JP3246932B2 - Metal-containing crystalline aluminosilicate catalyst for disproportionation of toluene - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a disproportionation reaction of toluene.
More specifically, the metal-containing crystalline aluminosilicate catalyst for use in the present invention ,
o, Ru, Rh, Pd, Os, Ir and Pt metal-containing crystalline aluminosilicate containing at least one metal component can be produced economically by a simple operation ,
It relates to a metal-containing crystalline aluminosilicate catalyst which can be advantageously utilized for the disproportionation reaction of toluene.

[0002]

2. Description of the Related Art Conventionally, a catalyst comprising crystalline aluminosilicate (commonly called zeolite) has been used for a conversion reaction of various kinds of hydrocarbons [for example, hydrocracking (hydrocracking, etc.), isomerization, alkylation, Dealkylation, disproportionation, oligomerization, aromatization, hydrogenation, dehydrogenation, reforming, etc.], conversion of oxygenated hydrocarbons such as methanol, hydrogenation of carbon monoxide, etc. Used for a wide range of catalytic reactions. When a crystalline aluminosilicate is used in these reactions, it is often necessary to have a hydrogenation / dehydrogenation ability in addition to the acid function of the crystalline aluminosilicate.
Group I metal) is supported. Known methods for supporting a metal on crystalline aluminosilicate include an ion exchange method and an impregnation method.

In order to obtain a highly active metal-containing crystalline aluminosilicate, it is important to support the transition metal in a highly dispersed state on the crystalline aluminosilicate. Therefore, various methods for supporting a metal in a highly dispersed state on crystalline aluminosilicate have been searched for. At that time, it is also important to support the crystalline aluminosilicate so as not to destroy the specific crystal structure.

Further, in view of controlling physical properties related to catalyst performance (particularly, structural stability such as acid properties important for control of activity and selectivity, and thermal stability such as hydrothermal resistance), crystalline aluminosilicate itself is difficult to control. Composition, eg, SiO ₂ / A
Important factors are the l ₂ O ₃ ratio, the Na ₂ O content, and the type and content of the supported metal. For example, SiO
It is known that those having a low ₂ / Al ₂ O ₃ ratio generally have low thermal stability such as hydrothermal resistance and acid resistance, and are liable to cause coking. When a carrier having a high Na ₂ O content is used as it is as a carrier, the H ⁺ content is correspondingly reduced, so that the acidity decreases and high activity cannot be expected. Used after replacement. By supporting an appropriate metal, structural stability such as catalytic function and thermal stability can be improved, and such means are often effective.

[0005] Such adjustment of the composition of the crystalline aluminosilicate is possible at the time of its synthesis (during hydrothermal synthesis) or at the time of ion exchange, but it is often insufficient in the conventional method. Therefore, the final adjustment of the SiO ₂ / Al ₂ O ₃ ratio, in particular, the removal of excess aluminum is carried out by a dealumination treatment by steaming at a high temperature to obtain structural stability such as thermal stability of crystalline aluminosilicate. It is often practiced to improve the catalytic function. However, since the steaming is performed at a high temperature, it is often difficult to sufficiently achieve dealumination without destroying the crystal structure of the crystalline aluminosilicate. Therefore, development of a method for stably achieving dealumination without necessarily using such a steaming process is also strongly desired. That is, in order to sufficiently utilize the crystalline aluminosilicate for the catalytic reaction, it is necessary to appropriately control the acid properties, suppress the destruction of the crystal structure, and sufficiently maintain the structural stability and catalytic function due to dealumination and the like. It is an important issue to stably support the transition metal with high dispersion and suppressed aggregation.

