JP3246933B2 - 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, for the metal-containing crystalline aluminosilicate catalyst for use , the crystalline aluminosilicate is converted to M
Metal-containing crystalline aluminosilicate containing at least one selected from o, Cu, Mn, Cr and Ga
A catalyst, advantageously utilize metal-containing crystalline aluminosilicates can be for the disproportionation reaction of toluene
Regarding the catalyst .

[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 for these reactions, the acid function of the crystalline aluminosilicate and the hydrogenation / dehydrogenation ability are often required, and therefore, a transition metal is usually supported. Also,
Depending on the type of metal supported, it is also possible to significantly improve the acid properties of crystalline aluminosilicate.
In denitration catalysts and the like, it is also widely practiced to introduce a metal having an oxidizing / reducing ability into crystalline aluminosilicate. That is, a specific catalytic function can be provided depending on the type of the metal to be supported. Known methods for supporting a metal on crystalline aluminosilicate include an ion exchange method and an impregnation method.

In order to obtain highly active metal-containing crystalline aluminosilicate, it is important to support the active metal on the crystalline aluminosilicate in a highly dispersed state. Therefore, various methods for supporting a metal in a highly dispersed state on crystalline aluminosilicate have been searched for.

[0004] At that time, in order to further enhance the catalytic activity,
It is desirable that a predetermined metal is supported in a highly dispersed state up to a high loading rate. In addition, in order to maintain stable catalyst activity, aggregation of active metal components is suppressed as much as possible, and the highly dispersed state can be stably maintained. Doing so is also important.

[0005] It is also important to support the crystalline aluminosilicate so as not to destroy its unique crystal structure. In addition, from the viewpoint of controlling physical properties related to catalyst performance (particularly, acid stability and structural stability such as thermal stability such as hydrothermal resistance, which are important for controlling the activity and selectivity), the composition of the crystalline aluminosilicate itself, for example, , SiO ₂ / Al ₂ O ₃ ratio, Na ₂ O content, type and content of supported metal are also important factors. For example, SiO ₂ / Al ₂ O ₃
It is known that those having a low ratio generally have low heat stability such as hydrothermal resistance and acid resistance, and are liable to cause caulking. 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.

[0006] 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,
There is also a strong demand for the development of a technique for stably achieving dealumination without necessarily using such a steaming treatment.

That is, in order to sufficiently utilize the crystalline aluminosilicate for the catalytic reaction, it is necessary to 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. In addition, it is an important issue to stably carry a suitable metal in a highly dispersed state while suppressing aggregation.

A number of techniques have been developed for supporting a metal on a crystalline aluminosilicate such as zeolite. Currently, many of the supporting methods are an ion exchange method and an impregnation method. In addition, kneading, dipping, and deposition methods are known.

[0009] For example, JP-A-63-190877 discloses a metal-containing crystalline material prepared by ion exchange using a metal salt aqueous solution, or kneading, impregnating, depositing, or dipping using a metal compound. An example is described in which aluminosilicate is used for the synthesis of pyridine bases. JP-A-2-40238 discloses a method in which a crystalline aluminosilicate is first ion-exchanged with a solution of a polyvalent metal salt, and then supported using a metal salt.

[0010] However, the kneading method, impregnation method, deposition method and immersion method can support a metal to a high concentration (high loading ratio), but as long as the conventional method is used, metal aggregation is likely to occur. It is difficult to carry the metal in the dispersion. On the other hand, the ion exchange method is excellent in that the metal is supported on the crystalline aluminosilicate in a highly dispersed state, but the ion exchange rate (that is, the loading rate) is low in the conventional simple ion exchange method. However, it takes a long time to sufficiently increase the crystallinity. In addition, the method of modifying the crystal lattice structure of the crystalline aluminosilicate itself (that is, for the purpose of removing aluminum or introducing metal substitution into the framework, etc.) However, there is a serious drawback that there is a limit in terms of improvement in structural stability such as hydrothermal resistance and improvement in acid function and metal function (hydrogenation / dehydrogenation ability, etc.).

