JP3427507B2 - Catalyst for producing paradialkylbenzene, method for producing the same, and method for producing para-xylene - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst capable of producing a product in which a paradialkylbenzene isomer is substantially in excess of an equilibrium concentration, a method for producing the catalyst, and toluene to paraxylene using the catalyst. The present invention relates to a method of manufacturing.

[0002]

BACKGROUND OF THE INVENTION Paradialkylbenzenes are industrially useful in many cases. For example, paradimethylbenzene (paraxylene) is useful as a raw material for terephthalic acid as a polyester raw material.

Therefore, a catalyst for producing paradialkylbenzene in an equilibrium composition or more is very useful, and several catalysts have been developed so far. For example, JP-A-56-1
One of them is the catalyst described in Japanese Patent No. 33223 and Japanese Patent Publication No. 4-54620. These catalysts use zeolite modified with an alkaline earth metal as a catalyst, but they are very active. It has the drawback of being low.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a catalyst having high activity and high paradialkylbenzene selectivity, a method for producing the catalyst, and a method for producing paraxylene from toluene using the catalyst. To do.

[0005]

In order to achieve the above object, the present invention has been earnestly studied, and as a result, the main cavity has a size of a 10-membered oxygen ring and a silica / alumina ratio of 50.
Zeola larger than a cube with a side of 0.5 micron
Ito crystal is composed mainly of zeolite, which is a main component, catalyst
Contains barium and the amount of binder in the catalyst is
The inventors have found that a catalyst having 10 parts or less with respect to 100 parts of light has a high activity and is excellent as a catalyst for producing paradialkylbenzene, and has reached the present invention.

The catalyst of the present invention has a main cavity size of oxygen 1
It is essential that the zeolite consists of a 0-membered ring and has a silica / alumina ratio of less than 50.

The reason why zeolite having a 10-membered oxygen ring as the main cavity size is used as a catalyst is that the paradialkylbenzene having a small minimum molecular diameter is likely to be produced because the pore diameter is small as is conventionally known.

If the silica / alumina ratio is 50 or more, sufficient activity cannot be obtained. The silica / alumina ratio is preferably 15 or more. If it is lower than this, sufficient acid strength cannot be obtained, which is not preferable.

The size of the main cavity used in the present invention is oxygen 1
Zeolites composed of 0-membered rings are described in, for example, US Pat.
No. 6, the composition and manufacturing method are described in Nature 271,30 Marc.
ZSM- whose crystal structure is described in h, 437 (1978)
5, ZSM-described in British Patent 1334243
8. ZSM-1 described in Japanese Patent Publication No. 53-23280
1, ZSM-described in US Pat. No. 4,001,346
21, ZSM described in JP-A-53-144500
-35, zeolite zeta 1 described in JP-A-51-67299, and zeolite zeta 3 described in JP-A-51-67298.

The zeolite most preferably used in the present invention is mainly composed of crystals having a silica / alumina ratio of less than 50 and larger than a cube in which one side of the zeolite crystal is 0.5 micron or more. The main component means that more than half of the crystals are crystals of such a size.

Such a zeolite is preferably JP-B-61
-8011. That is, an aqueous reaction mixture containing a silica source, an alumina source, an alkali source, and an aliphatic carboxylic acid or a salt thereof is used in the following composition range: SiO ₂ / Al ₂ O ₃ 5 to ₂₀₀ 5 to 100 H ₂ O / SiO ₂ 5 To 200 10 to 50 OH ⁻ / SiO ₂ 0.01 to 1.0 0.02 to 0.8 A / Al ₂ O ₃ 0.1 to 200 0.5 to 100, the crystal is adjusted. It can be produced by reacting until produced. As the silica source, for example, silica sol, silica gel, silica yellow gel, silica hydrogel, silicic acid, silicic acid ester, sodium silicate or the like is used.

As the alumina source, sodium aluminate,
Aluminum sulfate, aluminum nitrate, alumina sol,
Alumina gel, activated alumina, gamma alumina, alpha alumina, etc. are used. As the alkali source, caustic soda, caustic soda, etc. are used, but caustic soda is preferred. These alkali sources are OH in the system.
^- is preferably added as present in the composition.

