JPH02237644A - Production of catalyst - Google Patents

Abstract

PURPOSE:To obtain a catalyst having high activity in spite of a small amt. of an active metal supported by supporting an org. complex of the active metal on a carrier, carbonizing and calcining the complex. CONSTITUTION:An org. complex of a catalytically active metal such as Mo, Co or Ni, e.g., metallophthalocyanine, metallonaphthalocyanine or acetylacetonato-metal is used as starting material, supported on a carrier, carbonized by heating in an inert gas such as nitrogen and calcined by heating in the air. The active metal is prevented from being incorporated into the carrier and a catalyst having high activity is obtd. The catalytic activity can be controlled according to the used starting material and the amt. of the active metal supported can be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a catalyst, and more particularly to a method for producing a catalyst using Mo, Co,
Catalysts are prepared using various stable organic complexes of at least one metal such as Ni and W, and the aim is to develop new catalysts that differ from conventional catalyst functions. That is, by using a stable organometallic complex to immobilize the active metal species on the surface of the carrier, (1) the active metal species can be prevented from being incorporated into the carrier, making it possible to develop highly active catalysts. (2) By changing the type of organometallic complex, it becomes possible to develop a catalyst with controlled catalytic activity as required. (3) By immobilizing the active metal species on the surface of the carrier, it is possible to reduce the amount of active metal species used for the same activity, making it possible to significantly reduce costs.

Prior Art and Problems to be Solved by the Invention In recent years, with the depletion of fossil fuels, it has become increasingly important to efficiently produce gasoline, kerosene, light oil, etc. from hydrocarbons such as heavy and medium oil through desulfurization and hydrorefining. Research is being actively conducted to produce fuel oil. The catalyst used in this case is mainly γ-
Co-Mo, N supported on A1203 etc.
An i-Mo catalyst is used.

These catalysts are mainly prepared by impregnating a carrier with an aqueous solution of an inorganic salt of an active metal species, followed by drying, calcining, and sulfurization. However, during the preparation process, a portion of the metal species is incorporated into the support due to the interaction between the metal species and the support, resulting in a decrease in the surface concentration of the active metal species, and also causing non-uniform sulfidation of the metal during the sulfidation process. These phenomena occur, and the catalyst has the disadvantage that it cannot perform its original function as a hydrotreating catalyst. Furthermore, in order to overcome these drawbacks, it is necessary to increase the amount of active metal species supported on the carrier.

γ-A l 2 0 3 is a stable organic constituent of at least one metal from the chemical metal species Mo, Co, Ni, and W.
Catalysts were prepared by supporting them on carriers such as

As a result, the prototype catalyst had high hydrotreating activity,
Moreover, by changing the type of organic complex and the supporting method, basic functions such as hydrogenation activity and hydrogenolysis activity can be controlled.
It has also become clear that the amount of active metal species supported can be reduced.

The composition of the catalyst of the present invention is A I , Mo , Co
, N i , and W, and the catalyst carrier contains an oxide of AI, such as γ-A 12
0 i, etc., but the active metals include Mo, Ni, Co, and W.
Stable organic complexes of transition metals of at least one metal from are used.

These active metals are used as oxides in an amount of 0.1 to 20 wt%, preferably 0.15 to 10 wt%. Further, as organic constituents, metal phthalocyanine, metal naphthalocyanine, metal acetylacetonate, and metal dimethylglyoxime are used.

The following preparation methods are used for the catalyst preparation method of the present invention.

(1) Preparation method 1 Supporting an organic complex of active metal on a carrier,
Heat treatment (carbonization) is performed in an inert gas such as nitrogen, and then heat treatment (calcination) is performed in air.

(2) Preparation method 2 Supporting an organic complex of active metal on a carrier,
Baking in air.

(3) Preparation method 3 After carbonizing the active metal organic complex in an inert gas such as nitrogen, it is supported on a carrier and then calcined in air. (4) Preparation method 4 Supporting an organic complex of active metal on a carrier,
After firing in air, the second and third active #L organic components are added.

The catalysts prepared in each of the above preparations are subjected to various sulfurization treatments. However, sulfurization with sulfur contained in the hydrogenated product is also included in the meaning of this sulfurization treatment.

Examples of the organic solvent used to support the organometallic complex on the carrier in the above preparation include ethyl alcohol and n-hexane. Furthermore, the processing conditions are as follows.