That is, in the conventional supporting method, it is difficult to support the active metal on the crystalline aluminosilicate in a highly dispersed manner and with high stability up to a high loading ratio, or the crystal lattice structure of the crystalline aluminosilicate itself is difficult. Cannot be sufficiently modified, and even if it is possible, there are problems such as difficulties in selecting conditions for suppressing the destruction of the crystal structure and extremely complicated operation.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. The purpose of the present invention is
Without destroying the crystal structure of the crystalline aluminosilicate, it is possible to easily modify the crystal structure such as dealumination, etc., while improving the structural stability such as hydrothermal resistance,
Developed a method that can stably support metals having various catalytic functions in a highly dispersed state and with a high stability even when the supporting rate is sufficiently high, and has a catalytic function such as an acid function and / or a metal function. Has remarkably improved catalytic performance such as stability such as hydrothermal resistance, and is
An object of the present invention is to provide a metal-containing crystalline aluminosilicate catalyst for toluene disproportionation reaction having excellent reaction performance .

[0013]

Means for Solving the Problems In order to achieve the above-mentioned object, the present inventors first set forth, as active metals to be supported, periodic tables IIIA, IVA, VA, VIA, VIIA, IB, and IB.
Focusing on IIB, IIIB, and IVB group metals, intensive studies have been made on a method for stably supporting these metals in crystalline aluminosilicate such as zeolite in a highly dispersed state. As a result, a crystalline aluminosilicate having a specific composition in which the SiO ₂ / Al ₂ O ₃ 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 to a pH lower than a specific value. And Mo, C
By using a very simple operation of contacting an aqueous metal salt solution in which at least one metal salt containing at least one selected from u, Mn, Cr and Ga is dissolved, not only in the case of a low loading rate, It has been found that even if the loading ratio is sufficiently high, it is possible to easily obtain a desired metal-containing crystalline aluminosilicate in which the predetermined metal is stably supported in a highly dispersed state. In addition, when the metal-containing crystalline aluminosilicate is produced in this manner, the removal of aluminum from the crystalline aluminosilicate and the introduction of substitution of a metal into its crystal lattice structure upon contact with an aqueous solution of a metal salt also suitably proceed, and It was found that the thermal stability and structural stability such as hydrothermal resistance of the aluminosilicate carrier were significantly improved, and the catalyst performance such as durability could be significantly improved.

Further, various metal-containing crystalline aluminosilicate catalysts produced by this method are required to have an acid function and / or a metal function (hydrogenation / dehydrogenation ability, etc.), and furthermore to have stability such as heat resistance. that was applied to various catalytic reaction processes, the catalyst was confirmed to be a remarkably superior catalyst against disproportionation toluene.

The present inventors have completed the present invention based mainly on the above findings. That is, the present invention
A SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of 3.5 or more;
A crystalline aluminosilicate having a Na ₂ O content of 8.0% by weight or less and a pH of less than 1.5
there is provided o, Cu, Mn, disproportionation mold genus containing crystalline aluminosilicate catalyst toluene obtained by contacting a metal salt solution containing at least one selected from Cr and Ga .

[0016] Oite to the onset Ming, crystalline aluminosilicate subjected to contact treatment with the metal salt solution (hereinafter,
This may be referred to as a raw material crystalline aluminosilicate. )), The SiO ₂ / Al ₂ O ₃ ratio is 3.5 in molar ratio.
As described above, it is important to use a crystalline aluminosilicate having 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,
When the metal salt aqueous solution, that is, when the treatment is performed under a strong acidity of less than 1.5, troubles such as destruction of the crystal lattice structure specific to crystalline aluminosilicate are likely to occur, and the object of the present invention cannot be achieved. . In addition, preferable S
The range of the iO ₂ / Al ₂ O ₃ ratio (molar ratio) is usually 4.5.
Is 50, the range of preferred Na ₂ O content is 0.1
~ 5.0% by weight.

[0017] 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, Y-type zeolite, X-type zeolite,
Synthetic zeolites such as pentasil-type zeolites such as L-type zeolites, mordenites and ZSM-5; natural mineral zeolites such as natural faujasites and clinoptilite; and crystalline aluminosilicates can be used. Among these, Y-type zeolite and the like are particularly preferable. These crystalline aluminosilicates are Si
If the O ₂ / Al ₂ O ₃ ratio (molar ratio) and the Na ₂ O content satisfy the above specified criteria, for example, NH ₄ ⁺ type, H
Various cation exchange types such as the ⁺ 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. In addition, these crystalline aluminosilicates can be used in a form containing other components and additives as long as the object of the present invention is not impaired.

Further, it is also 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.

