JPH0717524B2 - Process for producing alkylated aromatic compounds - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an alkylated aromatic compound, and more specifically, to a monoalkylated aromatic compound (“monoalkylated aromatic compound” referred to herein). Means that there is one alkyl group newly introduced into the aromatic hydrocarbon by the method of the present invention. For example, dodecyltoluene obtained by alkylating toluene with dodecene based on the method of the present invention is For the sake of convenience will be referred to as monoalkylated aromatic compounds.) For the preparation of high selectivity and high conversion by reaction of aromatic hydrocarbons with alkylating agents.

(Prior Art and Technical Problem of the Invention) Alkylation of aromatic hydrocarbons with olefins has been known for a long time, and catalysts thereof include Lewis acids such as AlCl ₃ and BF ₃ ; protonic acids such as sulfuric acid; Solid acids such as silicates are known. It is also possible to use hydrogen type zeolite X, zeolite Y, etc. as the solid acid catalyst.
It is already known from the publication No. -3298.

Among the hydrogen-type zeolites, zeolite Y as a precursor has a high SiO ₂ / Al ₂ O ₃ ratio, is excellent in heat resistance, acid resistance, hydrothermal resistance, etc., and has a pore size suitable for the reaction. Since it is within the above range and has excellent coking resistance, it is particularly suitable for the alkylation catalyst.

A known method for producing hydrogen-type zeolite Y is that the silicic acid content, the alumina content, the sodium content and the water content are zeolite Y.
A step of preparing a composition within a production range and, if necessary, producing zeolite Y in the presence of a mineralizer, and the zeolite Y
Is contacted with an ammonium salt to produce an ammonium-type zeolite, and a step of firing the ammonium-type zeolite to convert it into a hydrogen-type zeolite. Hydrogen-type zeolite Y produced by a known method
Is still unsatisfactory in terms of reaction selectivity and conversion.

That is, when the alkylation reaction of aromatic hydrocarbons is taken as an example, in the case of the known hydrogen-type zeolite Y, when the relationship between the reaction time and the conversion rate is plotted, even if it shows a relatively high conversion rate at the initial stage of the reaction. However, even if the reaction time is extended, the conversion rate is small and the overall conversion rate tends to be saturated at a relatively low level. In addition to monoalkylated aromatic hydrocarbons, by-products such as polyalkylated aromatic hydrocarbons, olefin oligomers, and condensates of aromatic hydrocarbons such as bunaphtyl are produced, and the selectivity to the target substance is increased. There is also the problem that it is still low.

(Summary and Purpose of the Invention) The present inventors have developed an aromatic carbonized hydrogen-type zeolite Y having a certain acidity, which is synthesized from activated silicic acid or activated aluminosilicic acid obtained by acid treatment of clay minerals. It was found that the target monoalkylated aromatic hydrocarbon can be obtained with high selectivity and high conversion when used as a hydrogenation alkylation catalyst.

That is, an object of the present invention is to provide a method for alkylating an aromatic hydrocarbon in the presence of an aluminosilicate catalyst with high selectivity and high conversion.

Another object of the present invention is to maintain the production of a condensate of an aromatic hydrocarbon such as binaphthyl or a by-product such as a polyalkylated aromatic hydrocarbon at a low level while maintaining the desired monoalkylated aromatic hydrocarbon. It is to provide a method capable of producing a hydrocarbon in a high yield.

Still another object of the present invention is to provide a method for alkylating aromatic hydrocarbons, which is excellent in selectivity and conversion to monoalkylated aromatic hydrocarbons and which is also excellent in life.

(Structure of the Invention) According to the present invention, in a process for producing an alkylated aromatic compound, which comprises reacting an aromatic hydrocarbon with an alkylating agent in the presence of an aluminosilicate catalyst, a clay mineral of a clay mineral is used as an aluminosilicate catalyst. Use hydrogen type zeolite Y which is synthesized by using active silicic acid or active aluminosilicic acid obtained by acid treatment as a silica raw material, and has an acidity of −5.6 or less in the range of 0.5 to 1.0 meq / g in Hammett's acid strength function. Is provided.