[0006] A number of techniques have been developed for supporting a transition metal on a crystalline aluminosilicate such as zeolite. For example, Japanese Patent Application Laid-Open No. 52-156798 discloses that a crystalline aluminosilicate (zeolite) is used to improve the catalytic performance, particularly the thermal stability.
A method of performing metal ion exchange under conditions of 1.5 to 5.5 is disclosed. However, according to this conventional ion exchange method, even if the transition metal can be supported in a highly dispersed state, since the simple ion exchange is used, aggregation of the supported transition metal easily occurs, and the amount of the supported transition metal is reduced. There are also problems such as limitations. Further, Japanese Patent Laid-Open No. 58-2
No. 214 describes a method of treating a crystalline aluminosilicate (zeolite) with an aqueous solution of an iron salt having a pH of 2.0 or less to modify the crystalline aluminosilicate so as to give a specific structure and performance. Kaisho 60-2381
No. 50 discloses a supporting method in which crystalline aluminosilicate (zeolite) is treated with a nickel salt aqueous solution having a pH of less than 1.5 so that at least a part of nickel has a bond other than a so-called ionic bond. It is shown. However, since iron has a tendency to deposit, it is difficult to support iron in a high dispersion and a high concentration (high loading ratio) by the above-described method. On the other hand, nickel is also high in the above-described method. There is a disadvantage that the amount that can be supported in a dispersed state is extremely small. Therefore, in the case of iron and nickel, it is not possible to add sufficient functions specific to transition metals, such as sufficient hydrogenation and dehydrogenation ability, to crystalline aluminosilicate.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. The purpose of the present invention is
Dealuminization is performed without destroying the crystalline structure of the crystalline aluminosilicate, and the transition metal having hydrogenation and dehydrogenation ability is sufficiently high while increasing the structural stability such as hydrothermal resistance. In, also developed a method that can be supported in a highly dispersed state and with good stability,
Catalytic functions such as acid function and / or metal function, and further, catalytic performance such as stability such as hydrothermal resistance are significantly improved,
Excellent reaction results for disproportionation of toluene
An object of the present invention is to provide a metal-containing crystalline aluminosilicate catalyst for disproportionation reaction of toluene .

[0008]

In order to achieve the above-mentioned object, the present inventors first set forth a metal belonging to Group VIII of the periodic table other than iron and nickel (that is, Co, Ru, and R).
Focusing on h, Pd, Os, Ir and Pt), intensive studies have been made on a method for supporting these transition metals in a crystalline aluminosilicate such as zeolite in a highly dispersed state with good stability. As a result, SiO ₂ / Al ₂ O ₃
A crystalline aluminosilicate having a specific composition, in which the ratio is equal to or higher than a specific value and the Na ₂ O content is equal to or lower than a specific weight% value, is converted into a compound having a pH lower than a specific value and the specific transition metal. By using an extremely simple operation of bringing into contact with an aqueous solution of a metal salt in which at least one kind of the salt is dissolved, the predetermined transition metal is in a highly dispersed state even when the loading is sufficiently high as well as when the loading is low. It has been found that it is possible to easily obtain a desired metal-containing crystalline aluminosilicate supported stably by the above method. Also,
When the metal-containing crystalline aluminosilicate is manufactured in this manner, the dealumination from the crystalline aluminosilicate also proceeds favorably upon contact with the aqueous metal salt solution, and the thermal stability and structure of the crystalline aluminosilicate carrier such as hydrothermal resistance. It was found that the stability was also remarkably improved, and the catalyst performance such as durability could be remarkably improved.

Furthermore, various metal-containing crystalline aluminosilicate catalysts prepared by this method was confirmed that you have significantly superior to toluene disproportionation.

The present inventors have completed the present invention based mainly on the above findings. That is, the present invention
A crystalline aluminosilicate having a SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of 3.5 or more and a Na ₂ O content of 8.0% by weight or less has a pH of less than 1.5, and ,
A metal-containing crystalline aluminosilicate catalyst for disproportionation reaction of toluene obtained by contacting with an aqueous solution of a metal salt containing at least one metal selected from Co, Ru, Rh, Pd, Os, Ir and Pt. To provide.

In the method of the present invention, the crystalline aluminosilicate to be subjected to the contact treatment with the aqueous metal salt solution (hereinafter sometimes referred to as a raw material crystalline aluminosilicate) has a SiO ₂ / Al ₂ O ₃ ratio. It is important to use a crystalline aluminosilicate having a molar ratio of 3.5 or more and a Na ₂ O content of 8.0% by weight or less. Here, if the raw material crystalline aluminosilicate used has a SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of less than 3.5 or a Na ₂ O content of more than 8.0% by weight, the metal When the treatment is performed in a salt aqueous solution, that is, under a strong acidity having a pH of less than 1.5, troubles such as destruction of a crystal lattice structure specific to crystalline aluminosilicate are likely to occur, and the object of the present invention cannot be achieved. In addition,
The preferred range of the SiO ₂ / Al ₂ O ₃ ratio (molar ratio) is
Usually, a 4.5 to 50.0, the preferred range of Na ₂ O content is 0.1 to 5.0 wt%.

