JPH06339635A - Method for producing hydrotreating catalyst - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for producing a hydrotreating catalyst having high activity. The catalyst carrier is loaded with a metal containing at least one of Group 6 and Group 8 metals of the periodic table and an organic acid, more preferably phosphorus, and then supporting the metal, For hydrotreating, which comprises drying at ℃ or less, and then impregnating the supported metal with an organic acid or polyhydric alcohol in a molar amount of 0.1 to 2.0 times, and drying at 200 ℃ or less. Method for producing catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a catalyst for hydrotreating hydrocarbon oil.

[0002]

2. Description of the Related Art Conventionally, as a hydrotreating catalyst for hydrogenation, desulfurization, denitrification, hydrocracking of hydrocarbon oil such as petroleum fraction, inorganic oxides such as alumina, titania, silica and magnesia are used. A porous catalyst carrier having a periodic table group 6 metal and a group 8 metal supported as active metals is used. Generally, molybdenum or tungsten is used as the Group 6 metal, and nickel or cobalt is used as the Group 8 metal. Since the active sites in these hydrotreating catalysts are considered to be formed on the surface or crystal edge of the active metal sulfide on the carrier, the number of active sites increases as the surface area of the metal sulfide increases. , High activity will be obtained. That is, in order to obtain a catalyst having high activity, it is necessary to increase the surface area of the metal sulfide, and for this reason, the metal sulfide should be in a highly dispersed state, and therefore, the active metal should be supported in a highly dispersed state on the carrier. It is not possible to carry it.

Conventionally, a catalyst for hydrotreating a hydrocarbon oil is obtained by impregnating a catalyst carrier with a supporting liquid composed of a liquid containing a metal to be supported, and then calcining it at 400 ° C. or higher. However, during this firing step, the active metal carried on the surface of the carrier in a highly dispersed state is exposed to heat, causing agglomeration and particle formation to reduce the dispersibility of the metal. Furthermore, since the active metal is crystallized by the sintering of the metal caused by the calcination at 400 ° C. or higher, various treatments (eg, redispersion) for the purpose of improving the activation of the catalyst after calcination are effective. hard.

Recently, nitrogen-containing organic compounds (nitriloacetic acid,
(Ethylenediaminetetraacetic acid, diethylenetriamine) is used as a complexing agent at the time of preparing a supporting solution, and the supporting solution is impregnated into an alumina carrier or a silica carrier and then dried at 200 ° C. or lower to prepare a catalyst without firing A method is disclosed (Japanese Patent Laid-Open No. 61-114737). It has been revealed that the catalyst prepared by this method exhibits higher activity than the catalyst calcined at 400 ° C. or higher. In addition, it carries an active metal, and it is dried at less than 200 ° C,
A method has been proposed in which a carboxylic acid is added to this and the catalyst is prepared by drying at less than 200 ° C. (JP-A-4-1662).
33, JP-A-4-244238).

[0005]

However, due to the increasing environmental problems of the earth and the heavier crude oil, severer hydrogenation, desulfurization, denitrification, hydrocracking desulfurization, etc. are required more than ever before. In order to meet the demand, catalysts with further improved activity are required.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a hydrotreating catalyst having higher activity.

[0007]

Means for Solving the Problems The method of the present invention as a means for solving the above-mentioned problems comprises a catalyst carrier containing at least one metal selected from Group 6 metals and Group 8 metals of the periodic table and an organic acid,
More preferably, after supporting the metal using a solution containing phosphorus therein, it is dried at 200 ° C. or lower, and then 0.1 to 2.0 times the molar amount of the organic compound relative to the supported metal. It is impregnated with an acid or a polyhydric alcohol and dried at 200 ° C. or lower.

The catalyst carrier used in the present invention is preferably a porous inorganic oxide such as alumina, silica-alumina, titania, silica, magnesia, and molybdenum or tungsten is used as the metal of Group 6 of the periodic table. Cobalt or nickel is preferable as the Group 8 metal of the periodic table. These metals include oxides, carbonates, sulfates,
Any one of the nitrates, chlorides and ammonium salts can be used, or a combination of two or more of them can be used. The loading amount generally adopted as a hydrotreating catalyst, that is, the periodic rate in terms of oxide. Table 6 Group 6 metals are 5-3
It is preferable that 0% by weight and Group 8 metal be supported in an amount of 2 to 10% by weight.