Furthermore, based on the above method, a liquid phase, when reacting an aromatic hydrocarbon and an alkylating agent in a batch system, a method for producing an alkylated aromatic compound characterized by circulating an inert gas in a reaction vessel, Provided.

(Characteristics and Effects of the Invention) The method of the present invention is characterized by the aromatic hydrocarbon alkylation catalyst used. This catalyst is composed of hydrogen-type zeolite Y, which is obtained by acid treatment of clay minerals. Acid or active alumino-silicic acid is used as a silica raw material; the acidity of hydrogen-type zeolite Y is controlled within the range of 0.5 to 1.0 meq / g by -5.6 or less by Hammett's acid strength function. It is characterized by

Conventionally, it is already known to synthesize a zeolite of a type including zeolite Y using an acid-treated product of a clay mineral having a layered structure as a silica raw material (for example, US Pat.
1,062,064, U.S. Pat. No. 3,393,045, JP-A-52-62314). However, as far as the inventors of the present invention know, no example of producing hydrogen-type zeolite Y from zeolite Y using a clay acid-treated product as a raw material has been known.

However, the present inventors have found that among the hydrogen-type zeolite Y synthesized by using the clay acid-treated product as the silica raw material, the acidity of −5.6 or less in the specific range of Hammett's acid strength function is within a specific range. It has been found that the hydrogen-type zeolite Y has novel characteristics not found in the hydrogen-type zeolite, and that the hydrogen-type zeolite Y provides a high selectivity and a high conversion rate as an aromatic hydrocarbon alkylation catalyst.

The drawbacks that occur when hydrogen-type zeolite Y synthesized from synthetic silicic acid or alkali silicate as a silica raw material is used as an alkylation catalyst have already been pointed out, but the most serious drawback is a practically negligible amount of by-products. Is to occur.

For example, when alkylating naphthalene, a condensate of aromatic hydrocarbons such as binaphthyl is considerably produced as a by-product. Such a condensate is a solid having a high melting point, and its incorporation into the product, an alkylated aromatic hydrocarbon, is unacceptable because it adversely affects the quality of the product. When the condensation product is separated by a means such as distillation, the condensate has a high melting point and has a sublimation property, which causes great difficulty.

On the other hand, in the above-mentioned specific hydrogen type zeolite Y used in the present invention, since the tendency to form a condensate of aromatic hydrocarbons is extremely small, the obtained alkylated aromatic hydrocarbon product has high purity. At the same time, there is an advantage that product separation and purification operations can be performed easily.

Also, during the alkylation reaction, the condensation reaction between aromatic hydrocarbons is suppressed, so the reaction should be performed while maintaining the molar ratio of aromatic hydrocarbon to alkylating agent higher than in the past. As a result, it is possible to improve the conversion rate while further significantly suppressing the formation of the dialkylated product.

Table A below shows typical hydrogen-type zeolite Y that has been conventionally used for alkylation of aromatic hydrocarbons and hydrogen-type zeolite Y used in the method of the present invention using an acid-treated product of smectite group clay as a raw material. The relationship between various characteristics, that is, specific surface area, pore volume, acidity, and the selectivity and conversion obtained in the alkylation of naphthalene with α-olefin (having 20 carbon atoms) is shown.

According to the results shown in Table A, the hydrogen-type zeolite Y used in the present invention is inferior to the conventionally known hydrogen-type zeolite Y in all of the specific surface area, the pore volume and the acidity. It is expected that the catalyst will have poor performance. However, according to the present invention, contrary to such prediction, far superior selectivity and conversion ratio can be obtained as compared with the conventional one, which is an unexpected effect of the present invention. Is.

