JPH04197448A - Preparation of catalyst for hydrogenation - Google Patents

Abstract

PURPOSE:To allow uniform impregnation of a carrier with a highly concentration activated metal containing carboxylic acid by adding a carboxylic acid to a mixed solution of the VI group metal and the VIII group metal of a periodic table, then saturating with an alumina hydrate to be dissolved, and allowing this dissolution to be carried by a carrier. CONSTITUTION:Five to thirty % of the VI group metal of a periodic table such as molybdenum and tungsten, in terms of an oxide, for the total weight of a catalyst carrier are mixed with 1 to 8% of the VIII group metal such as nickel and cobalt prepared likewise. After that, a material containing a carboxylic acid such as citric acid and tartaric acid is added at a rate of 0.5 to 5 times one mol of the VI group metal of the periodic table to be dissolved. Then an alumina hydrate is added to this aqueous solution, dispersed and mixed. This mixture is saturated to be dissolved and filtrated. This filtrate thus obtained is allowed to be carried by a carrier such as alumina and alumina- silica. Subsequently, it is possible to impregnate the carrier with a highly concentrated aqueous solution of an activated metal containing the carboxylic acid to the center without addition of a large amount of ammonia gas.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a catalyst for hydrotreating in which an active metal impregnating liquid containing a carboxylic acid can be uniformly dispersed in a catalyst carrier.

(Prior art) In hydrotreating, in which hydrocarbon oil is hydrogenated, desulfurized, denitrified, decomposed, etc. in the presence of hydrogen, a catalyst carrier such as alumina or alumina-silica is used as an active ingredient in the periodic table. 6th
Catalysts on which group metals and group 8 metals are supported are often used.

Conventionally, aqueous solutions containing these salts or aqueous ammonia solutions have been used to support these active metal components, but these are unstable and require short-term release or impregnation into a catalyst carrier. There was a problem in that precipitation occurred in stages. Moreover, in this supporting method, there is a problem that after the active metal is supported, the metals of group 6 and group 8 of the periodic table form composite oxide crystals and become inactive.

As a means to solve these problems, Japanese Patent Application Laid-Open No. 59-69147
The publication discloses a preparation method in which an active metal liquid containing a carboxylic acid such as citric acid or malic acid as a complexing agent is contained in a catalyst carrier such as alumina and fired. The characteristics of this preparation method are that the immersion liquid is stabilized by adding these complexing agents to complex the active metal, and
It is thought that the purpose of this is to suppress the occurrence of precipitation phenomena due to condensation and aggregation of active metals. However, this preparation method has the problem that it is difficult to uniformly impregnate the catalyst carrier with the immersion liquid containing the carboxylic acid described above, and the component distribution is concentrated on the outer surface of the catalyst carrier. There is. This phenomenon is particularly severe when the amount of active metal supported is high, making it impossible to support the active metal uniformly.

On the other hand, in Japanese Patent Application Laid-Open No. 59-102442,
The reason for this is that the viscosity of the immersion liquid was significantly increased by the addition of the above-mentioned organic ligands.Therefore, there is a method of making an active metal liquid containing carboxylic acid such as citric acid or malic acid weakly basic with ammonia gas. A method is disclosed in which viscosity reduction can be achieved with.

(Problems to be Solved by the Invention) However, in the method of JP-A-59-102442, it is not always possible to There is a problem that it is not suitable for mass adjustment.

An object of the present invention is to provide a method for uniformly impregnating a highly concentrated aqueous solution of an active metal containing a carboxylic acid such as citric acid or malic acid.

(Means for Solving the Problems) As a result of intensive research to solve the above problems and achieve the above objects, the present inventors have discovered that alumina hydrate is added to a highly concentrated aqueous solution of an active metal containing a carboxylic acid. The present invention has been completed based on the discovery that the object can be achieved by supporting an immersion liquid in which a saturated amount of is dissolved on a catalyst carrier. That is, the first embodiment of the present invention contains 5 to 30% of the periodic table group 6 metal in terms of oxide and 1 to 8% of the periodic table group 8 metal in terms of oxide based on the weight of the catalyst carrier. as a mixed solution,
Next, at least one of citric acid, tartaric acid, malic acid, and glycolic acid is added and dissolved in an amount of 0.5 to 5 times per mole of Group 6 metal of the periodic table, and subsequently, in this aqueous solution,
This is a method for producing a catalyst for hydrotreating, in which the alumina hydrate is added, dispersed, and stirred to dissolve the alumina hydrate in a saturated amount and filtered, and the filtrate is impregnated and supported on a catalyst carrier, and the second embodiment is 5 to 30% in terms of oxide based on the weight of the catalyst carrier.
Phosphoric acid is added to a mixed dispersion of a Group 6 metal of the periodic table and a Group 8 metal of the periodic table in an amount of 1 to 8% in terms of oxide, and then citric acid and tartaric acid are added. , malic acid, and glycolic acid are added and dissolved in an amount of 0.5 to 5 times per mole of Group 6 metal of the periodic table, and then alumina hydrate is added and dispersed in this aqueous solution.・This is a method for producing a catalyst for hydrogenation treatment in which a saturated amount of alumina hydrate is dissolved by stirring and filtered, and the filtrate is impregnated and supported on a catalyst carrier.