The aliphatic carboxylic acid or salt thereof has 1 to 12 carbon atoms, preferably 3 to 6 carbon atoms, and more specifically glycolic acid which is a monobasic oxycarboxylic acid,
Lactic acid, hydroacrylic acid, oxybutyric acid or salts thereof, dibasic and polybasic oxycarboxylic acids tartronic acid, malic acid, tartaric acid, citric acid or salts thereof, monobasic carboxylic acids such as formic acid, acetic acid, propionic acid, Butyric acid, valeric acid, acrylic acid, crotonic acid, methacrylic acid or salts thereof, dibasic and polybasic carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid or their Salt is used. As the salt, a water-soluble salt is preferable.
For convenience, one kind or two or more kinds of these aliphatic carboxylic acids or salts thereof may be used.

The thus-prepared aqueous reaction mixture is crystallized in the form of a slurry which is as uniform as possible in a closed container such as an iron, stainless steel or Teflon-lined autoclave. The reaction condition for crystallization is a reaction temperature of 80 to 250 ° C., preferably 1
The reaction time is 5 hours to 30 days,
It is preferably 10 hours to 10 days. The reaction mixture is preferably stirred continuously or periodically during crystallization to maintain a uniform state. The crystallized reaction product is taken out from the closed container after cooling, washed with water, filtered, and dried if necessary. Table 3 shows a typical X-ray diffraction pattern of the zeolite thus synthesized.

The X-ray diffraction pattern was measured by a usual method. That is, for the X-ray irradiation, a diffraction pattern is obtained with a K-α ray of copper by using a Geiger counter spectrometer equipped with a recording device. From this diffraction pattern, a relative intensity of 10
0I / I ₀ (I ₀ is the strongest line) and the lattice spacing d (unit: nm) are determined.

[0016]

[Table 1]

The catalyst of the present invention has a main cavity size of oxygen 1
Zeolite having a 0-membered ring and having a silica / alumina ratio of less than 50 is the main component, but the silica-alumina ratio can usually be measured by Si-NMR or the like. Zeolites having a silica / alumina ratio of less than 50 can be obtained by charging such a composition during the synthesis charging step.
Zeolite has a side of 0 . Zeolite crystals larger than 5 μm cubic are preferred as the main component, which can be measured by a scanning electron microscope.

Zeolite having a main cavity size of 10-membered oxygen ring and having a silica / alumina ratio of less than 50 has a suitable strength as a catalyst when mixed with a binder and molded by extrusion. It is preferable in that it can be obtained. As the binder, fine particles of inorganic oxide such as alumina sol, alumina gel, silica sol, titania sol and zirconia sol, and clays such as kaolin, bentonite and montmorillonite are usually used. The amount of binder added should be 10 parts or less with respect to 100 parts of zeolite .
Need to The absence of any binder is not preferable in terms of catalyst strength. In addition to such extrusion molding, compression molding or the like may be used. After molding, it is usually dried and fired.
Drying is performed at 50 to 250 ° C. for 0.1 hour or more, preferably 0.5 to 48 hours. Firing is performed at 300 to 700 ° C. for 0.1 hour or longer, preferably at 400 to 600 ° C. for 0.5.
~ 24 hours.

It is necessary to contain barium in the catalyst . Ba
The form in which the lithium is contained is not particularly limited, but is preferably an oxide. It does not matter if it enters the ion exchange site as ions. The amount contained is not particularly limited, but 1% by weight or more is preferable as barium . More preferably, it is 2% by weight or more. If the amount is small, sufficient paraselectivity may not be obtained.