The exact reason for this is unknown, but it is presumed as follows. That is, the conventional hydrogen-type zeolite Y causes a side reaction because the acidity is too large, whereas the hydrogen-type zeolite Y used in the present invention has an acidity suppressed to an appropriate range, which is a side reaction. It is presumed that this has a positive effect on the suppression of the heat generation and the improvement of the conversion rate.

The alkylation reaction based on the method of the invention described so far proceeds at a rate sufficient to withstand commercialization. However, the inventors of the present invention, when performing this alkylation reaction in a liquid phase or batch system, the reaction rate can be increased by circulating an inert gas such as nitrogen gas in the reaction vessel, for example, in the space above the reaction solution. We have found that it can be further accelerated. It was also found that the selectivity to the monoalkylated aromatic compound at that time was not different from the case where an inert gas was not flowed, when compared at the same conversion rate. For example, using hydrogen-type zeolite Y as a catalyst, α of naphthalene in liquid phase and batch
-When alkylated with an olefin (carbon number 2.0), when nitrogen gas was passed, a high conversion rate was achieved in half the reaction time compared to when nitrogen gas was not passed under the same conditions. did it. Further, when the olefin conversion rate was 95% or more, the selectivity to monoalkylnaphthalene was about 92%, which was good regardless of whether the nitrogen gas was distributed or not, and no difference was found.

DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION The present invention is described in detail below.

Preparation and Properties of Catalyst In the present invention, as the alkylation catalyst, a hydrogen-type zeolite Y synthesized using activated silicic acid or activated aluminosilicic acid obtained by acid treatment of clay mineral as a silica raw material is used.

i. Clay minerals Clay minerals are minerals that are characterized by the presence of layered silica. Generally, the layered structure of clay minerals has a three-layer structure (smectite) represented by montmorillonite,
A two-layer structure represented by kaolin and halloysite is known.

Smectite-type clay minerals are generally based on a three-layer structure in which two tetrahedral layers of SiO ₄ are sandwiched with an AlO ₆ octahedral layer sandwiched therebetween, and this basic three-layer structure is further laminated in the C-axis direction. It has a multi-layered crystal structure. As the smectite group clay mineral, for example, so-called montmorillonite group clay minerals such as acid clay, bentonite, subbentonite, and frass earth, and one kind or a combination of two or more kinds of beidellite, saponite, nontronite and the like are used. These clay minerals may be in the form of a mixture of, for example, a smectite group clay mineral and another clay mineral, and a clay mineral in which the smectite group clay mineral is slightly modified in nature, for example, a crystal in which the multilayer structure of smectite is slightly destroyed. Sanko clay from Shibata City, Niigata Prefecture, which exhibits a structure, can be used for the purpose of the present invention.

On the other hand, the clay mineral having a two-layer structure is basically a two-layer structure composed of the tetrahedral layer of SiO ₄ and the AlO ₆ octahedral layer, and has a layered structure in which the basic structure is laminated in the C-axis direction. ing.
Suitable examples thereof are halloysite and kaolin, the former being capable of being directly acid-treated to produce active silicic acid or active alumino-silicic acid, and the latter being difficult to be directly acid-treated, however, milling and If the crystal structure is destroyed by calcination treatment, activated silicic acid or activated aluminosilicic acid can be produced by acid treatment.

Other examples of clay minerals having a layered structure include attapulgite, palygorskite, and sepiolite.These clay minerals are composed of AlO ₆ or MgO ₆ octahedral layers between layers of SiO ₄ tetrahedral layers. It has a structure in which the face layers are inserted intermittently and alternately.

All of these clay minerals have a tetrahedral layer of SiO ₄ ,
It is common in that acid treatment gives active silicic acid or active aluminosilicic acid having a layered silica as a skeleton.

ii. Acid Treatment First, the clay mineral is subjected to an acid treatment under the condition that the X-ray diffraction peak of the surface index [001] disappears, that is, under the condition that at least the multilayer laminated structure of clay is destroyed.