(Function) The sixth metal of the periodic table used to prepare the immersion liquid in the present invention includes molybdenum and tungsten, and their respective salts are used as oxides, such as molybdenum trioxide and molybdate acid. Examples include ammonium, tungsten trioxide, and ammonium tungstate. On the other hand, it is possible to use 12-molybdophosphoric acid, 12-tungstophosphoric acid, and ammonium salts thereof. Further, examples of metals of Group 8 of the periodic table include nickel, cobalt, iron, and chromium, and examples thereof include nitrates, carbonates, and carboxylate ammine complex salts.

Thus, in addition, by adding small amounts of phosphoric acid, very stable and highly concentrated immersion liquids can be prepared. In particular, molybdenum trioxide and tungsten trioxide are used as raw materials for Group 6 metals of the periodic table.
When used in combination with either basic nickel carbonate or basic cobalt carbonate as Group 8 metal salts of the periodic table, by adding a small amount of phosphoric acid, this active metal dip can be Since it does not contain various ions, although it is a highly concentrated immersion liquid, it does not have an unduly high viscosity.

The amount of addition of Group 6 metals and Group 8 metals in the periodic table is as follows: The amount of Group 6 metals in the periodic table in the final composition of the catalyst is 5
-30%, preferably 15-20%, and the Group 8 metal is 1-8%, preferably 3-7% in terms of oxide, and below this lower limit, it cannot be used as a catalyst. A sufficient effect cannot be obtained, and even if the upper limit is exceeded, there is no significant difference in the effect. are listed, and at least one of these is used in the sixth periodic table.
Add 0.5 to 5 times per mole of group metal. Addition amount is 0.
If it is less than 5 times, the effect will be small, and even if it exceeds 5 times, no further increase in effect can be expected, which will impair economic efficiency.

One method is to add alumina hydrate to the immersion solution to dissolve it in a saturated amount, but this is not suitable for use in supporting a high amount of metal due to the low solubility of aluminum carboxylates and sulfates in water. This is because sulfates have high solubility, but at high concentrations the nitrate radicals begin to react with carboxylic acids, which is undesirable.If the immersion liquid contains a high degree of carboxylic acid, alumina hydrate should be used. This is because it is optimal to add and dissolve the maximum amount. After the addition treatment, undissolved alumina hydrate is filtered and used.

As the catalyst carrier, conventionally used alumina, alumina-silica, etc. are used.

An immersion liquid prepared by appropriately selecting the active metal and complexing agent as described above, dissolving them in the proportions described above, dissolving a saturated amount of alumina hydrate, and separating undissolved alumina hydrate by filtration is prepared. By impregnating and supporting the catalyst on a catalyst carrier, it is possible to obtain a product catalyst in which each component is uniformly distributed inside the catalyst carrier.

(Example) Next, examples of the present invention will be described.

Example 1 Molybdenum trioxide (1st class reagent) 64.6g and nickel nitrate (1st class reagent) 62.2g were added to water and heated and stirred.
40% aqueous ammonia was added and completely dissolved.

Next, tartaric acid (reagent grade 1 > 80.75 g) was added and completely dissolved. To this solution, aluminum hydroxide (reagent grade 1 > 80.75 g) was added and completely dissolved.
10g of the solution was added, dispersed, and stirred at 50°C for 3 hours. After stirring further, filter to remove insoluble matter.
Adjust the tL amount to 261 cc to obtain the immersion liquid. This immersion liquid has a specific surface area of 300 m2/g and a pore volume of 0.87 m! !
/ g to 300 g of a cylindrical γ-alumina molded catalyst carrier with a diameter of 1.8 mm, and left at room temperature for 30 minutes. During this time, the immersion liquid almost permeated into the catalyst carrier, and a transparent impregnated body could be obtained. Thereafter, it was dried at 120°C for 16 hours to obtain "Catalyst A".