[0012] As the crystalline aluminosilicate to be used in this onset bright as Oite the material crystalline aluminosilicate, and a SiO ₂ / Al ₂ O ₃ ratio is in a molar ratio of 3.5 or more and, Na ₂ O If the content is 8.0% by weight or less, various crystalline aluminosilicates,
Specifically, for example, synthetic zeolites such as pentasil-type zeolites such as Y-type zeolite, X-type zeolite, L-type zeolite, mordenite and ZSM-5; natural mineral-type zeolites such as natural faujasite and clinoptilite Or crystalline aluminosilicates can be used. Among these, Y-type zeolite and the like are particularly preferable. These crystalline aluminosilicates
If the SiO ₂ / Al ₂ O ₃ ratio (molar ratio) and the Na ₂ O content satisfy the above specified criteria, for example, NH ₄ ⁺
Various cation exchange types, such as a type and an H ⁺ type, can be used. For example, NH ⁺ type Y zeolite can be mentioned as an example of a particularly preferable raw material crystalline aluminosilicate. These various crystalline aluminosilicates may be used alone or, if necessary, in combination of two or more as a mixture. Also, these crystalline aluminosilicates
As long as the object of the present invention is not impaired, it can be used in a form containing other components and additives.

Further, it is effective that the crystalline aluminosilicate is subjected to a steaming treatment under appropriate conditions before being brought into contact with the aqueous metal salt solution. This steaming treatment can be suitably performed usually at a temperature in the range of 300 to 810 ° C. At this time, it is usually preferable to use a normal steaming method in which steam is added to the system for treatment.However, depending on the case, the water contained in the crystalline aluminosilicate is steamed by heating, and treated with this steam. Alternatively, a self-steaming method may be employed. In addition, this steaming process is a distribution system,
It can be performed by various methods such as a sealed system.

[0014] The onset Oite bright, the aqueous metal salt solution is contacted with the crystalline aluminosilicate, the specific transition metal namely Co, Ru, Rh, Pd, Os, desired transition metal of Ir and Pt It is important that one or two or more of the above-mentioned salts are dissolved and the pH is less than 1.5. If the pH of the aqueous metal salt solution used here is 1.5 or more, the dealumination from the crystalline aluminosilicate does not proceed sufficiently, and therefore, the improvement of the stability of the crystalline aluminosilicate, such as hydrothermal resistance, is sufficiently performed. It is not possible to achieve this, and it is not possible to stably support a predetermined transition metal in a highly dispersed state because of insufficient introduction of the transition metal into lattice defects formed by dealumination. An obstacle occurs, and the object of the present invention cannot be sufficiently achieved. As a method for adjusting the pH of the aqueous metal salt solution to less than 1.5, various methods can be used. Usually, for example, a method of adding an appropriate acid such as hydrochloric acid, nitric acid, sulfuric acid or the like is suitably adopted. You. Note that hydrofluoric acid as an acid to be added is not preferable because it destroys the structure of the crystalline aluminosilicate.

The form of the transition metal used in the preparation of the aqueous metal salt solution is not particularly limited as long as it can be prepared in the aqueous metal salt solution in consideration of pH and the use of addable components such as an acid to be added. Without, depending on the case, a predetermined transition metal can be used as various compounds or in a metal state such as a simple metal, but usually, a nitrate,
Inorganic salts such as sulfates, chlorides, bromides and iodides, organic acid salts such as acetates, metal chlorides such as chloroplatinic acid or salts thereof, various complexes or complex salts, oxides, hydroxides, carbonates Are preferably used. Among these, nitrates,
Chloride or metal chlorides are particularly preferably used. Note that the aqueous metal salt solution may contain one desired transition metal component among the transition metals,
It may contain a desired combination of two or more transition metal components. Further, the metal salt aqueous solution may contain other components, if necessary, as long as the object of the present invention is not impaired.