[0019] The onset Oite bright, the aqueous metal salt solution is contacted with the crystalline aluminosilicate, Mo, Cu,
It is important that the aqueous solution contains at least one metal salt selected from Mn, Cr and Ga and has a pH of 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 because the introduction of metal into lattice defects formed by dealumination becomes insufficient, problems such as the inability to stably support a given metal in a highly dispersed state can occur. As a result, 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. As an acid to be added, hydrofluoric acid is
It is not preferable because it destroys the structure of the crystalline aluminosilicate.

[0020] The more than one or two of the metal as used as the metal salt solution, may be used with suitable Yichun selected. If for the purpose of obtaining an effective metal-containing crystalline aluminosilicate improvement of disproportionation yield in disproportionation toluene, among the various metal, especially molybdenum suitably used.

The form of the metal used in preparing the aqueous metal salt solution is not particularly limited as long as it can be prepared into an aqueous metal salt solution in consideration of the pH and the use of an addable component such as an acid to be added. Without, depending on the case, a predetermined metal can be used as various compounds or in a metal state such as a simple metal, but usually, a nitrate, a sulfate,
Inorganic salts such as chlorides, bromides and iodides, organic acid salts such as acetates, metal oxo acids such as perrhenic acid and heteropoly acid or salts thereof (for example, ammonium perrhenate and the like), various complexes or complex salts, Oxides, hydroxides, carbonates and the like are preferably used. Among these, nitrates and chlorides are particularly preferably used. The aqueous metal salt solution may contain one desired metal component among the metals, or may contain two or more metal components in a desired combination. 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 metal component in the aqueous solution of the metal salt is not particularly limited, but is usually selected as appropriate from the range of 0.01 to 2.5 mol / l, calculated as the concentration of the metal. Is preferred.

Various methods can be applied as a method of bringing the raw material crystalline aluminosilicate into contact with the metal salt aqueous solution, but 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. Further, by repeating this contact treatment a plurality of times, a crystalline aluminosilicate having a predetermined high metal content can be easily obtained. This contact treatment is usually performed at a temperature in the range of 0 to 100 ° C. for 0.5 to 10
It can be suitably achieved by performing the treatment for about a time.

As described above, by carrying out the contact treatment with a predetermined metal salt aqueous solution, it is possible to obtain a crystalline aluminosilicate in which a desired metal component is supported and contained in various supported amounts, that is, a metal-containing crystalline aluminosilicate. it can. 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 to 80.
It is preferably carried out at a temperature in the range of 0 ° C.

The metal-containing crystalline aluminosilicate obtained by the treatment with the metal salt aqueous solution may be formed before the firing or after the firing. This molding can be carried out according to a conventional method, and at the time of molding, a suitable binder component may be added as necessary.

As described above, from the predetermined crystalline aluminosilicate, a metal-containing crystalline aluminosilicate containing at least one metal component among the metals belonging to the predetermined group can be economically produced by a simple operation. It can be manufactured with good quality.

In the metal-containing crystalline aluminosilicate catalyst thus produced, the above-mentioned metal component having various catalytic functions such as hydrogenation and dehydrogenation properties is added to the crystalline aluminosilicate having acidity in a highly dispersed state. It can be supported and contained with good stability, and can be suitably dealuminized without destroying the crystal lattice structure peculiar to crystalline aluminosilicate. The crystalline aluminosilicate carrier and, consequently, the metal-containing crystalline aluminosilicate catalyst Can also remarkably improve the structural stability such as hydrothermal resistance. In addition, at the time of dealumination, at least a part of the metal can be incorporated into the lattice structure of the crystalline aluminosilicate, so that the catalyst performance can be remarkably improved from this point as well. For example, the aggregation of the metal components can be significantly suppressed, and the desired metal components can be stably supported and contained in a highly dispersed state until the loading ratio is sufficiently high. Metals containing crystalline aluminosilicate catalyst thus produced present invention, conventional kneading method, impregnation method, as compared with the case of the deposition method, a conventional supporting method such as dipping method or an ion exchange method, the catalyst It is possible to greatly improve catalyst performance such as improvement of activity, improvement of selectivity, suppression of coking, improvement of structural stability such as hydrothermal resistance, and increase of catalyst life.

[0028] That is, metals-containing crystalline aluminosilicate catalyst of the present invention is excellent in various points above, it can be advantageously used for the disproportionation reaction of toluene.

[0029]

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. 0.1
6N hydrochloric acid was added to 800 ml of an aqueous solution of mol / l molybdenum chloride 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 molybdenum-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the molybdenum-containing crystalline aluminosilicate thus produced.