As a result of analyzing the composition of catalyst A, it was found that molybdenum was 17% by weight in terms of MoO, nickel was 4% by weight in terms of NiO, and the remaining 79% by weight was γ-alumina. Further, the amount of tartaric acid added was 1.0 times the molar ratio of the molybdenum contained.

Furthermore, the distribution of active metals and tartaric acid in catalyst A was determined by EPMA. The results are shown in FIG. 1(a), and all of the molybdenum, nickel, and tartar agents were uniformly supported, and the effect of the alumina hydrate addition treatment was recognized.

Example 2 Ammonium paramolybdate [(NHa)s[M07
024] ・nH2O; f4055.6%]77.5
2g of cobalt nitrate (Co20.2%) and 62.2g of cobalt nitrate (Co20.2%) were added to water, heated and stirred, and 40% aqueous ammonia was added to completely dissolve. Subsequently, citric acid (first class reagent) 85.
3g was added and completely dissolved. To this solution, 10 g of aluminum hydroxide (1st grade reagent) was added and dispersed, and the mixture was stirred at 50° C. for 3 hours, filtered, and the liquid volume was adjusted to 261 CC. This immersion liquid was added to 300 g of the same day-alumina molded catalyst carrier as in Example 1, and left at room temperature for 30 minutes.

During this time, the immersion liquid almost permeates into the catalyst carrier, making it impossible to obtain a transparent impregnated body. Then, at 120℃
After drying for hours, "Catalyst B" was obtained.

Analysis of the composition of catalyst B revealed that molybdenum was 17% by weight in terms of HoO, cobalt was 4% by weight in terms of COO, and the remaining 79% by weight was γ-alumina. The amount of citric acid added was 0.6 times the molar ratio of the molybdenum contained.

Further, the distribution of active metal and citric acid in catalyst B was determined in the same manner as in Example 1, and is shown in FIG. 1(b).

Molybdenum, cobalt, and citric acid were all uniformly supported, and the effect of the alumina hydrate addition treatment was observed.

Example 3 93.0 g of molybdenum trioxide (1st grade reagent) and 27.0 g of cobalt carbonate (Go49.2%) were added to water and brought to a boil, then heated and stirred for 30 minutes, and 20.3 g of orthophosphoric acid was added. It was completely dissolved. After that, 85.3 g of citric acid (1st grade reagent) was added and completely dissolved, and 10 g of aluminum hydroxide (1st grade reagent) was added and dispersed.
After stirring at ℃ for 3 hours, insoluble matter was removed and the liquid volume was reduced to 26℃.
Adjusted to 1 cc. This immersion liquid was mixed with γ similar to that in Example 1.
- Added to 300 g of alumina shaped catalyst carrier and left at room temperature for 30 minutes. During this time, the immersion liquid almost permeated into the catalyst carrier, and a transparent impregnated body could be obtained. Thereafter, it was dried at 120°C for 16 hours to obtain "Catalyst C".

Analysis of the composition of catalyst C revealed that molybdenum was 22% by weight in terms of MoO, cobalt was 4% by weight in terms of COO, 3% by weight in terms of linker mark 205, and the remaining 71% by weight was γ-alumina. Further, the amount of citric acid added was 0.6 times in molar ratio to the molybdenum contained.

In addition, the distribution of active metal and citric acid in catalyst C was determined in the same manner as in Example 1, and is shown in FIG. 1(C).

Molybdenum, cobalt, and citric acid were all uniformly supported, and the effect of the alumina hydrate addition treatment was observed.

Comparative Example 1 261 was prepared in the same manner as in Example 1, except that aluminum hydroxide was added and dissolved and the insoluble matter was not filtered out.
An immersion liquid of cc was prepared, and it was supported on 300 g of γ-alumina molded catalyst carrier in the same manner as in Example 1. During this period, the immersion liquid penetrated incompletely and did not penetrate to the center of the catalyst carrier. After 30 minutes, the mold was dried at 20°C for 16 hours to obtain a "catalyst DJ. The composition determined in the same manner as in Example 1 was 17% by weight of molybdenum in terms of 800, 4% by weight of nickel in terms of NiO, and the balance 79% by weight. % is γ-alumina, and the amount of tartaric acid added was 1.0 times in molar ratio to the molybdenum contained.