The concentration of the transition metal component in the aqueous metal salt solution is not particularly limited, but is usually 0.01 to 2.5 mol / mol, calculated as the transition metal concentration.
It is preferable to appropriately select from the range of l.

Although various methods can be applied as a method for bringing the raw material crystalline aluminosilicate into contact with the metal salt aqueous solution, usually, the raw material crystalline aluminosilicate is simply immersed in the predetermined metal salt aqueous solution. It is enough to do. At that time, by improving the contact efficiency by stirring or the like, the object can be achieved with a shorter contact treatment. In addition, by repeating this contact treatment a plurality of times, a crystalline aluminosilicate having a predetermined high transition metal content can be easily obtained. This contact treatment is usually carried out at a temperature in the range of 0 to 100 ° C and 0.5 to 1
This can be suitably achieved by performing for about 0 hours.

As described above, by carrying out the contact treatment with an aqueous solution of a predetermined metal salt, it is possible to obtain a crystalline aluminosilicate in which a desired transition metal component is supported and contained in various amounts, ie, a metal-containing crystalline aluminosilicate. Can be. The metal-containing crystalline aluminosilicate thus obtained can be used as it is as a catalyst or a catalyst component, but usually, after the metal salt aqueous solution treatment, the obtained metal-containing crystalline aluminosilicate is subjected to a conventional method. After sufficiently washing with water and drying appropriately, it is preferable to bake it under appropriate conditions. This firing is usually performed at 300
It is suitably carried out at a temperature in the range of -800 ° C.

The metal-containing crystalline aluminosilicate obtained by the treatment with the aqueous metal salt solution may be appropriately shaped according to a conventional method and then subjected to the calcination. Also,
It may be molded at any point before firing. . This molding can be performed according to a conventional method.
If necessary, a suitable binder component may be added.

As described above, from the predetermined crystalline aluminosilicate, Co, Ru, Rh, Pd, Os,
A metal-containing crystalline aluminosilicate containing at least one metal component of Ir and Pt can be produced economically by a simple operation.

[0021] Thus, the present onset facie Thus obtained metal-containing crystalline aluminosilicate catalyst may be contained supported good stability of the transition metal component of the in a highly dispersed state, moreover, the crystalline aluminosilicate specific Can be suitably carried out without destroying the crystal lattice structure of the above, and the structural stability such as hydrothermal resistance of the crystalline aluminosilicate carrier and thus the metal-containing crystalline aluminosilicate catalyst can be remarkably improved. In addition, at the time of dealumination, at least a part of the transition metal can be incorporated into the lattice structure of the crystalline aluminosilicate, so that the catalyst performance can be significantly improved from this point as well. For example, aggregation of the transition metal component can be significantly suppressed, and the desired transition metal component can be stably supported and contained in a highly dispersed state until the loading ratio is sufficiently high. By producing a metal-containing crystalline aluminosilicate according to the method of the present invention in this manner, a conventional method such as an impregnation method using a high-pH metal salt aqueous solution or a conventional metal-containing metal containing nickel or iron is used. Compared with crystalline aluminosilicate, it is possible to easily improve catalyst performance such as improvement of catalyst activity, improvement of selectivity, suppression of coking, and increase of catalyst life.

[0022] That is, metals-containing crystalline aluminosilicate catalyst of the present invention can be advantageously used for the disproportionation reaction of toluene.

[0023]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples. Example 1 80 g of a powdery NH ₄ Y-type zeolite (crystalline aluminosilicate) having a Na ₂ O content of 1.2% by weight and a SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of 5.0 was concentrated at a concentration of 80 g. 1.0
A solution prepared by adding 6N nitric acid to 800 ml of an aqueous mol / l cobalt nitrate solution to adjust the pH to 0.3, and adding
The contact treatment was carried out by stirring at 2 ° C. for 2 hours. The powder thus treated was filtered, washed with warm water, dried at 90 ° C., and then calcined at 500 ° C. for 2 hours in an air stream to obtain a desired cobalt-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the cobalt-containing crystalline aluminosilicate thus produced.