Carbonization conditions: Temperature increase rate approximately 100°C/lhr Carbonization time approximately 2br~31+rs Atmosphere Firing conditions in inert gas such as N2: Firing temperature approximately 400~600°C Firing time approximately 3~51+rs Atmosphere Sulfiding conditions in air: Sulfiding temperature: about 400-500°C Sulfurizing time: about 1-3 hrs Atmosphere: H2/H2S In the catalysts obtained by the preparation methods (1) to (3) of the present invention, the active metal is a stable organic complex having a certain structure. Because it is added as an active metal, the interaction between the active metal and the support is suppressed during the carbonization and sintering process, and active sites are formed evenly distributed on the surface. Therefore, if the amount of active metal supported is the same, the catalyst has a higher surface concentration than the catalyst prepared by the conventional method. As a result, the catalyst of the present invention exhibits high activity with a low loading.

In addition, the results of measuring the state of the catalyst obtained in the present invention after sulfidation using an X-ray diffraction device or an X-ray photoelectron spectrometer indicate that CO
The sulfidation of active metals, such as catalytic converters, is much easier than with conventional catalyst systems due to the high degree of dispersion of metal species. A further characteristic feature of the catalyst prepared by preparation method (4) is that a stable organic complex skeleton exists on the support surface, and the active metal is fixed by the organic complex, so that it remains in the sulfided state even after sulfidation. It is also conceivable that it may show activity as a metal species.

1st craftsman Next, the present invention will be explained in more detail with reference to Examples.

Example 1 The active metal species of the catalyst include Co or Ni acetylacetoner (an amount equivalent to 3wL% supported amount as Coo or NiO on 100wt% of the carrier) and MO acetylacetonate (7.2wt as MoO3). These organometallic constituents are added to γ-Al 2 O 3 as a carrier, stirred for 24 hours in an organic solvent, and the solvent is distilled off, followed by thorough drying. Next, carbonization treatment was performed at 400°C for 4 hours in a nitrogen stream, and further
The catalyst was air-calcined at 0° C. for 4 hours, and then sulfurized in a H 2 S/H 2 stream at 400° C. for 2 hours (Preparation method 1). The hydrogenation activities were as follows.

1-methylnaphthalene was used as a model compound to measure the hydrogenation activity of the catalyst.
The reaction was carried out under the conditions of a catalyst amount of 1.0 g, an initial hydrogen pressure of 30 kg 7 cm2, a reaction temperature of 350 DEG C., and a reaction time of 2 hours, and the amount of 1-methyltetralin and 5-methyltetralin produced was defined as the hydrogenation activity.

Catalyst Hydrogenation activity (activity of conventional catalyst)/γ-AI. 0. Example 2 Next, a catalyst was prepared using Preparation Method 1 by changing the type of organic complex that was the starting material for Ni and Co. Support γ-Al20
The amount supported on 3 is 3wt% as Coo or NiO,
A catalyst was prepared in the same manner as in Example 1 using 7.2 wt% MoOz. The results are shown below.

Catalyst Hydrogenation Activity/γ-A 120 3 /γ-A 120 3 /γ-Al20, Example 3 The mixture was stirred for 24 hours, the solvent was distilled off, and then thoroughly dried. After drying, air baking was performed at 550°C for 4 hours, and 2
The results of a catalyst prepared by stirring for 4 hours, distilling off the solvent, thoroughly drying, immediately calcining in air at 550°C for 4 hours, and performing sulfurization treatment in the same manner as in Example 1 (preparation method 2) are shown below. Catalyst Hydrogenation activity/γ-Ah○, /γ-A 120:1 Example 4 Mo acetylaceta, the starting material for the active metal Mo, was stirred for a period of time, the solvent was distilled off, and then dried. (Preparation method 4). This was further heated at 400°C for 2 hours with H
The hydrogenation activity was 26.00% when the reaction was sulfurized in a 2S/H2 gas stream.

In addition, as shown in Figure 1, the results of structural analysis using X-ray diffraction showed that CO cyanine, an active metal, was present on the catalyst surface, and Co was fixed on the surface of the carrier by a stable marker. It is clear that the interaction with is suppressed.

Example 5 Catalyst preparation methods 1 to 4 (
However, Mo acetylacetonate was contained in an amount corresponding to the same supported amount as in Example 1, and the results for the hydrogenation activity of the sample (prepared under the sulfiding conditions of Example 4) are shown below. Catalyst preparation method Hydrogenation activity 1st method 18.54% 2nd method 22.24% 3rd method 17.83% 4th method 26.00% Conventional method 14.05% Stable organic name for starting material of metal species It is clear that in all preparation methods, the hydrogenation activity is higher than that in the conventional method.