The acid treatment of the smectite group clay mineral can be performed under conditions known per se except that the above-mentioned requirements are satisfied. For example, as the acid, any of mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as benzenesulfonic acid, toluenesulfonic acid and acetic acid can be used, but mineral acids such as sulfuric acid are generally used. The method of contacting the clay mineral and the acid may be any method, including Japanese Examined Patent Publication Nos. 28-5666 and 29-11.
2, 29-2169, 32-2960, 45-11208, 45-11209, 47-44154
Acid treatment of clay minerals disclosed in, for example, is particularly suitable for the present invention. For example, a so-called slurry activation method of contacting clay and acid in a slurry state, solidification of granulated clay and acid-
A so-called granular activation method of contacting with a liquid, a so-called dry activation method of reacting a mixture of clay and an acid by a dry method (granular material), and then extracting a basic salt can be applied to the acid treatment of the present invention.

The concentration of acid used for acid treatment, treatment temperature and treatment time are
It differs depending on the type of clay mineral and the acid treatment method, and it is difficult to specify unconditionally, but for example, when acid treatment is performed by a dry method, the smectite group clay mineral and the basic component in the clay mineral are 0.3 to 1.5 equivalents, especially 0.4 to
0.95 equivalents of an acid or an aqueous solution thereof is added to 0.3 part of the acid or an aqueous solution thereof based on 1 part by weight of the clay based on the dried clay.
To 2.5 parts by weight so that they are in close contact with each other so as to directly form a plastic or solid reaction product,
Then, the reaction product is treated in an aqueous medium at a pH of 1 or less to extract and remove the basic metal component in the product. The basic metal component to be removed in the clay means the amount of all the basic components such as the alkali metal component, the alkaline earth metal component, the iron component and the aluminum component contained in the clay. By maintaining the liquid ratio of the clay and the acid or the aqueous solution thereof within the above range, the mixture becomes solid or creamy, and the mixture is heated at a temperature in the range of 60 to 300 ° C. for 10 to 600 minutes. Among them, the reaction is completed by maintaining the conditions under which the X-ray diffraction peak of the plane index [001] substantially disappears. Then, the soluble base component in the reaction product was adjusted to pH 1
Thereafter, it is preferably treated in an aqueous medium having a pH of 0.5 or less and extracted and removed. At this time, it is important to extract and remove the soluble base component in the reaction product under the above-mentioned pH conditions in order to prevent hydrolysis of the base component, and it is generated by hydrolysis in the aluminosilicate component. When colloidal iron is contained, the yield or crystallinity of the synthetic zeolite seems to be considerably lowered.

In order to produce the acid-treated alumino-silicic acid raw material by bringing the granulated clay into solid-liquid contact with a mineral acid, 10
~ 98% concentration of mineral acids, 1: 0.01 to
A non-disintegrating granule is prepared under the conditions of the subsequent acid treatment, which is added in an amount of 1: 0.1 by weight. Then, the non-disintegrating clay granules are immersed in a 5 to 72%, particularly 10 to 50%, aqueous solution of a mineral acid, at room temperature to the boiling point of the solution and 0.5 to 100 hours in the clay. The treatment is performed under the condition that the X-ray diffraction peak of the [001] plane of (1) disappears substantially.

The acid treatment of the clay mineral can be carried out by wet-dispersing the clay in a slurry in a mineral acid such as 5 to 98% sulfuric acid,
The acid treatment conditions in this case can be based on the above-mentioned granular acid treatment.

Thus, activated silicic acid or activated alumino-silicic acid can be obtained by acid treatment of clay used in the synthesis of the catalyst of the present invention. The smectite group clay mineral or its acid-treated product is 5
20% by weight or more, especially 30% by weight or more of particles with a particle size of μ or less, and 30% by weight of particles with a particle size of 20 μ or more
It is desirable to adjust the particle size so as to be smaller than 10% by weight, particularly for easy synthesis of zeolite Y.

iii. Synthesis of Zeolite Y The above-mentioned active silicic acid or active aluminosilicic acid, an additional amount of alumina component, sodium content and water are mixed and aged to form a homogeneous composition in which each component is in the zeolite Y forming range.