Various methods can be used for adding barium . Zeolite powder or a molded body may be impregnated with an aqueous solution of a salt of an alkaline earth metal, or may be evaporated to dryness. However, in the case of using these methods, it is preferable to treat the powder as a powder rather than the molded body if the treatment is to be performed uniformly. However, in the case of treating powder, it is often difficult in the steps such as drying and firing. Therefore, as the simplest method, there is a method of kneading zeolite, barium salt, a binder made of an inorganic oxide, and water and then molding, and this method is the most convenient and is most preferably used. Also, it seems that the effect is the effect of the metal salt of barium , but the kneaded product becomes more sticky than the kneaded product of only the binder and zeolite, and it becomes very easy to mold. The strength of the molded product can also be obtained with a relatively small amount of binder.

The zeolite molded body obtained as described above does not have solid acidity as it is. In order to use it as a catalyst for the production of paradialkylbenzene, it is necessary to add a protonic acid site to the zeolite to give it an acid form. As is well known, the acid type zeolite has, as cations in the zeolite, hydrogen ions or polyvalent cations having two or more valences such as alkaline earth metal ions and rare earth ions. At least part of the valent alkali metal ion is hydrogen ion,
It can be obtained by ion-exchange with ammonium ion which is a hydrogen ion precursor or a polyvalent cation and baking.

In the present invention, an ion exchange treatment is preferred in which treatment with a solution containing an acid and / or ammonium salt compound is carried out, and hydrogen ions and / or hydrogen ion precursors are introduced into the zeolite. The ion exchange treatment is generally performed with an aqueous solution. The acid that can be used is an inorganic acid or an organic acid, but the inorganic acid is more common. Examples of the inorganic acid include hydrochloric acid, nitric acid, phosphoric acid, carbonic acid and the like.
Of course, other materials may be used as long as they contain hydrogen ions. When an inorganic acid is used, it is not preferable to treat it with a solution having a too high concentration because the crystal structure is destroyed. The concentration of the acid used preferably varies greatly depending on the type of the acid, so it is difficult to determine uniquely, and it is necessary to pay sufficient attention so that the crystal structure will not be destroyed during use.

As the ammonium salt compound, an inorganic ammonium salt such as ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium carbonate and aqueous ammonia, or an ammonium salt of an organic acid such as ammonium formate, ammonium acetate and ammonium citrate can be similarly used. Are more preferably inorganic ammonium salts. The concentration of the ammonium salt used is preferably a solution of 0.05 to 4 N, but more preferably about 0.1 to 2 N. As a method for ion-exchanging zeolite with an acid and / or ammonium salt solution, either a batch method or a flow method is preferably used. When the treatment is carried out in a batch system, the solid-liquid ratio is preferably such that the zeolite is in sufficient contact with the liquid, about 1 liter / kg or more. A treatment time of 0.1 to 72 hours is sufficient, preferably 0.5 to 24 hours.
The treatment temperature may be equal to or lower than the boiling point, but it is preferably heated to accelerate the ion exchange rate. When the treatment is carried out by the flow system, a fixed bed system, a fluidized bed system or the like can be used, but it is necessary to take care so that the fluid does not flow unevenly or the ion exchange treatment does not become non-uniform. The ion-exchanged zeolite is then washed with water. Ion-exchanged water or distilled water is preferably used as the washing liquid, and the washing may be either batch type or flow type.

In this way, hydrogen ions and / or ammonium ions, which are hydrogen ion precursors, are introduced into the zeolite and calcined to impart protonic acid points. The step of adding a proton to the above-mentioned zeolite is preferably carried out after shaping the zeolite and, if the catalyst contains an alkaline earth metal, after modifying the catalyst with the alkaline earth metal. The reason is that the treatment in the state of zeolite powder requires a great deal of labor for filtration and the like, and when the alkaline earth metal is modified after the protonation treatment, the acid point is replaced with the alkaline earth metal. The activity may be decreased.

There is no problem of modification with an alkaline earth metal after completion of the protonation step. The modification with an alkaline earth metal, the protonation treatment, and the subsequent treatment with a small amount of the alkaline earth metal are effective in improving the para selectivity. However, the activity is reduced.