Next, the powdery molybdenum-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) 4 hr ^-1 , supply rate of hydrogen and hydrogen sulfide 210 cc
The disproportionation reaction of toluene under the pressure of hydrogen and hydrogen sulfide was performed under the conditions of 0.2 vol./min and a fraction of hydrogen and hydrogen sulfide (toluene as a gas) of 0.2 vol%. Table 2 shows the results.

Example 2 Powdery 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 subjected to the self-steaming treatment was added to a concentration of 0.
To 800 ml of a 1 mol / l molybdenum chloride aqueous solution, 6N hydrochloric acid was added to adjust the pH to 0.3, and then added.
The contact treatment was carried out by stirring at 75 ° C. for 2 hours. The powder thus treated is filtered, washed with warm water and dried at 90 ° C.
Subsequently, it was calcined at 500 ° C. for 2 hours in an air stream to obtain a desired molybdenum-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the molybdenum-containing crystalline aluminosilicate thus produced.

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

Next, the powdered copper 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 3 shows the results.

Example 4 (Reference Example) In Example 1, 6N hydrochloric acid was added to 800 ml of a 0.1 mol / l aqueous solution of molybdenum chloride to adjust the pH to 0.1.
In place of the solution adjusted to 3, the contact treatment was performed using a solution adjusted to pH 0.3 by adding 6 N nitric acid to 800 ml of a 1.0 mol / l aqueous zinc nitrate solution. By performing the same operation as in Example 1, a desired zinc-containing crystalline aluminosilicate was obtained. Table 1 shows the composition and physical properties of the zinc-containing crystalline aluminosilicate thus produced.

Next, the powdery zinc-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 hydrochloric acid was added to 800 ml of a 0.1 mol / l aqueous solution of molybdenum chloride to adjust the pH to 0.1.
PH 6 by adding 6N nitric acid to 800 ml of a 1.0 mol / l aqueous manganese nitrate solution instead of the solution adjusted to 3.
A desired manganese-containing crystalline aluminosilicate was obtained by performing the same operation as in Example 1 except that the contact treatment was performed using a solution in which was adjusted to 0.3. Table 1 shows the composition and physical properties of the manganese-containing crystalline aluminosilicate thus produced.

Next, the powdery manganese-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 hydrochloric acid was added to 800 ml of a 0.1 mol / l molybdenum chloride aqueous solution to adjust the pH to 0.1.
The contact treatment was performed using a solution adjusted to pH 0.3 by adding 6N nitric acid to 800 ml of a 1.0 mol / l aqueous solution of chromium nitrate instead of the solution adjusted to 3. By performing the same operation as in Example 1, a desired chromium-containing crystalline aluminosilicate was obtained. Table 1 shows the composition and physical properties of the chromium-containing crystalline aluminosilicate thus produced.

Next, the powdery chromium-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 hydrochloric acid was added to 800 ml of a 0.1 mol / l molybdenum chloride aqueous solution to adjust the pH to 0.1.
In place of the solution adjusted to 3, a 6 N nitric acid was added to 800 ml of a 1.0 mol / l aqueous gallium nitrate solution to adjust the pH.
A gallium-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 the content was adjusted to 0.3. Table 1 shows the composition and physical properties of the gallium-containing crystalline aluminosilicate thus produced.

Next, the powdery gallium-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 1 shows the results.

Comparative Example 1 In Example 1, 6N hydrochloric acid was added to 800 ml of a 0.1 mol / l molybdenum chloride aqueous solution to adjust the pH to 0.1.
800 ml of an aqueous solution of ammonium molybdate (pH 4.6) having a concentration of 0.1 mol / l instead of the solution adjusted to 3.
A conventional molybdenum-containing crystalline aluminosilicate was obtained by performing the same operation as in Example 1 except that the contact treatment was carried out by using. Table 1 shows the composition and physical properties of the molybdenum-containing crystalline aluminosilicate thus produced.

Next, the powdery molybdenum-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 80 g of 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. With a concentration of 1.0
800 ml of mol / l cupric chloride aqueous solution (pH 4.0)
Then, the mixture was stirred at 75 ° C. for 2 hours to perform ion exchange. The powder thus ion-exchanged is filtered, washed with warm water, dried at 90 ° C., and subsequently dried in an air stream at 500 ° C.
C. for 2 hours to obtain a conventional copper-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the copper-containing crystalline aluminosilicate thus produced.