As the alumina component, amorphous alumina such as aluminum hydroxide hydrogel and xerogel: alumina monohydrate such as boehmite and pseudoboehmite: alumina trihydrate such as vialite, gibbsite and nordstrandite: eg γ, η It is possible to use fine powder of activated alumina such as alumina of δ, κ, κ, θ, χ and ρ type.
Further, sodium hydroxide is particularly preferably used as the sodium content. Armin component and sodium component,
They may be used in combination in the form of compounds or mixtures, and are preferably used in the form of sodium aluminate. Of course, at this time, if an alumina component or sodium component in excess of sodium aluminate is required, these components can be mixed with sodium aluminate and supplied to the reaction system.

In the present invention, the active aluminosilicic acid content, the additional amount of alumina component, the sodium component and water are mixed in a component ratio known per se. Conventionally, according to a known method, the zeolite Y forming component is used in the following component ratio (based on oxide).

Na ₂ O / SiO ₂ = 0.2 to 1.4 SiO ₂ / Al ₂ O ₃ = 6 to 40 H ₂ O / Na ₂ O = 12 to 90 Generally, an aqueous slurry of activated silicic acid or activated aluminosilicate and sodium aluminate are used. And an aqueous solution containing sodium are preferably mixed to form a slurry having the above composition ratio.

In the present invention, when these samples are mixed, the components in the mixture are gelled to form a heterogeneous slurry. The gelled slurry is sufficiently stirred to form a homogenized slurry, and then aged. The aging temperature and time are
There is no particular limitation, but generally 0 to 50 ° C, especially 10 to 30 ° C
It is desirable to perform aging at the temperature of 0.1 to 100 hours, especially 1 to 50 hours.

Crystallization of zeolite is carried out by maintaining the above-mentioned homogeneous composition at the zeolite crystallization temperature. Generally, when the temperature is low, it takes a long time to crystallize, while when the temperature is high, the primary particle size becomes large, and atmospheric pressure treatment becomes difficult. Therefore, at a temperature of 50 to 100 ° C., A crystallization treatment of 1 to 100 hours is advantageous.

Although not always necessary, in order to improve the yield of zeolite Y and develop its crystal structure, it is preferable to coexist a mineralizer known per se in the crystallization system. As the mineralizer, chlorides, sulfates, nitrates and phosphates of alkali metals, especially sodium are used. The mineralizer may be added at the time of preparing the homogenized composition, or may be added at a stage after aging and before crystallization. The amount of the mineralizer added is preferably 0.1 to 2 times the amount of alumina.

The produced zeolite Y is separated from the mother liquor excessively, washed with water, and then subjected to the next ammonium exchange.

iv. Ammonium exchange treatment The produced zeolite Y was brought into contact with an aqueous solution of ammonium salt, and the final hydrogen type zeolite had a Na ₂ O / Al ₂ O ₃ molar ratio of 0.1.
Ammonium exchange is carried out so as to be 0 to 0.40, particularly 0.15 to 0.35.

When the Na ₂ O / Al ₂ O ₃ molar ratio is out of the above range, effective acid sites are not formed, and the activity as a solid acid catalyst tends to decrease, which is not preferable.

The ammonium exchange treatment is advantageously carried out using an aqueous solution of ammonium chloride, but it can also be carried out using other ammonium salts such as ammonium sulfate. Generally, the concentration of ammonium chloride used is preferably in the range of 5 to 150 g / l, and the contact between the zeolite and the ammonium chloride solution can be carried out in one step or in multiple steps, or both are contacted in a countercurrent manner. A continuous method or a method of passing an ammonium chloride solution through a column packed with zeolite can also be used.