The catalyst of the present invention may contain a small amount of hydrogenated metal component. The most preferably used hydrogenated metal component is rhenium. Examples of the method of adding these metal components include a kneading method, an impregnation method, and a physical mixing method of powders. Examples of rhenium that can be used include rhenium oxide, perrhenic acid, ammonium perrhenate, and rhenium sulfide. If the hydrogenated metal is added in a too large amount, the non-aromatic component increases and the aromatic yield decreases. The effect of the addition is, for example, in the production of para-xylene by toluene disproportionation, it is possible to suppress the production of ethylbenzene and ethyltoluene and increase the xylene yield.

The catalyst prepared as described above is subsequently dried and then calcined. 50-250 drying
It is carried out at 0 ° C. for 0.1 hour or longer, preferably 0.5 to 48 hours. The firing is performed at 300 to 700 ° C. for 0.1 hour or more, preferably 400 to 600 ° C. for 0.5 to 24 hours.
By such calcination, the ammonium ions introduced by the ion exchange treatment are converted into hydrogen ions, and the hydrogen ions are further converted into the decationized type by further increasing the calcination temperature. The resulting catalyst can also be used satisfactorily.

Paradialkylbenzene is produced by the catalyst prepared as described above. Paradialkylbenzene is produced by disproportionation, transalkylation or alkylation of monoalkylbenzene. Examples thereof include disproportionation of toluene, methylation of toluene with methanol, ethylation of ethylbenzene, disproportionation of ethylbenzene, methylation of ethylbenzene, and ethylation of toluene. The reaction conditions vary depending on the reaction,
The most industrially useful disproportionation reaction of toluene is carried out, for example, under the following reaction conditions. That is, the reaction operation temperature is 300 to 600 ° C, preferably 350 to 550 ° C. The reaction operation pressure is from atmospheric pressure to 10 MPa, preferably from atmospheric pressure to 5 MPa. Time factor W / F (g-cat * hr / g-mol feedstock) which means contact time of reaction
(W: catalyst weight, F: mol feedstock per hour) is 0.1 to 200, preferably 1 to 100. It is preferable that the reaction system contains hydrogen. A low hydrogen concentration can lead to a deterioration of the activity over time due to the deposition of carbonaceous material on the catalyst. The hydrogen concentration is preferably 1 to 50 in terms of the molar ratio of hydrogen to the feedstock in the reaction system (hydrogen / F).

The preferred reaction conditions have been shown above by taking the disproportionation reaction of toluene as an example. A catalyst having high activity and high para-selectivity for disproportionation of toluene is the same acid reaction as other paradialkylbenzenes. It goes without saying that even when used in the production reaction, the activity is high and the para selectivity is high.

The present invention will be described below with reference to examples.

Comparative Example 1 A zeolite having a silica / alumina ratio of 50 was prepared by the method described in JP-A-59-62347 Example 1.
The product obtained was a zeolite having an X-ray diffraction pattern as shown in Table 1. Crystal size is 0.8 ×
The main component was 0.9 × 0.3 μm crystals.

Comparative Example 2 50 parts of the zeolite prepared in Comparative Example 1 was mixed with 50 parts of silica powder.
Part, 15 parts of silica sol as silica was added, and the mixture was kneaded in a mortar while adding a small amount of water and then extruded to form 1
It was dried at 20 ° C. overnight and calcined at 550 ° C. for 2 hours. An isopropanol solution containing the same amount of titanium isopropoxide as zeolite was brought into contact with the solution at L / S = 2 at room temperature for 1 hour. After the liquid was cut off by decantation, it was dried and fired again, and 60 wt% of nitric acid Ba was added to the catalyst molded product.
Aqueous solution containing 0wt% ammonium chloride and L at 80 ℃
/ S = 2 was contacted for 4 hours. Then L / with 80 ° C water
It was washed 5 times with S = 2. Dry overnight at 120 ° C, 500
Calcination was carried out for 2 hours.

This catalyst was packed in a flow reactor and the reaction was carried out under the following reaction conditions.

Reaction temperature 480 ° C., W / F = 23 g · h /
mol, H ₂ / F = 3 mol / mol, pressure 3 MPa,
Feed composition Toluene (TL) 100% The reaction results are toluene conversion (TL conversion 19%), para-xylene concentration in xylene (PX / (PX + OX + M
X)) = 35%.