Example 6 FIG. 2 shows the results of a reaction using a catalyst prepared by Preparation Method 4 by changing the amount of Co lid cyanine added (other conditions being the same as in Example 4). When Co lid cyanine is used, the maximum value of hydrogenation activity is around the Co concentration of 0.3 to 0.4 wt%, and compared with Co-Mo/7-Al2 prepared by the conventional method.
03 The best catalyst! It can be seen that the iCo◯ concentration may be about -1/2 or less. In other words, it is the original. Example 7 The state of the catalysts according to the present invention (preparation methods 1 to 3) after sulfidation was measured using an X-ray photoelectron spectrometer (XPS), and the results are shown in Figure 3. In some cases, some of the active metals remain in an oxidized state even after sulfidation,
Sulfidation has not progressed sufficiently. Since the catalyst according to the present invention has a high degree of dispersion of active metal species, it is easily sulfided, and the peak representing the oxidation state is extremely small. This means that the concentration of active ingredient is high. This is explained by the preparation method 2 shown below.
This is also clear from the results of XPS measurements of the Ni Mo/7 Ah○3-based catalyst. In other words, a catalyst with a small Ni/A1 ratio and a high degree of dispersion using Ni dimethylglyoxime as a starting material has a higher S/N i + M o
It has a large ratio and is easily sulfided, and also exhibits a high hydrogenation activity.

Starting material Ni/AI' S/Mo+N
iNi acetylacetoner}- 11.97
0.796Ni dimethylglyoxime 9.46
0.955 Starting material Hydrogenation activity N
iAcetylacetonate 21.20%Ni dimethylglyoxime 27.53%Also, in the case of CO phthalocyanine prepared by Preparation Method 4, the active metal is fixed in the skeleton of a stable organic component, so it is not sulfurized and the metal is not sulfurized. It is possible that it remains in this state, showing high activity.

[Brief explanation of drawings]

Figure 1 shows C measured by preparation method 4 using an X-ray diffraction device.
o (lid cyanine)/Mo (acetylacetonate)
/γ-A 1 2 0 3 catalyst spectrum. The horizontal axis indicates the diffraction angle 2θ. FIG. 2 shows the reaction results of catalysts prepared by varying the amount of Co lid cyanine added. The vertical axis shows the hydrogenation activity, and the horizontal axis shows the amount of active metal added in terms of Coo. FIG. 3 shows the measurement results of an X-ray photoelectron spectrometer (x p s ), which is the Co2P3/2 photoelectron spectrum of the active metal. 1 is a co-Mo/γ-A1203 catalyst prepared by a conventional method, 2 is a Co (futacyanine)/Mo (acetylacetonate)/γ-A120, catalyst (preparation method 2), and 3 is a Co
(lid cyanine)/Mo (acetylacetonate)/
γ-Al203 catalyst (preparation method 4).

Claims (1)

[Claims] 1. An organometallic complex selected from the group consisting of catalytically active metals phthalocyanine, naphthalocyanine, acetylacetonate, and dimethylglyoxime is used as a starting material, carbonized, and optionally calcined. A method for producing a catalyst, which comprises: 2. In the method for producing a catalyst for hydrotreating, an organometallic complex in which the catalytically active metal is at least one metal selected from the group consisting of Mo, Co, Ni, and W is used as a starting material, where the complex is The above-mentioned production method comprises a metal phthalocyanine, a metal naphthalocyanine, a metal acetylacetonate, and a metal dimethylglyoxime. 3. Supporting the organometallic complex according to claim 2 on a carrier, subjecting the complex to a heat treatment to carbonize it in an inert gas, then a heat treatment to sinter the carbide in air, and then a sulfiding treatment. The manufacturing method according to claim 2, comprising: 4. The production method according to claim 2, which comprises supporting the organometallic complex according to claim 2 on a carrier, heat-treating the complex by directly firing it in air, and then subjecting it to sulfurization treatment. 5. The organometallic complex according to claim 2 is heat-treated to carbonize in an inert gas, the carbide is supported on a carrier, the carbide is heat-treated to be fired in air, and then sulfurization treatment is performed. The manufacturing method according to claim 2. 6. Supporting the organometallic complex according to claim 2 containing the main catalytically active metal on a carrier, heat-treating the complex by directly firing it in air, and then adding the remaining catalytically active metal to the fired product. 3. The production method according to claim 2, which comprises adding the organometallic complex contained therein and then subjecting it to sulfurization treatment.