This exchange treatment is sufficient at room temperature, but it can also be carried out by heating to a temperature up to the boiling point of the liquid.

The zeolite after ammonium exchange is washed with water to remove by-produced salts to obtain ammonium type zeolite.

V. Calcining Treatment In preparing the catalyst of the present invention, ammonium-type zeolite is calcined to be converted into hydrogen-type zeolite.

Incidentally, in producing a hydrogen-type zeolite having an acidity in the range used in the present invention, it is essential to use active silicic acid or active aluminosilicic acid by acid treatment of a clay mineral, but if the above raw materials are used, It is not always possible to obtain an acidity within the desired range, and it is necessary to select certain conditions for ammonium exchange treatment and calcination treatment.

Although the conditions for ammonium exchange have already been described, the baking treatment is preferably carried out at a temperature of 380 to 580 ° C., particularly 400 to 550 ° C., for 0.5 to 20 hours, particularly 1 to 10 hours. That is, if the temperature and time are within the above ranges, the ammonium groups are almost completely decomposed and converted into hydrogen type zeolite. However, if the temperature is higher than the above range and / or
Alternatively, when the time is longer than the above range, the activity of the solid acid catalyst is likely to decrease. On the other hand, when the temperature is lower than the above range and / or when the time is shorter than the above range, the ammonium group tends to remain without being decomposed into hydrogen form, and an effective acid site may not be formed. .

Vi. Characteristics of Catalyst The specific surface area of the hydrogen-type zeolite Y used in the present invention by the BET method is generally in the range of 400 to 600 m ₂ / g.

This hydrogen-type zeolite Y can be generally used in the form of powder having an average particle diameter of 0.1 to 100 μm by a sedimentation method, and pellets, tablets, spherical granules, and columnar particles having a particle diameter of 1 to 10 mm using various clay binders. It can be used for the reaction in the form of extruded granules or the like.

Aromatic Hydrocarbon Alkylation Reaction The method for producing an alkylated aromatic hydrocarbon of the present invention can be carried out under any conditions as long as the above-mentioned specific hydrogen type zeolite Y is used.

Examples of aromatic hydrocarbons include benzene, naphthalene, anthracene, and substituted aromatic hydrocarbons such as toluene, xylene, and methylnaphthalene, but the present invention is applicable to alkylation of naphthalene where condensation of aromatic hydrocarbons easily occurs. It is very effective.

As the alkylating agent, olefins having 2 to 28 carbon atoms, corresponding alkyl halides, alcohols and the like are used, and olefins are preferable in terms of cost. Examples of the olefins include ethylene, hexene, decene, hexadecene, eicosene and the like. The alkyl chain of these olefins may have a branch.
It may also be a mixture of two or more of these olefins.

The reaction can be carried out in the liquid phase, in which case both raw materials are maintained in the liquid phase and brought into contact with the hydrogen-type zeolite catalyst. The reaction can be carried out without solvent or in the presence of an inert solvent such as saturated hydrocarbon. From the viewpoint of reaction operation, a solvent-free liquid phase heterogeneous reaction is desirable.

The reaction temperature and pressure are generally known per se,
Generally, a temperature of 100 to 300 ° C, particularly 100 to 250 ° C is desirable. Further, the pressure may be normal pressure, but may be increased if necessary.

The reaction can be carried out batchwise or continuously.
In the former case, both raw materials and hydrogen-type zeolite Y can be charged all at once and reacted, or at least one of these can be added in portions or added dropwise to react. The amount of the catalyst added is appropriately in the range of 1 to 30% by weight, particularly 1 to 15% by weight, based on the alkylating agent. Further, the molar ratio of aromatic hydrocarbon: alkylating agent is generally 1: 1 to 10: 1, and particularly 1: 1 to 4: 1. The reaction time is appropriately in the range of 1 to 10 hours, and the unreacted aromatic hydrocarbon or alkylating agent can be reused in the reaction after being separated from the product.