Next, the powdery cobalt-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was performed as follows, and its catalytic performance was evaluated. That is, using a pressurized fixed bed flow reactor as a reactor, 5 cc of the catalyst body was placed in a stainless steel reactor having an inner diameter of 6 mm.
At a reaction temperature of 350 ° C. and a pressure of 60 kg / cm ^2.
G, liquid hourly space velocity (LHS
V) Disproportionation reaction of toluene was performed under hydrogen pressure under the conditions of 4 hr ^-1 , a supply rate of hydrogen of 210 cc / min, and a hydrogen fraction (toluene as a gas) of 0.2 vol%. Table 2 shows the results.

Example 2 Powdered NH ₄ Y-type zeolite (crystalline aluminosilicate) 2 having a Na ₂ O content of 1.2% by weight and a SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of 5.0 2,000 g was put into a rotary kiln and subjected to a self-steaming treatment at 700 ° C. for 3 hours. Next, 50 g of the crystalline aluminosilicate that had been subjected to the self-steaming treatment was used at a concentration of 1.
6N nitric acid was added to 800 ml of a 0 mol / l aqueous solution of cobalt nitrate to adjust the pH to 0.3.
The contact treatment was carried out by stirring at 5 ° C. for 2 hours. The powder thus treated was filtered, washed with warm water, dried at 90 ° C., and then calcined at 500 ° C. for 2 hours in an air stream to obtain a desired cobalt-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the cobalt-containing crystalline aluminosilicate thus produced.

Next, the powdery cobalt-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Example 3 In Example 1, 6N nitric acid was added to 800 ml of a 1.0 mol / l aqueous cobalt nitrate solution to adjust the pH to 0.3.
6N nitric acid was added to 800 ml of a 0.1 mol / l ruthenium chloride aqueous solution instead of the adjusted solution to adjust the pH.
The same operation as in Example 1 was performed, except that the contact treatment was performed using a solution in which the content was adjusted to 0.3, to obtain a desired ruthenium-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the ruthenium-containing crystalline aluminosilicate thus produced.

Next, the powdery ruthenium-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Example 4 In Example 1, 6N nitric acid was added to 800 ml of a 1.0 mol / l aqueous solution of cobalt nitrate to adjust the pH to 0.3.
The contact treatment was performed using a solution in which 6N nitric acid was added to 800 ml of a 0.1 mol / l rhodium nitrate aqueous solution to adjust the pH to 0.3, instead of the solution adjusted to 0.1 mol / l. By performing the same operation as in 1, the desired rhodium-containing crystalline aluminosilicate was obtained. Table 1 shows the composition and physical properties of the rhodium-containing crystalline aluminosilicate thus produced.

Next, the powdery rhodium-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Example 5 In Example 1, 6N nitric acid was added to 800 ml of a 1.0 mol / l aqueous solution of cobalt nitrate to adjust the pH to 0.3.
6N nitric acid was added to 800 ml of 0.1 mol / l aqueous palladium nitrate solution instead of
The same operation as in Example 1 was performed, except that the contact treatment was performed using a solution of which was adjusted to 0.3, to obtain a desired palladium-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the thus produced palladium-containing crystalline aluminosilicate.

Next, the powdery palladium-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Example 6 In Example 1, 6N nitric acid was added to 800 ml of a 1.0 mol / l aqueous solution of cobalt nitrate to adjust the pH to 0.3.
6N nitric acid was added to 800 ml of a 0.01 mol / l osmium chloride aqueous solution instead of the solution adjusted to
A desired osmium-containing crystalline aluminosilicate was obtained in the same manner as in Example 1, except that the contact treatment was performed using a solution in which H was adjusted to 0.3. Table 1 shows the composition and physical properties of the osmium-containing crystalline aluminosilicate thus produced.

Next, the powdery osmium-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Example 7 In Example 1, 6N nitric acid was added to 800 ml of a 1.0 mol / l aqueous solution of cobalt nitrate to adjust the pH to 0.3.
The contact treatment was performed using a solution in which 6N nitric acid was added to 800 ml of an aqueous solution of iridium (IV) chloride having a concentration of 0.1 mol / l to adjust the pH to 0.3 instead of the solution adjusted to 0.1 mol / l. The same operation as in Example 1 was performed to obtain a desired crystalline iridium-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the iridium-containing crystalline aluminosilicate thus produced.