Example 1 The amount of raw materials added was adjusted so that the composition of the reaction mixture became SiO 2 / Al 2 O 3 50 H 2 O / SiO 2 20 OH- / SiO 2 0.17 A / Al 2 O 3 4.2 (A is tartaric acid). Zeolite was synthesized in the same manner as Comparative Example 1 except that it was adjusted. The silica / alumina ratio of the produced zeolite was about 35. An X-ray diffraction pattern as shown in Table 1 was obtained for this zeolite. Observation of the crystals with an electron microscope revealed that most of the crystals had a side of 0 . It was larger than the 5 micron cube.

Comparative Example 3 50 parts of the zeolite prepared in Example 1 and 50 parts of silica powder
Part, 15 parts of silica sol as silica was added, and the mixture was kneaded in a mortar while adding a small amount of water and then extruded to form 1
It was dried at 20 ° C. overnight and calcined at 550 ° C. for 2 hours. An isopropanol solution containing the same amount of titanium isopropoxide as zeolite was brought into contact with the solution at L / S = 2 at room temperature for 1 hour. After the liquid was cut off by decantation, it was dried and fired again, and 60 wt% of nitric acid Ba was added to the catalyst molded product.
Aqueous solution containing 0wt% ammonium chloride and L at 80 ℃
Contact for 4 hours at / S = 2. Then L / with 80 ° C water
Wash 5 times with S = 2, dry at 120 ° C overnight, 500 ° C
It was baked for 2 hours.

This catalyst was filled in a flow reactor and a toluene disproportionation reaction was carried out under the following reaction conditions.

Reaction temperature 480 ° C., W / F = 23 g · h /
mol, H ₂ / F = 3 mol / mol, pressure 3 MPa,
Feed composition Toluene (TL) 100% Reaction result is TL conversion 26%, PX / (PX + OX + M
X) = 41%. The activity was higher and the para-selectivity was also higher than the comparative example.

Comparative Example 4 100 parts of the zeolite prepared in Example 1, Ba19 nitrate
And 200 parts of water were sufficiently stirred and then evaporated to dryness. 100 parts of this zeolite and silica sol (15 as silica)
Part) was kneaded and then extruded and molded. This was dried at 120 ° C overnight, baked at 550 ° C for 2 hours, and then 10% at 80 ° C.
After being treated with L / S = 2 for 5 times with the ammonium chloride aqueous solution of No. 3, it was washed with water at 80 ° C. for 5 times with L / S = 2. afterwards,
After drying at 120 ° C. overnight, it was baked at 500 ° C. for 2 hours.

The sample for adsorption measurement was fired at 500 ° C. overnight, then allowed to cool in a desiccator, weighed quickly and filled in an adsorption measuring device, and the temperature was raised to 400 ° C. while drawing a vacuum with a rotary pump in the measuring device. It was heated and held at 400 ° C. for 1 hour while being pulled by a diffusion pump. Then, the temperature of the measurement part was lowered to 120 ° C. and kept constant at 120 ° C. After that, the vacuum line was closed and exposed to ice water temperature (about 0 ° C.) of para-xylene vapor pressure. After 60 minutes, the adsorption of para-xylene almost reached equilibrium. The amount of adsorption at that time was 3.7 wt% with respect to the catalyst. When the adsorption rate of ortho-xylene was measured in the same manner as above, only 10% of the para-xylene equilibrium adsorption amount was adsorbed after 1000 minutes.

When the amount of Ba contained in the catalyst was measured by the atomic absorption method, it was 2%. This catalyst was filled in a flow reactor and a toluene disproportionation reaction was carried out under the following reaction conditions.

Reaction temperature 460 ° C., W / F = 23 g · h /
mol, H ₂ / F = 3 mol / mol, pressure 3 MPa,
Feed composition Toluene (TL) 100% Reaction result is TL conversion 30%, PX / (PX + OX + M
X) = 66%. The aromatic yield was 98.9%.