Next, the powdered copper-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
2.46 g of copper acetate [Cu (CH ₃ COO) ₂ .H ₂ O] is dissolved in 50 g of powdery NH ₄ Y zeolite (crystalline aluminosilicate) having a ratio (molar ratio) of 5.0. The solution was impregnated with 20 ml of an aqueous copper acetate solution having a pH of 4.7. After completion of the impregnation, the obtained powder was dried at 120 ° C. for 4 hours, and then calcined in an air stream at 500 ° C. for 2 hours to obtain a conventional copper-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the copper-containing crystalline aluminosilicate thus produced.

Next, the powdery copper-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 1 shows the results.

Comparative Example 4 Comparative Example 3 was repeated except that 20 ml of the aqueous copper acetate solution was replaced with 20 ml of an aqueous chromium acetate solution (pH 4.2) in which 5.32 g of chromium acetate [Cr (CH ₃ COO) ₃ ] was dissolved. By performing the same operation as in Comparative Example 3, a conventional chromium-containing crystalline aluminosilicate was obtained. Table 1 shows the composition and physical properties of the chromium-containing crystalline aluminosilicate thus produced.

Next, the powdery chromium-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 1 shows the results.

Comparative Example 5 The same operation as in Comparative Example 3 was performed, except that 20 ml of an aqueous gallium nitrate solution (pH 4.2) in which 1.36 g of gallium nitrate was dissolved was used instead of 20 ml of the aqueous copper acetate solution. Was carried out to obtain a conventional gallium-containing crystalline aluminosilicate. Table 1 shows the composition and physical properties of the gallium-containing crystalline aluminosilicate thus produced.

Next, the powdery gallium-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, manganese acetate [Mn (CH ₃ COO) ₂ .4H ₂ O] 2.24 was used instead of 20 ml of an aqueous copper acetate solution.
g aqueous manganese acetate solution (pH 5.3) 2
A conventional manganese-containing crystalline aluminosilicate was obtained by performing the same operation as in Comparative Example 3 except that 0 ml was used. Table 1 shows the composition and physical properties of the manganese-containing crystalline aluminosilicate thus produced.

Next, the powdery manganese-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. The results are shown in Table 2.

Comparative Example 7 In Comparative Example 3, 20 ml of an aqueous zinc acetate solution (pH 5.4) in which 2.86 g of zinc acetate [Zn (CH ₃ COO) ₂ .2H ₂ O] was dissolved in place of 20 ml of an aqueous copper acetate solution. A conventional zinc-containing crystalline aluminosilicate was obtained by performing the same operation as in Comparative Example 3 except for using. Table 1 shows the composition and physical properties of the zinc-containing crystalline aluminosilicate thus produced.

Next, the powdery zinc-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.
Manufactured by impregnation method and ion exchange method using
The disproportionation yield of toluene is clearly improved
ing.

[0060]

The metal-containing crystalline aluminosilicate of the present invention
The salt catalyst converts a specific crystalline aluminosilicate having a SiO ₂ / Al ₂ O ₃ ratio of not less than a specific value and a Na ₂ O content of not more than a specific value of specific weight to a pH value.
Is less than a specific value, and uses a specific treatment method of contacting a strongly acidic metal salt aqueous solution that dissolves a specific metal salt, destroying the crystalline structure of the crystalline aluminosilicate If the loading rate is high enough for metals that have various catalytic functions such as hydrogenation and dehydrogenation capacity while effectively performing aluminum removal and increasing their structural stability such as hydrothermal resistance without performing in, nor Ki de be stable well supported only in a highly dispersed state, torr
It can be advantageously used for the disproportionation of ene.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C07C 15/08 C07C 15/08 // C07B 61/00 300 C07B 61/00 300 (58) Field surveyed (Int.Cl. ⁷ , DB name) C01B 39/00-39/54 B01J 29/00-29/78

Claims (2)

(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.
Toluene obtained by contacting the following crystalline aluminosilicate with a metal salt aqueous solution having a pH of less than 1.5 and containing at least one selected from Mo, Cu, Mn, Cr and Ga Metal-containing crystalline aluminosilicate catalyst for disproportionation reaction . Wherein this contacting a metal salt solution containing Mo
The disproportionation reaction of toluene according to claim 1 obtained by
Use metal-containing crystalline aluminosilicate catalyst.