JPH0386241A - Production of hydrogenation catalyst - Google Patents

Abstract

PURPOSE:To efficiently and uniformly distribute Ru and/or Pt from the surface of a catalyst toward the interior by dissolving an Ru compd. and/or a Pt compd. in an ethanol-water mixture having a certain ethanol content or above. CONSTITUTION:When a catalyst supporting groups VI and VIII metals of the periodic table is produced, a soln. prepd. by dissolving an Ru compd. and/or a Pt compd. in an ethanol-water mixture having >=50% ethanol content is used as a soln. to be impregnated. This soln. is impregnated into a catalyst and this catalyst is dried and calcined or dried and/or calcined and subjected to proper reduction treatment to obtain a hydrogenation catalyst. Since the viscosity of the soln. is lowered and the affinity of Ru and/or Pt for the catalyst is reduced, Ru and/or Pt is uniformly dispersed even in the interior of the catalyst and high activity is ensured.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to a hydrogenation process containing metals from group Ⅰ and group Ⅰ of the periodic table, and ruthenium and/or platinum, which is used in the hydrotreatment of coal liquefaction solvents. The present invention relates to a method for producing a treated catalyst.

[Prior Art] It is well known that catalysts containing platinum group metals as active components are useful substances that have been used in various oxidation reactions, acetoxylation reactions, hydrogenation reactions, etc., and are widely used. ing. By the way, when using a catalyst supporting an active metal component under conditions where the reaction rate is high, such as in exhaust gas treatment, the reactants do not diffuse into the pores of the catalyst and react only on the surface or surface layer. happens. In this case, since the active component within the pores will not be used effectively, it is desirable that the metal serving as the active component be supported on the surface or surface layer of the catalyst. Under these circumstances, all exhaust gas treatment catalysts currently produced containing platinum group metals as active ingredients have platinum group metals supported only on the surface or surface layer of the catalyst. However, when such catalysts are used under conditions where the reaction rate is slow, such as in petroleum refining or coal liquefaction solvent hydrogenation, reactants can diffuse into the pores of the catalyst and cause a reaction. The metal, which is an active component, exists only on the outer surface or surface layer of the catalyst, which inevitably leads to low efficiency.

For this reason, there is a great deal of effort being made to develop catalysts in which platinum group metals are uniformly supported from the surface to the inside for petroleum refining or coal liquefaction solvent hydrogenation.

[Problems to be Solved by the Invention] In recent years, various methods have been proposed to satisfy this requirement by uniformly supporting active metal species from the surface to the inside of the catalyst. For example, after acid or alkali treatment is applied to a porous carrier such as alumina, alumina-silica, or silica, the carrier is impregnated with a desired platinum group active metal salt solution, and then dried or calcined, or after drying or calcining, an appropriate It performs a reduction process. This is done because of the strong affinity between platinum group ions and porous carriers when impregnated with a platinum group active metal salt solution without acid or alkali treatment.
This is because platinum group ions are supported only on the surface or surface layer of the catalyst and are not distributed inside the catalyst.

The above method involves treating a catalyst in which group Ⅰ metals and group Ⅰ metals of the periodic table are supported on a porous carrier with an acid or alkali to infiltrate a platinum active metal salt solution into the catalyst. It homogenizes the distribution of active metals,
When treated with acid or alkali, metals from Group ■ and Group ■ of the periodic table
There is a problem in that it is not possible to prevent the group metals from being partially eluted and reducing the catalytic ability.

The object of the present invention is to provide a hydrotreating catalyst that can be used for hydrogenation of coal liquefaction solvents by supporting ruthenium and/or platinum on a catalyst in which metals of group Ⅰ and group Ⅰ of the periodic table are supported on a porous carrier. Hereinafter, it will be referred to as a catalyst for hydrogenation of coal liquefaction solvent.

), it is an object of the present invention to provide a method for efficiently and uniformly supporting the catalyst from the surface to the inside thereof.

