JPS6044013B2 - Method for producing a catalyst for hydrotreating hydrocarbons - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for hydrogenating coarse-grained spent hydrocarbons in which a transition metal compound is supported on an amorphous carrier in a state where it can be eluted when it comes into contact with an alumina hydrosol or an alumina-silica hydrosol. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises pulverizing a treatment catalyst to a volume average particle diameter of 200 μm or less, and mixing and molding the pulverized product with alumina hydrosol or alumina silica hydrosol. Regarding.

Catalysts consisting of carriers and transition metal compounds are widely used in the chemical industry, both organic and inorganic, and the amount used continues to rise year by year as production increases and new products are developed. It's on.

Therefore, the amount of so-called spent catalysts that must be disposed of is also enormous. However, since these catalysts contain harmful heavy metal components, they cannot be disposed of by dumping or landfilling, and rendering them harmless requires a heavy economic burden and causes secondary pollution. These disposals are becoming a major problem in the industry. Of course, methods for recovering metal components from these catalysts or reusing them are also being researched, but currently the number of target catalysts is extremely limited. On the other hand, since the sulfur or nitrogen content contained in hydrocarbons causes environmental pollution when burned, it is difficult to remove them by hydrotreating them under high hydrogen pressure and high temperature in the presence of a catalyst. It is being carried out on a regular basis.

However, in the removal process by hydrogenation treatment of these sulfur or nitrogen components, V, Ni, Fe, Cr,
Since oil-soluble metal compounds such as Cu are removed at the same time, these metals are deposited on the catalyst, resulting in an accelerated decline in the desulfurization and denitrification activities of the catalyst. For this reason, the amount of hydrotreating catalysts used has become extremely large, and there is a demand for supplying these catalysts as inexpensive and highly active catalysts. Under such current circumstances, the present inventors
We aim to develop and provide an excellent hydrotreating catalyst using so-called spent catalysts.

In the present invention, the spent catalyst is a coarse-grained transition metal compound supported on an amorphous carrier in a state that can be eluted when it comes into contact with alumina hydrosol or alumina-silica hydrosol. ) is pulverized to a volume average particle diameter of 200 μm or less. This used catalyst raw material is usually pulverized as is, but if it contains impurities such as carbon, it may be pulverized after being fired. The pulverization method may be a wet method, a dry method, or a combination of both methods. Fine pulverization in this case removes some of the carbonaceous matter and metals deposited on the surface of the coarse catalyst, exposes the active pores inside the catalyst to the surface, and also This is carried out for the purpose of easily dissolving the water-soluble catalytic metal component and dispersing it uniformly in the mixture. Therefore, the diameter of the pulverized particles is arbitrarily determined depending on the purpose of use of the catalyst raw material or the obtained catalyst, but usually the smaller the particle diameter, the better. Generally, an average particle diameter of 200 μm or less is effective for the purpose of the present invention, but if necessary. Depending on the situation, it may be finely pulverized to a size of 10 μm or less. In the catalyst produced by the method of the present invention, the transition metals include Zn, Cu, Ag, and Pd.
, Pt, Ni, CO, Fe, Mn, Cr, MO, W, ■
These metals, as well as oxides, sulfides, and halogens, are effective! compounds, sulfates or other compounds can be used. It can be obtained by adding one or more porous minerals such as sepiolite, bauxite, laterite, or allofene to the spent catalyst in the crushing process and crushing them simultaneously, or by crushing both separately and then mixing them. It can contribute to improving catalyst activity, reaction selectivity, catalyst life, and catalyst strength. Next, the raw material that has been pulverized is mixed with alumina hydrosol or alumina silica hydrosol to obtain a homogeneous mixture.

In this case, the alumina hydrosol may be one obtained by hydrolyzing an aluminum salt, one obtained by hydrolyzing an alkali aluminate or precipitating an alumina hydrate with carbon dioxide gas, or an alumina obtained by a hydration reaction of aluminum alkoxide. The hydrosol may be used as it is, or if necessary, a large amount of water may be partially or substantially replaced with a water-soluble solvent such as alcohol. As the alumina-silica hydrosol, one obtained by a neutralization reaction between an aluminum salt and an alkali silicate, or a mixture of an alumina hydrosol and a silica hydrosol is used. The composition, properties, etc. of these hydrosols are determined by the required properties of the catalyst, especially the pore volume. These hydrosols act as effective binders in the molding and firing processes, and the large amount of water contained in the hydrosols elutes metal components from the finely ground raw material, and these elute during mixing with the finely ground material. It functions to uniformly disperse the metal components into the finely ground material. This effect is extremely important as the process of the present invention utilizes a spent catalyst. Furthermore, most of the water contained in the hydrosol is lost during the drying and calcination steps after shaping, with the effect of leaving a large specific surface area and pore volume in the catalyst product. The proportion of alumina hydrosol or alumina silica hydrosol to be added depends largely on the type of pulverized raw materials and their particle size distribution, but assuming a standard distribution between 200μ and 1μ, the ratio of anhydrous to the weight of the pulverized raw materials is The amount used is 1 to 8% by volume, preferably 50 to 7% by volume. This ratio is arbitrarily selected depending on the required catalyst properties. The molding is carried out by a conventional catalyst molding method.