Further, it is presumed that phosphorus acts as a stabilizer on the active metal, but it is recognized that the catalyst performance such as activity is further improved by supporting phosphorus. In this case, phosphorus is preferably supported in an amount of 0.1 to 5% by weight in terms of oxide, and various phosphoric acids such as orthophosphoric acid are used as a raw material for supplying phosphorus.

A solution containing an organic acid or a polyhydric alcohol is supported on the above metal or phosphorus. The organic acid or the polyhydric alcohol acts as a ligand for the active metal to form a complex to disperse the metal. It seems that the crystal morphology of the metal improves and maintains the property, and at the same time, the crystal form of the metal forms a preferable state for the expression of active sites on the surface of the carrier. This organic acid is preferably used in an amount of 0.1 to 2.0 mols based on the total mols of the active metal. As the organic acid, citric acid, malic acid,
Tartaric acid, malonic acid, ethylene carbonate, acetic acid, methoxyacetic acid, and polyhydric alcohol such as ethylene glycol can be used.

The catalyst carrier is impregnated with these solutions.
For this impregnation, it is advisable to prepare an amount of the solution that can be absorbed by the catalyst carrier, and spray the solution while gently stirring the catalyst carrier. Then, the impregnated product is dried, and the drying temperature at this time is 200 ° C. or lower in order to prevent the aggregation of the active metal on the surface of the carrier, and particularly 110 to 15 from the viewpoint of drying efficiency.
The temperature is preferably 0 ° C.

In the present invention, the metal-supported material prepared by the above method is further impregnated with an organic acid or / and an aqueous polyhydric alcohol solution, whereby further improvement of the catalytic performance is recognized. At this time, the organic acid or polyhydric alcohol impregnated on the catalyst seems to act as a recomplexing agent for the active metal once supported on the surface of the carrier. In other words, it seems to increase the number of active sites by acting as a ligand again on the metal part that is not involved in the bond with the carrier to form a complex and adsorbing it on the surface of the carrier on which the active metal is not yet supported. Is. The amount of the organic acid or / and the polyhydric alcohol impregnated in this case is 0.1 to 0.1 with respect to the total molar amount of the active metal.
The molar amount is preferably 2.0, and the organic acid and the polyhydric alcohol may be the same as or different from those used for supporting the metal.

After impregnating these organic acids or / and polyhydric alcohol aqueous solution, the impregnated product is dried. The drying temperature at this time is 200 ° C. or less in order to prevent aggregation of the active metal on the catalyst surface. , Particularly preferably 110-150
The temperature is preferably set to ° C.

The hydrotreating catalyst of the present invention maintains a high dispersion state of the active metal by the organic acid added at the time of preparing the supporting liquid, and exhibits a higher dispersion state by the organic acid or / and the polyhydric alcohol impregnated after the catalyst is dried. Then, the high dispersion state is maintained until the reaction by not performing the firing step that is generally performed.

The catalyst of the present invention is suitably used for hydrotreating hydrocarbon oils such as various petroleum fractions and distillation residues, such as hydrogenation, desulfurization, denitrification and hydrocracking.

[0016]

The activity of the catalyst prepared by the method of the present invention is extremely high, and as a result, it is possible to perform deep hydrotreating such as deep desulfurization and denitrification of hydrocarbon oil.

[0017]

Example: Specific surface area 240 m ² / g, pore volume 0.616 ml /
29.3 g of molybdenum trioxide on 150 g of g-alumina carrier
9g, cobalt carbonate 13.07g, 85% phosphoric acid 14.55
g, 30 g of citric acid and 150 ml of a supporting solution prepared from water were impregnated and dried at 130 ° C. for 20 hours. Next, the organic acid or polyhydric alcohol described in Table 3 was added to the dried product.
The catalysts A, B, C, D, E, F, G, and H according to the catalyst preparation method of the present invention were impregnated with (indicated as an impregnating agent) in the amount shown in Table 3 and dried at 130 ° C. for 20 hours. Prepared. The amount of organic acid or polyhydric alcohol in Table 3 is a multiple of the total number of moles of the active metal supported on the catalyst.