In addition, the distribution of active metals and tartaric acid in the catalyst was determined in the same manner as in Example 1, and is shown in Figure 1 ((1).Molybdenum,
It was observed that both nickel and tartaric acid were non-uniform and the concentration was low in the center.

Comparative Example 2 A 261 CC immersion liquid was prepared in the same manner as in Example 2, except that the addition treatment of aluminum hydroxide was not performed, and a γ-alumina shaped catalyst carrier 30 was prepared in the same manner as in Example 2.
0 g was loaded. During this period, the immersion liquid penetrated incompletely and did not penetrate to the center of the catalyst carrier. After 30 minutes, the mold was dried at 20°C for 16 hours to obtain catalyst EJ.

The composition obtained in the same manner as in Example 1 was such that molybdenum was Ho
17% by weight in terms of O, and 4% by weight in cobalt in terms of COO.
The remaining 79% by weight was γ-alumina, and the amount of citric acid added was 0.6 times the molar ratio of molybdenum contained.

In addition, the distribution of active metal and citric acid in catalyst E was determined in the same manner as in Example 1, and is shown in FIG. 1(e). molybdenum,
It was observed that both cobalt and citric acid were non-uniform and the concentration was low in the center.

Comparative Example 3 A 261 CC immersion liquid was prepared in the same manner as in Example 3, except that no aluminum hydroxide was added, and a γ-alumina molded catalyst carrier 30 was prepared in the same manner as in Example 3.
0 g was loaded. During this period, the immersion liquid penetrated incompletely and did not penetrate to the center of the catalyst carrier. After 30 minutes, the mold was dried at 20°C for 16 hours to obtain "Catalyst F".

The composition obtained in the same manner as in Example 1 was such that molybdenum was Ho
22% by weight in terms of O, 4% by weight in terms of Cobalt
, 3% by weight in terms of linker mark 205, the remaining 71% by weight is γ-
The amount of citric acid added was 0.6 times the molar ratio of the molybdenum contained.

Furthermore, the distribution of active metal and citric acid in catalyst F was determined in the same manner as in Example 1, and is shown in FIG. 1(f). molybdenum,
It was observed that both cobalt and citric acid were non-uniform and the concentration was low in the center.

(Effects of the Invention) In the present invention, an immersion liquid in which a saturated amount of alumina hydrate is dissolved in a highly concentrated aqueous solution of an active metal containing a carboxylic acid is supported on a catalyst carrier. It is possible to uniformly impregnate the catalyst support even in the center with a highly concentrated aqueous solution of metal, there is no need to add large amounts of ammonia gas, and there is no large amount of heat generated due to neutralization reaction.
Remarkable effects such as the possibility of large-scale preparation are recognized.

[Brief explanation of the drawing]

FIG. 1 (a), (b), and (c) are component distribution diagrams of catalysts A, B, and C produced by the method of the present invention, and (d
), (e), and (f) are component distribution diagrams of catalysts E and F produced by conventional methods. Patent applicant Sumitomo Metal Mining Co., Ltd.

Claims (1)

[Scope of Claims] 1) a) A mixture of 5 to 30% of a metal from Group 6 of the Periodic Table in terms of oxide and 1 to 8% of a metal of Group 8 of the Periodic Table in terms of oxide based on the weight of the catalyst carrier. b) Next, at least one of citric acid, tartaric acid, malic acid, and glycolic acid is added and dissolved in an amount of 0.5 to 5 times per mole of Group 6 metal of the periodic table; c) Subsequently, alumina hydrate is added to this aqueous solution, dispersed, and stirred to dissolve the alumina hydrate in a saturation amount and filtered, and d) a hydrogenation treatment characterized by impregnating and supporting this filtrate on a catalyst carrier. Method for producing catalyst for use. 2) a) Phosphoric acid is added to a mixed dispersion of a metal from group 6 of the periodic table in an amount of 5 to 30% in terms of oxide and a metal in group 8 of the periodic table in an amount of 1 to 8% in terms of oxide based on the weight of the catalyst carrier. b) Next, at least one of citric acid, tartaric acid, malic acid, and glycolic acid is added in an amount of 0.5 to 5 times per mole of Group 6 metal of the periodic table. c) Subsequently, alumina hydrate is added to this aqueous solution, dispersed, and stirred to dissolve a saturated amount of alumina hydrate and filtered, and d) This filtrate is impregnated and supported on a catalyst carrier. A method for producing a characteristic hydrotreating catalyst.