The mixture mixed with alumina hydrosol or alumina silica hydrosol is water-adjusted and molded using a press, an extruder, a pelletizing machine, etc. The shape of the molded body is appropriately selected depending on the raw materials used and the purpose of use.
When the resulting catalyst is used for hydrotreating hydrocarbons, particularly for demetalization, it is preferable that the molded body be a spherical body with a diameter as small as possible, but a cylindrical body with a diameter of 5TIun or less may also be used. can. The molded catalyst is
Usually, it is fired after passing through a drying process, but either the drying process or the firing process, or both of these processes can be omitted.

The catalyst according to the present invention is a catalyst developed for the purpose of effectively utilizing catalyst metals contained in so-called spent hydrocarbon hydrotreating catalysts, and the metal components required for the produced catalyst are as follows: If a used catalyst is selected and used in advance, there is no need to add other metal components, but if necessary, it can be supported by a normal method after calcination, or
It can also be added during the mixing step with alumina hydrosol or the like or during the grinding step.

As mentioned above, the metal components in the spent catalyst are uniformly dispersed in the raw material during the mixing process with the hydrosol, but if the dispersion is insufficient, an organic or inorganic aqueous solution or acid Alternatively, by adding an alkali, metals with poor solubility in the hydrosol can be dissolved in advance to improve uniform dispersion. Alternatively, the catalyst after shaping and firing may be treated with the above aqueous solution to uniformly disperse the metal components within the catalyst. Pore surface area as well as pore volume have a significant influence on catalyst life rather than catalyst activity. The products for hydrogenation treatment range from so-called guard reactors to those for selective demetalization.If there are more severe requirements under the above conditions, alumina, alumina-silica, or A porous carrier is added and molded to produce the desired catalyst. The catalyst obtained by the method of the present invention can be suitably used as a catalyst for hydrotreating hydrocarbons containing sulfur, nitrogen or soluble metal compounds.

For example, hydrogen pressure 20~200k9/Cltl3OO~4
It can be used for simultaneous demetalization, deasphaltenization, or desulfurization of hydrocarbons at a temperature of 50°C.
The catalyst can be used in a fixed bed, fluidized bed, or moving bed. When utilizing a spent catalyst from a hydroprocessing process intended for the use of the catalyst to be produced as the raw material spent catalyst, the process of the invention forms a complete recycling of the catalyst and is highly preferred.

Next, the present invention will be explained by examples. Example 1 A catalyst suitable for hydrotreating heavy oil, particularly for demetalization, was obtained by this method using as a raw material a desulfurization catalyst using degraded alumina as a carrier, which had been used for hydrodesulfurization of residual oil.

The properties of the spent catalyst used in this experiment are shown below. 4 parts of alumina as anhydride for 1 (4) parts of the above spent catalyst
Alumina hydrosol (alumina content: 10%) was added in an amount of (1) part and thoroughly ground and mixed in a ball mill packed with magnetic balls.

The spent catalyst was thoroughly ground, and 50μ
After no more solid content was observed, the mixture was filtered to obtain a cake consisting of a homogeneous mixture of spent catalyst powder and alumina hydrosol. The moisture content of this cake was 71.2%. Next, the cake was extruded into a cylinder having a diameter of 0.8 TI$L, and thoroughly dried at 120°C for 2 hours and at 3000C for 2 hours.

After firing this dried product at 450°C for 2 hours, it was impregnated with a 6N ammonia aqueous solution to approximately 50% of the fired product, and then left at room temperature overnight to remove the metals in the fired product. Part of it was solubilized so that it was uniformly distributed in the fired product. This was further dried at 120°C for 2 hours and further calcined at 650'C for 1 hour to obtain a catalyst for hydrogenation treatment. The physical properties of the obtained catalyst were as follows. In addition, most of the carbon and sulfur content in the raw material used catalyst were removed by calcination.

Using the catalyst obtained above and the used desulfurization catalyst, tar sand yumene having the following properties and containing 0.78% ash was hydrogenated.

Viscosity (50℃, Cp) 2100 The reaction conditions are as follows.

The properties of the produced oil 5 minutes after the start of the reaction are as follows.

Example 2 --- Using the same used catalyst as in Example 1, alumina-silica hydrosol was added and molded in the same process as in Example 1 to obtain a catalyst for hydrogenation treatment.

That is, in the same manner as in Example 1, 10% alumina sol was added to 1 (1) part of the spent catalyst so that the alumina was 200 parts, and 2 (4) parts of water was added to adjust the viscosity. The mixture was thoroughly ground and mixed using a ball mill.

Next, after confirming that the spent catalyst has been pulverized,
% silica sol as anhydrous silicic acid was added to the spent catalyst, and the mixture was thoroughly mixed.

Claims (1)

[Claims] 1. A coarse-grained spent hydrocarbon hydrotreating catalyst supported on an amorphous carrier in a state where it can be eluted when the transition metal compound comes into contact with alumina hydrosol or alumina silica hydrosol is prepared using a catalyst with a volume average particle diameter of 200 μm. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises finely pulverizing the following, and mixing the finely pulverized product with an alumina hydrosol or an alumina silica hydrosol and molding the mixture.