The molybdenum content of the catalysts A, B, C, D, E, F, G, and H is 15% by weight in terms of oxide, and the cobalt content is 3.8% by weight in terms of oxide. Was 4.6% by weight in terms of oxide.

These catalysts A, B, C, D, E, F,
Using G and H, a catalytic activity test was carried out on the Middle East straight-run light oil having the properties shown in Table 1 under the conditions shown in Table 2.

[Table 1]

[Table 2]

An average reaction rate constant was determined from the obtained hydrodesulfurization data result, and the rate constant of the catalyst I of Comparative Example 1 was set to 1
The desulfurization activity was represented by a relative value of 00 and is shown in Table 3. In this case, the rate constant is that the desulfurization reaction rate is proportional to the 1.5th power of the sulfur concentration in the feed gas oil, and the average reaction rate constant is the average value of the three reaction rate constants of 320 ° C, 340 ° C, and 360 ° C. I was there.

[Table 3]

[0021]

[Comparative Example 1] Specific surface area 240 m ² / g, pore volume 0.616 m
29 g of molybdenum trioxide on 150 g of l / g γ-alumina carrier.
39g, cobalt carbonate 13.07g, 85% phosphoric acid 14.5
Impregnate 150 ml of a carrier solution prepared from 5 g and water with 1
It was dried at 30 ° C. for 20 hours. Next, for the dried product,
Impregnated with methoxyacetic acid in the amount shown in Table 3,
Catalyst I was prepared by drying at 20 ° C. for 20 hours.

The catalyst I had a molybdenum content of 15% by weight in terms of oxide, and a cobalt content of 3.8 in terms of oxide.
The weight% and the phosphorus content were 4.6 weight% in terms of oxide.

Using this catalyst I, a catalytic activity test was conducted in the same manner as in the example, and the obtained results are also shown in Table 3.

[0024]

[Comparative Example 2] Specific surface area 240 m ² / g, pore volume 0.616 m
29 g of molybdenum trioxide on 150 g of l / g γ-alumina carrier.
39g, cobalt carbonate 13.07g, 85% phosphoric acid 14.5
150 ml of carrier solution prepared from 5 g, 30 g of citric acid and water
Was impregnated and dried at 130 ° C. for 20 hours, and this was used as a catalyst J as it was.

The molybdenum content of this catalyst J was 15% by weight in terms of oxide, the cobalt content was 3.8% by weight in terms of oxide, and the phosphorus content was 4.6% by weight in terms of oxide.
Met. Using this, a catalytic activity test was conducted in the same manner as in the example, and the obtained results are also shown in Table 3.

[0026]

[Comparative Example 3] Molybdenum is 15 wt% in terms of oxide, cobalt is 3.8 wt% in terms of oxide, phosphorus is 4.6 wt% in terms of oxide, and any organic acid and / or polyhydric alcohol is used. Using a commercially available catalyst which was not impregnated and calcined at 500 ° C. or higher, a catalytic activity test was conducted in the same manner as in the example, and the obtained results are also shown in Table 3.

From the above results, it can be seen that the activity of the catalyst prepared by the method of the present invention is extremely high.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10G 45/08 ZAB B 2115-4H 49/04 ZAB 2115-4H

Claims (2)

[Claims] 1. A metal of Group 6 and 8 of the periodic table in the catalyst carrier.
After supporting the metal using a solution containing any one or more of the group metals and an organic acid, drying at 200 ° C. or lower,
Next, this is impregnated with 0.1 to 2.0 times the molar amount of the organic acid or polyhydric alcohol with respect to the supported metal.
A method for producing a hydrotreating catalyst, which comprises drying at a temperature of not higher than ° C. 2. A metal of Group 6 and 8 of the periodic table in the catalyst carrier.
After supporting the metal using a solution containing any one or more of the group metals and phosphorus and an organic acid, it is dried at 200 ° C. or lower, and then 0.1 to 2.0 times the supported metal. Impregnated with a molar amount of organic acid or polyhydric alcohol,
A method for producing a hydrotreating catalyst, which comprises drying at a temperature of not higher than ° C.