Comparative Example 5 The zeolite prepared in Example 1 was calcined at 500 ° C. for 2 hours and stirred in a solution of barium isopropoxide in isopropanol at room temperature for 1 hour. The amount of barium isopropoxide is 90 wt% with respect to the zeolite. After that, it was filtered, dried, and calcined at 550 ° C. for 2 hours. After 100 parts of this zeolite and silica sol (15 parts as silica) were kneaded, extrusion molding was performed. This was dried at 120 ° C. overnight, calcined at 500 ° C. for 2 hours, treated with a 10% ammonium chloride aqueous solution at 80 ° C. at L / S = 2 five times, and then 8
It was washed with water at 0 ° C. 5 times with L / S = 2. Then 120
After drying at ℃ overnight, it was baked at 500 ℃ for 2 hours.

The sample for adsorption measurement was fired at 500 ° C. overnight, then allowed to cool in a desiccator, weighed quickly and charged into an adsorption measuring device, and the temperature was raised to 400 ° C. while pulling a vacuum with a rotary pump in the measuring device. It was heated and held at 400 ° C. for 1 hour while being pulled by a diffusion pump. Then, the temperature of the measurement part was lowered to 120 ° C. and kept constant at 120 ° C. After that, the vacuum line was closed and exposed to ice water temperature (about 0 ° C.) of para-xylene vapor pressure. After 60 minutes, the adsorption of para-xylene almost reached equilibrium. The amount of adsorption at that time was 3.5 wt% with respect to the catalyst. When the adsorption rate of ortho-xylene was measured in the same manner as described above, after 1000 minutes, only 20% of the para-xylene equilibrium adsorption amount was adsorbed.

When the amount of Ba contained in the catalyst was measured by an atomic absorption method, it was 15%. This catalyst was filled in a flow reactor and a toluene disproportionation reaction was carried out under the following reaction conditions.

Reaction temperature 455 ° C., W / F = 23 g · h /
mol, H ₂ / F = 3 mol / mol, pressure 3 MPa,
Feed composition Toluene (TL) 100% Reaction result is TL conversion 30%, PX / (PX + OX + M
X) = 72%. The aromatic yield was 98.9%.

Example 2 100 parts of the zeolite prepared in Example 1, 18.6 parts of barium acetate, alumina sol (7.5 parts as alumina)
After kneading, it was extruded and molded. This was dried at 120 ° C. overnight, calcined at 550 ° C. for 2 hours, treated at 80 ° C. with a 10% ammonium chloride aqueous solution at L / S = 2 five times, and then
It was washed 5 times with water at 80 ° C. at L / S = 2. Then 12
After drying overnight at 0 ° C., it was baked at 500 ° C. for 2 hours.

The sample for adsorption measurement was fired at 500 ° C. overnight, then allowed to cool in a desiccator, weighed quickly and filled in an adsorption measuring device, and the temperature was raised to 400 ° C. while drawing a vacuum with a rotary pump in the measuring device. It was heated and held at 400 ° C. for 1 hour while being pulled by a diffusion pump. Then, the temperature of the measurement part was lowered to 120 ° C. and kept constant at 120 ° C. After that, the vacuum line was closed and exposed to ice water temperature (about 0 ° C.) of para-xylene vapor pressure. After 30 minutes, the paraxylene adsorption had almost reached equilibrium. The amount of adsorption at that time was 3.5 wt% with respect to the catalyst. When the adsorption rate of ortho-xylene was measured in the same manner as above, only 10% of the para-xylene equilibrium adsorption amount was adsorbed after 1000 minutes.

When the amount of Ba contained in the catalyst was measured by the atomic absorption method, it was 3%. This catalyst was filled in a flow reactor and a toluene disproportionation reaction was carried out under the following reaction conditions.

Reaction temperature 455 ° C., W / F = 23 g · h /
mol, H ₂ / F = 3 mol / mol, pressure 3 MPa,
Feed composition Toluene (TL) 100% Reaction result is TL conversion 30%, PX / (PX + OX + M
X) = 84%. The aromatic yield was 98.76%.