Further, when the reaction is carried out in a liquid-phase batch system, an inert gas can be circulated in the reaction vessel, for example, in the space above the reaction solution, in order to increase the reaction rate. Examples of the inert gas include nitrogen, hydrogen and helium. Even if a small amount of inert gas is circulated, the reaction acceleration effect can be recognized, but if the amount of distribution is too small, substantial merit cannot be expected, and if it is too large, necessary reactants are transported outside the system. Generally, a flow rate of 0.5 to 5 liters per hour per reaction liquid head space is suitable, although it depends on the reaction charge amount.

In the case of the continuous system, it can be carried out, for example, by filling the column with granular material of hydrogen-type zeolite Y and supplying the aromatic hydrocarbon and the alkylating agent in the liquid phase to the packed column.

According to the present invention, an alkylated aromatic hydrocarbon is obtained at a high selectivity and a high conversion rate by alkylating an aromatic hydrocarbon in the presence of a specific hydrogen type zeolite Y. For example, when alkylating naphthalene with C10-20 olefins, the major feature is that even if the olefin conversion reaches a value as high as 99%, the selectivity to monoalkylnaphthalene based on olefin reaches a high level of 92% or more. Is.

Therefore, the alkylated aromatic hydrocarbon according to the present invention, particularly alkylnaphthalene, has excellent purity and is useful for applications such as synthetic lubricating oil, heat carrier oil, and oil for diffusion pump.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below by way of examples. First, the production method and physical properties of the hydrogen-type zeolite Y (hereinafter referred to as HY zeolite) used in Examples and Comparative Examples are shown, and thereafter, aromatic compounds are prepared by using these. The result of having carried out the alkylation of a hydrocarbon is shown.

Manufacture of Zeolite No. 1-Example Tests HY zeolite was manufactured by using acid clay from Nakajo Town, Niigata Prefecture as a clay mineral having a layered structure.

The acid clay from Nakajo Town, Niigata Prefecture, which was used, had a moisture content of 45
% By weight, the main component of which is dry weight% by weight
(Dried at 110 ℃) SiO ₂ 72.1, Al ₂ O ₃ 14.2, Fe ₂ O ₃ 3.87, MgO
It was 3.25, CaO1.06, and loss on ignition 3.15. This raw material acid clay was molded into a cylindrical shape with a diameter of 5 mm and a length of 5 to 20 mm, and an amount equivalent to 76.5 g in terms of dry matter was collected in a 500 ml conical beaker, and 200 ml of a 50 wt% concentration sulfuric acid solution was added to it. After heating at 90 ° C. for 20 hours for acid treatment, the mother liquor was separated by a decantation method and subsequently washed with water until the sulfate radicals disappeared to obtain a granular acid-treated product of activated aluminosilicate. Next, the obtained granules are wet-milled in an aqueous medium using a ball mill, and coarse particles are removed through a 200 mesh (mesh opening = 74 micron) screen to obtain a homogenized 28.1 wt% concentration with an average particle size of 5.7 micron. An active aluminosilicate slurry was obtained. (First Step) Table B shows the chemical composition of the obtained activated aluminosilicate based on a 110 ° C. dried product, and Table C shows the particle size distribution by the sedimentation method.

