity of the catalyst was determined from the conversion of 1-methylnaphthalene.

The results are shown in the following table. Catalytic hydrogenation activity Example 1 17.1% Comparative example 1 11.2% Example 2 59.4% Comparative example 2 51.2% [Effect of the invention] According to the method for producing a hydrotreating catalyst of the present invention, nickel supported as an active metal , Molybdenum, particularly nickel, is suppressed from being aluminated, and most of them are supported in an oxide form. For this reason, almost all nickel components are activated in the pre-sulfurization step performed before the hydrogenation treatment, so that they exhibit higher activity than a conventional nickel-based or nickel-molybdenum-based catalyst for hydrogenation.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication C10G 45/50 9547-4H C10G 45/50 (72) Inventor Yuji Yoshimura 1-chome, Higashi, Tsukuba, Ibaraki Prefecture No. 1 Institute of Chemical Technology, Industrial Technology Institute (72) Inventor Hiromichi Shimada 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Toshio Niida, Examiner, Institute of Chemistry, Gakuin (56) References JP-A-64-47447 (JP, A) JP-B-34-2675 (JP, B1)

Claims (1)

(57) [Claims] 1. A γ-alumina carrier is calcined at 800 to 1,100 ° C. (excluding 1050 ° C.), and then at least one of a nickel salt and a molybdenum salt is supported on the carrier, and then the carrier is heated to 300 to 600 ° C. A method for producing a hydrotreating catalyst, the method comprising calcining at ℃.