Next, the powdery iridium-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Example 8 In Example 1, 6N nitric acid was added to 800 ml of a 1.0 mol / l aqueous cobalt nitrate solution to adjust the pH to 0.3.
The contact treatment was performed using a solution in which 6N nitric acid was added to 800 ml of a 0.1 mol / l aqueous solution of chloroplatinic acid to adjust the pH to 0.3, instead of the solution adjusted to 0.1 mol / l. The same operation as in Example 1 was performed to obtain a desired platinum-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the platinum-containing crystalline aluminosilicate thus produced.

Next, the powdery platinum-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Comparative Example 1 In Example 1, 6N nitric acid was added to 800 ml of a 1.0 mol / l aqueous solution of cobalt nitrate to adjust the pH to 0.3.
The contact treatment was performed using a solution in which 6N nitric acid was added to 800 ml of a 1.0 mol / l aqueous solution of nickel nitrate to adjust the pH to 0.3, instead of the solution adjusted to 1. By performing the same operation as in Example 1, a nickel-containing crystalline aluminosilicate was obtained. Table 1 shows the composition and physical properties of the nickel-containing crystalline aluminosilicate thus produced.
Shown in

Next, the powdery nickel-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Comparative Example 2 In Example 1, 6N nitric acid was added to 800 ml of a 1.0 mol / l aqueous solution of cobalt nitrate to adjust the pH to 0.3.
Except that the contact treatment was performed using a solution in which 6N nitric acid was added to 800 ml of an aqueous solution of ferric nitrate having a concentration of 1.0 mol / l to adjust the pH to 0.3 instead of the adjusted solution. The same operation as in Example 1 was performed to obtain an iron-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the iron-containing crystalline aluminosilicate thus produced.

Next, the powdery iron-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst.
Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Comparative Example 3 The same crystalline aluminosilicate used in Example 1 having a Na ₂ O content of 1.2% by weight and SiO ₂ / Al ₂ O
₃ ratio powdered NH ₄ Y-type zeolite (molar ratio) of 5.0 (crystalline aluminosilicate) 50 g, cobalt acetate _{[Co (CH 3 COO) 2} · 4H 2 O] 2.66g
Is dissolved in an aqueous solution of cobalt acetate having a pH of 5.4.
ml. After completion of impregnation, the obtained powder is heated to 120 ° C.
For 4 hours, and then calcined in an air stream at 500 ° C. for 2 hours to obtain a cobalt-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the cobalt-containing crystalline aluminosilicate thus produced.

Next, the powdery cobalt-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Comparative Example 4 In Comparative Example 3, ammonium ruthenate [(NH ₄ ) ₄ RuC was replaced with 20 ml of an aqueous solution of cobalt acetate.
l ₆ ] A ruthenium-containing crystalline aluminosilicate was obtained in the same manner as in Comparative Example 3, except that the solution was impregnated with 20 ml of an aqueous solution of ammonium ruthenate chloride having a pH of 4.7 and dissolved in 1.40 g. . Table 1 shows the composition and physical properties of the ruthenium-containing crystalline aluminosilicate thus produced.

Next, the powdery ruthenium-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Comparative Example 5 In Comparative Example 3, ammonium rhodate [(NH ₄ ) ₃ RhCl was used instead of 20 ml of an aqueous cobalt acetate solution.
₆ ] A rhodium-containing crystalline aluminosilicate was obtained in the same manner as in Comparative Example 3, except that 20 ml of an aqueous ammonium rhodate solution having a pH of 5.3 in which 1.17 g was dissolved was impregnated. The composition and physical properties of the rhodium-containing crystalline aluminosilicate thus produced are shown in Table 1.
Shown in

Next, the powdery rhodium-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Comparative Example 6 In Comparative Example 3, ammonium chloride [(NH ₄ ) ₂ PdC] was replaced with 20 ml of an aqueous solution of cobalt acetate.
l ₄ ], and palladium-containing crystalline aluminosilicate was obtained in the same manner as in Comparative Example 3, except that the solution was impregnated with 20 ml of an aqueous solution of ammonium palladium chloride having a pH of 4.9 and dissolving 1.51 g. . Table 1 shows the composition and physical properties of the thus produced palladium-containing crystalline aluminosilicate.