[Means for Solving the Problems] The method of the present invention for solving the above problems involves applying an impregnating liquid containing ruthenium and/or platinum to a catalyst in which a metal of group Ⅰ or a metal of group ② of the periodic table is supported on a porous carrier. In a method for producing a hydrogenation catalyst by impregnating, drying or calcination, or by performing an appropriate reduction treatment after drying and/or calcination, a ruthenium compound is added to an ethyl alcohol-water mixture having an ethyl alcohol content of 50% or more. and/or a solution in which a platinum compound is dissolved is used as an impregnating solution.

[Function] Metals of group Ⅰ and group ② of the periodic table used in the method of the present invention
The catalyst in which a group metal is supported on a porous carrier is a generally commercially available hydrogenation catalyst.

The ruthenium compound and/or platinum compound used in the present invention may be any compound that can be dissolved in an ethyl alcohol-water mixed solution containing 50 ffij 1% or more of ethyl alcohol, such as nitrates, chlorides, ammonium salts, and the like. Considering economic efficiency, it is preferable to use chloride.

The reason why the solution for dissolving the ruthenium compound and/or platinum compound is an ethyl alcohol-water mixed solution containing 50% by weight or more of ethyl alcohol is because if the proportion of ethyl alcohol is less than 5% by weight, the viscosity of the solution will increase, and the ruthenium This is because the affinity between ruthenium or platinum and a supported catalyst such as Mo-Ni becomes strong, making it difficult to uniformly support ruthenium or platinum inside the catalyst. It is also possible to use only ethyl alcohol in the method of the present invention.

There is no need to particularly limit the amount of ruthenium and/or platinum supported, and if the amount to be supported is large, the impregnation operation may be carried out several times.

After impregnating with ruthenium and/or platinum using the above impregnating solution, a catalyst for hydrogenation of coal liquefaction solvent is obtained by drying or calcination, or by performing an appropriate reduction treatment after drying and/or calcination.
The conditions for this operation may be normal conditions and do not need to be particularly limited.

[Example-1] Commercially available hydrotreating catalyst KF-153S (manufactured by Nippon Ketchien Co., Ltd. MoO3 15% by weight, Ni0 3% by weight
The impregnating liquid was prepared by dissolving 2.7 g of ruthenium chloride containing 44.5% by weight of Ru in ethyl alcohol and bringing the total volume to 90 ml. It was impregnated into 100 g of supported catalyst, then dried with hot air at 110°C, and then calcined in soo'c to prepare catalyst A for hydrogenation of coal liquefaction solvent. This catalyst A is 1
．． Containing 0% Rub, we performed line analysis along the cross section of the catalyst using an X-ray microanalyzer to examine the distribution of Ru, and found that Ru was supported almost uniformly throughout the interior. .

This catalyst A is expected to exhibit high performance as a coal liquefaction solvent hydrogenation reaction.

[Example-2] Instead of ethyl alcohol in Example-1, a mixed solution of ethyl alcohol and water with a weight ratio of 1=1, 2:1, and 3:l was used, and other conditions were set as in Example-1. Coal liquefaction solvent hydrogenation catalysts B, C, and D were obtained in the same manner as in Example 1. All of these catalysts contain 1.0% of Rub, and when we performed line analysis along the cross section of the catalyst using an X-ray microanalyzer to examine the distribution of Ru, we found that in all of them, Ru was almost uniform throughout the interior. I found out that it was being carried.

These catalysts B, C, and D can be expected to exhibit high performance for coal liquefaction solvent hydrogenation reactions.

[Example-3] Same as Example-1 using an impregnating solution obtained by dissolving ruthenium chloride in ethyl alcohol in an amount such that the supported amount is 0.5.3.5.7% by weight as Ru5t. A catalyst for hydrogenation of coal liquefaction solvent ESFSG,H was obtained. Line analysis was performed on these catalysts along the cross section of the catalyst using an X-ray microanalyzer to investigate the distribution of Ru.
was found to be supported almost uniformly throughout the interior.

These catalysts E, F, G, and H can be expected to exhibit high performance for coal liquefaction solvent hydrogenation reactions.