Comparative Example 6 100 parts of the zeolite prepared in Example 1, 18.6 parts of barium acetate and alumina sol (15 parts as alumina) were kneaded and extruded. This was dried at 120 ° C. overnight, calcined at 550 ° C. for 2 hours, treated with a 10% ammonium chloride aqueous solution at 80 ° C. at L / S = 2 five times, and then 8
It was washed with water at 0 ° C. 5 times with L / S = 2. Then 120
After drying at ℃ overnight, it was baked at 500 ℃ for 2 hours.

This catalyst was filled in a flow reactor and a toluene disproportionation reaction was carried out under the following reaction conditions.

Reaction temperature 440 ° C., W / F = 23 g · h /
mol, H ₂ / F = 3 mol / mol, pressure 3 MPa,
Feed composition Toluene (TL) 100% Reaction result is TL conversion 30%, PX / (PX + OX + M
X) = 47%. The aromatic yield was 99.44%.

Comparative Example 7 100 parts of the zeolite prepared in Example 1, 18.6 parts of barium acetate and silica sol (7.5 parts as silica) were kneaded and extruded. This was dried at 120 ° C. overnight, calcined at 550 ° C. for 2 hours, treated at 80 ° C. with a 10% ammonium chloride aqueous solution at L / S = 2 five times, and then 80
It was washed with water at 0 ° C. 5 times at L / S = 2. After that, 120 ℃
After being dried overnight at 500 ° C., it was baked at 500 ° C. for 2 hours.

This catalyst was filled in a flow reactor and a toluene disproportionation reaction was carried out under the following reaction conditions.

Reaction temperature 450 ° C., W / F = 23 g · h /
mol, H ₂ / F = 3 mol / mol, pressure 3 MPa,
Feed composition Toluene (TL) 100% Reaction result is TL conversion 30%, PX / (PX + OX + M
X) = 64%. The aromatic yield was 99.3%.

Example 3 100 parts of the zeolite prepared in Example 1, 18.6 parts of barium acetate and silica sol (7.5 parts as silica) were kneaded and extruded. This was dried at 120 ° C. overnight, calcined at 550 ° C. for 2 hours, treated at 80 ° C. with a 10% ammonium chloride aqueous solution at L / S = 2 five times, and then 80
It was washed with water at 0 ° C. 5 times at L / S = 2. After that, 120 ℃
After being dried overnight at 500 ° C., it was baked at 500 ° C. for 2 hours.

This catalyst was packed in a flow reactor and a toluene disproportionation reaction was carried out under the following reaction conditions.

Reaction temperature 460 ° C., W / F = 23 g · h /
mol, H ₂ / F = 3 mol / mol, pressure 3 MPa,
Feed composition Toluene (TL) 100% Reaction result is TL conversion 30%, PX / (PX + OX + M
X) = 80%.

The aromatic yield was 99.2%.

[0061]

The catalyst of the present invention can be prepared very easily,
Moreover, when this catalyst is used in the production of paradialkylbenzene, both the activity and the para selectivity are increased. The aromatic yield is also high.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A 52-120292 (JP, A) JP-A 1-125333 (JP, A) JP-A 59-162952 (JP, A) JP-A 59- 174518 (JP, A) JP-A-59-176219 (JP, A) JP-B-49-45996 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) B01J 21/00-38 / 74 C07B 61/00 C07C 6 / 12,15 / 02,15 / 08

Claims (16)