Next, the powdery palladium-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Comparative Example 7 In Comparative Example 3, ammonium chloride osmate [(NH ₄ ) ₂ OsC was replaced with 20 ml of an aqueous solution of cobalt acetate.
l ₆ ] is obtained by performing the same operation as in Comparative Example 3 except that 20 ml of an aqueous solution of ammonium osmium chloride having a pH of 6.1 in which 1.09 g is dissolved is impregnated to obtain an osmium-containing crystalline aluminosilicate. . Table 1 shows the composition and physical properties of the osmium-containing crystalline aluminosilicate thus produced.

Next, the powdery osmium-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Comparative Example 8 In Comparative Example 3, ammonium chloride iridate [(NH ₄ ) ₃ IrC was used instead of 20 ml of an aqueous cobalt acetate solution.
l ₆ ] An iridium-containing crystalline aluminosilicate was obtained by performing the same operation as in Comparative Example 3, except that 20 ml of an aqueous solution of ammonium chloride iridate having a pH of 5.3 in which 1.67 g was dissolved was impregnated. . Table 1 shows the composition and physical properties of the iridium-containing crystalline aluminosilicate thus produced.

Next, the powdery iridium-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

Comparative Example 9 In Comparative Example 3, ammonium chloride [(NH ₄ ) ₂ PtCl ₄ ] was replaced with 20 ml of an aqueous solution of cobalt acetate.
A platinum-containing crystalline aluminosilicate was obtained by performing the same operation as in Comparative Example 3, except that 20 ml of an aqueous solution of ammonium chloroplatinate having a pH of 5.2 and 1.06 g dissolved therein was impregnated. Table 1 shows the composition and physical properties of the platinum-containing crystalline aluminosilicate thus produced.

Next, the powdery platinum-containing crystalline aluminosilicate obtained above was molded at a pressure of 600 kg / cm ² , and the particle size was adjusted to 32 to 65 mesh to obtain a catalyst. Using the catalyst as a catalyst, a disproportionation reaction of toluene was carried out in the same manner as in Example 1, and the catalyst performance was evaluated. Table 2 shows the results.

[0057]

[Table 1]

[0058]

[Table 2]

As can be seen from the results shown in Tables 1 and 2.
The present inventionNo goldGenus-containing crystalline aluminosilicatecatalyst
Is a conventional aqueous solution of a metal salt having a high pH of 1.5 or more.
Compared to those produced by the impregnation method using
The disproportionation yield of toluene is clearly improved. Also book
inventionNo goldGenus-containing crystalline aluminosilicatecatalystIs known
Conventional metal-containing crystalline aluminosilicate
Aluminium containing nickel and iron
The disproportionation yield of toluene is significantly higher than that of
It can be seen that it has improved.

[0060]

According to the onset Akira, according to the present invention, SiO ₂ / Al ₂ O ₃
The specific crystalline aluminosilicate whose ratio is equal to or higher than a specific value and whose Na ₂ O content is equal to or lower than a specific specific weight% value is converted to a specific transition metal having a pH below a specific value and a specific transition metal. Because a specific treatment method of contacting a strongly acidic metal salt aqueous solution that dissolves the salt is used, without destruction of the crystalline structure of the crystalline aluminosilicate, effective dealumination is performed. while increasing the structural stability of such hydrothermal resistance, transition metal even when the high supporting ratio ten minutes, to provide efficiently only in a highly dispersed state was also stable with good supported catalyst by a simple operation
Can be used advantageously for the disproportionation reaction of toluene.
You.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification symbol FI // C07B 61/00 300 C07B 61/00 300 (58) Investigated field (Int. Cl. ⁷ , DB name) C01B 39/00 -39/54 B01J 29/00-29/78

Claims (1)

(57) [Claims] An SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of at least 3.5 and a Na ₂ O content of 8.0% by weight.
Contacting the following crystalline aluminosilicate with an aqueous solution of a metal salt having a pH of less than 1.5 and containing at least one metal selected from Co, Ru, Rh, Pd, Os, Ir and Pt. Of toluene obtained by
Metal-containing crystalline aluminosilicate catalyst for chlorination reaction .