[Example-4] 200 g of commercially available hydrogenation catalyst KP-153S catalyst carrier (manufactured by Nippon Ketchien Co., Ltd.), 37.8 g of tungstic acid, #R28 wt ffi% ammonia water 2
W- was dissolved in a solution of 5 μl and 10 ml of water, and after filtering the undissolved residue, 15.2 g of nickel nitrate was added, and water was added so that the total liquid volume was 90 + * 1. Impregnated with Ni impregnating solution and dried at 110°C for 20 hours, then heated to 600°C.
The mixture was calcined for 2 hours to obtain a W-Nt supported catalyst.

Example 1 was carried out using this W-Ni supported catalyst and using an impregnating solution obtained by dissolving ruthenium chloride in ethyl alcohol in an amount such that the supported amount was 3.5% by weight as Rub.
A coal liquefaction solvent hydrogenation catalyst I%J was obtained in the same manner as above. When these catalysts were subjected to line analysis along the cross section of the catalyst using an X-ray microanalyzer and the distribution of Ru was investigated, it was found that Ru was almost uniformly supported throughout the catalysts.

These catalysts (1) and (J) are expected to exhibit high performance for coal liquefaction solvent hydrogenation reactions.

[Example-5] Instead of ruthenium chloride in Example-1, 37% by weight of p
Using an impregnating solution in which 3.2 g of chloroplatinic acid containing T was dissolved in ethyl alcohol and the total volume was 90 ml, other conditions were the same as in Example 1 to obtain catalyst K for hydrogenation of coal liquefaction solvent. . This catalyst contains 1.0ffiffi% PtO□, and line analysis was performed along the cross section of the catalyst using an X-ray microanalyzer to investigate the Pt distribution.
was found to be supported almost uniformly throughout the interior.

These catalysts are expected to exhibit high performance for coal liquefaction solvent hydrogenation reactions.

[Comparative Example-1] A catalyst for hydrogenating a coal liquefaction solvent was obtained in the same manner as in Example-1 except that an impregnating liquid obtained by dissolving ruthenium chloride in water was used. The amount of Ru0z supported on this catalyst is z, oilt%
When the distribution of Ru was investigated by line analysis along the cross section of the catalyst using an X-ray microanalyzer, it was found that Ru was only supported on the surface layer within 200 μm from the surface.

This catalyst cannot be expected to exhibit high performance for coal liquefaction solvent hydrogenation reactions.

[Comparative Example-2] Instead of ethyl alcohol in Example N-1, a mixed solution of ethyl alcohol and water with a weight ratio of 1:2 and 1:3 was used, and other conditions were the same as in Example-1. A catalyst MSN for coal liquefaction solvent hydrogenation was obtained. Ru5 of these catalysts
The amount of T supported was 1.0% by weight in each case, and line analysis was performed along the cross section of the catalyst using an X-ray microanalyzer.
When we investigated the distribution of u, we found that M is within a range of 500 μm from the surface, and N is within a range of 300 μm from the surface.
It was found that only u was supported.

These catalysts MSN cannot be expected to exhibit high performance for coal liquefaction solvent hydrogenation reactions.

[Effect of the invention] According to the method of the present invention, the ethyl alcohol content can be reduced to 50
Since the impregnating liquid is a liquid obtained by dissolving a ruthenium compound and/or a platinum compound in a mixed solution of ethyl alcohol and water of % or more, the viscosity of the impregnating liquid can be reduced, and the affinity of ruthenium and/or platinum with the catalyst can be reduced. Therefore, ruthenium and/or platinum can be uniformly dispersed and supported inside the supported catalyst such as Mo-Ni. Therefore, a high-performance catalyst can be obtained easily and efficiently.

Claims (1)

[Claims] A catalyst in which a porous carrier is supported with a Group VI metal or a Group VIII metal in the periodic table is impregnated with an impregnating solution containing ruthenium and/or platinum, and then dried or calcined, or after drying and/or calcining, an appropriate reduction treatment is performed. A method for producing a hydrogen treatment catalyst by performing hydrogenation, characterized in that the impregnating liquid is a solution in which a ruthenium compound and/or a platinum compound is dissolved in an ethyl alcohol-water mixture having an ethyl alcohol content of 50% or more. A method for producing a chemical treatment catalyst.