(57) [Claims] 1. A less than the size of the main cavity is a 10-membered oxygen ring, and a silica / alumina ratio of 50, one side 0.5
Mainly composed of zeolite crystals larger than micron cubes
Contains a certain zeolite as the main component and contains barium in the catalyst.
And the amount of binder in the catalyst is 100 parts of zeolite
On the other hand, a catalyst for the production of paradialkylbenzene which is 10 parts or less . 2. A zeolite having a lattice spacing d (nm) display,
1.12 ± 0.02, 1.01 ± 0, 02, 0.386
± 0.008, 0.372 ± 0.008 and 0.365
X-ray diffraction pattern with peak at ± 0.008
The catalyst for producing paradialkylbenzene according to claim 1, wherein 3. At least a cation site of zeolite
Part of which is also hydrogen ion.
Or a catalyst for producing a paradialkylbenzene according to item 2 . 4. Paraxy at 0 to 2 ° C. at 120 ° C.
The adsorption amount when para-xylene is adsorbed at the vapor pressure
3g or more per 100g of catalyst and at 120 ° C
At 0-2 ° C ortho-xylene vapor pressure,
Adsorbs ortho-xylene up to 30% of its adsorption capacity
It requires 1000 minutes or more to
A catalyst for producing a paradialkylbenzene according to any one of 1 to 3 . 5. The amount of barium in the catalyst is 1% by weight or more.
The catalyst for producing paradialkylbenzene according to any one of claims 1 to 4, characterized in that: 6. The production of paradialkylbenzene is toluene.
Characterized by the production of para-xylene by the disproportionation of
The catalyst for producing paradialkylbenzene according to any one of claims 1 to 5 . 7. The size of the main cavity is composed of a 10-membered oxygen ring.
And the silica / alumina ratio is less than 50, 0.5 per side
Mainly composed of zeolite crystals larger than micron cubes
A zeolite, a barium salt, and an inorganic oxide
For the process of molding after kneading the inder and water and the molded product
Characterized by including a step of imparting protonic acid points by
A method for producing a catalyst for producing paradialkylbenzene . 8. A zeolite having a lattice spacing d (nm) display,
1.12 ± 0.02, 1.01 ± 0, 02, 0.386
± 0.008, 0.372 ± 0.008 and 0.365
X-ray diffraction pattern with peak at ± 0.008
For the production of paradialkylbenzene according to claim 7.
Catalyst manufacturing method . 9. The barium salt is barium acetate.
Paradialkyl ester according to claim 7 or 8, characterized in that
Method for producing catalyst for production of Nzen . 10. Proton acid points are imparted to a molded product.
After the step of treating with an aqueous solution of ammonium salt, baking
Any of claims 7 to 9, characterized in that
Or a catalyst for the production of paradialkylbenzene according to claim 1
Construction method . 11. The size of the main cavity is composed of a 10-membered oxygen ring.
And the silica / alumina ratio is less than 50, 0.5 per side
Mainly composed of zeolite crystals larger than micron cubes
Contains a certain zeolite as the main component and contains barium in the catalyst.
And the amount of binder in the catalyst is 100 parts of zeolite
In contrast, it is characterized by using a catalyst of 10 parts or less
A method for producing para-xylene from toluene. 12. Zeolite display of lattice spacing d (nm)
Then, 1.12 ± 0.02, 1.01 ± 0.02, 0.3
86 ± 0.008, 0.372 ± 0.008 and 0.3
X-ray diffraction pattern having a peak at 65 ± 0.008
Toluene to para-xylene according to claim 11
A method of manufacturing . 13. A part of the cation site of zeolite is
The hydrogen ion is a hydrogen ion.
A method for producing para-xylene from toluene according to 2 above. 14. At 120 ° C., a parac of 0 to 2 ° C.
Adsorption amount when para-xylene is adsorbed with silene vapor pressure
Is 3 g or more with respect to 100 g of the catalyst, and 120 ° C.
At ortho-xylene vapor pressure of 0 to 2 ° C.
Adsorbs ortho-xylene up to 30% of its adsorption capacity
Claims characterized by requiring 1000 minutes or more to complete
Paragraph 1 to paraffin from toluene according to any one of Items 11 to 13.
Method for producing siren . 15. The amount of barium in the catalyst is 1% by weight or more.
15. There is any one of Claims 11-14 characterized by the above-mentioned.
A method for producing para-xylene from the described toluene . 16. Para-xylene is produced from toluene.
A method characterized in that the method is the disproportionation of toluene.
Paragraph 11 from the toluene according to any one of 11 to 15
Method of manufacturing ren .