To the active aluminosilicate slurry 378 g, sodium aluminate solution (Al ₂ O ₃ 23.2 wt%, Na ₂ O18.7 wt% content) 96.5 g and sodium hydroxide contents solution (Na ₂ O37.0 wt% content) 90.8 g Mix a solution of and diluted in 140 g of water and mix at room temperature for 4
After stirring for 8 hours, seal the reaction vessel and place in a water bath at 95 ° C for 48 hours.
Crystallization was carried out by standing still for a time. Subsequently, the solid was separated by suction and washed with water until the pH of the washing liquid reached 10.5. The product obtained by X-ray diffraction and chemical composition analysis, it was confirmed that the sodium zeolite Y of SiO ₂ / Al ₂ O ₃ molar ratio 3.79 (hereinafter referred to as Na-Y zeolite). (Second step) 50 g of the above Na-Y zeolite (converted at 110 ° C dry matter) to 53.5 g /
Dispersed in 1000 ml of ammonium chloride solution of l concentration, 80 ℃
After stirring for 3 hours, the mixture was suctioned and washed with 1000 ml of water. After repeating the ion exchange operation 3 times with an ammonium chloride solution having a concentration of 53.5 g / l, washing with water until no chlorine ions were detected from the washing solution, and the obtained ammonium-type zeolite Y (hereinafter referred to as NH ₄ -Y zeolite)
Was dried at 110 ° C. for 20 hours. (Third Step) Finally, 30 g of the above NH ₄ —Y zeolite was placed in an alumina dish and baked in an electric furnace at 450 ° C. for 5 hours to be converted into HY zeolite. (Fourth Step) Production of Zeolite No. 2-Examples for Testing HY zeolite was produced using acid clay from Odo, Shibata City, Niigata Prefecture.

The main component of the acid clay from Odo, Shibata City, Niigata Prefecture, used was SiO ₂ 74.6, Al ₂ O ₃ 14.1, Fe ₂ O based on the dry matter standard weight% (110 ° C dry).
₃ 2.99, MgO1.84, CaO1.77, and loss on ignition of 4.65. This raw material acid clay was treated by the method shown in the first step of producing zeolite No. 1 to obtain an active aluminosilicate slurry having an average particle size of 5.9 microns and a concentration of 27.4% by weight.

(First Step) Table D shows the chemical composition of the obtained activated aluminosilicate based on a 110 ° C dried product, and Table E shows the particle size distribution by the sedimentation method.

To the active aluminosilicate slurry 390 g, sodium aluminate solution (Al ₂ O ₃ 23.2 wt%, Na ₂ O18.7 wt% content) and 79.4g sodium hydroxide solution (Na ₂ O37.0 wt% content) 113 g Mix the diluted solution in 210 g of water and mix at room temperature for 5
After stirring for 12 hours, 12.2 g of sodium chloride was added, and the mixture was stirred for 20 hours in a water bath at 95 ° C. for crystallization. After suctioning, washing was carried out with water until the pH of the washing solution became 10.5. The obtained product was analyzed by X-ray diffraction and chemical composition analysis to obtain SiO ₂ /
It was confirmed to be a Na—Y zeolite having an Al ₂ O ₃ molar ratio of 3.90. (Second step) 50 g of the above Na-Y zeolite (converted at 110 ° C dry matter) to 53.5 g /
The mixture was dispersed in 1000 ml of a 1-concentration ammonium chloride solution, stirred at room temperature for 20 hours, then suctioned, and washed with 1000 ml of water. 53.5 g / l After repeated three times the ion exchange operation with ammonium chloride solution concentration, followed by washing with water from the cleaning solution until chlorine ions were no longer detected, NH ₄ resulting -Y
The zeolite was dried at 110 ° C for 20 hours. (Third Step) Finally, 30 g of the above NH ₄ —Y zeolite was placed in an alumina dish and baked in an electric furnace at 450 ° C. for 5 hours to be converted into HY zeolite. (Fourth Step) Manufacture of Zeolite No.3-Examples for Testing Using the active aluminosilicate slurry obtained in the first step of manufacture of zeolite No.2 as a raw material, an HY zeolite was manufactured by another method.

390 g of the activated aluminosilicate slurry obtained by the method shown in the first step of zeolite No. 2 production, sodium aluminate solution (Al ₂ O ₃ 23.2 wt%, Na ₂ O 18.7 wt% contained) 61.
3g and 136g of sodium hydroxide solution (containing 7.0% by weight of Na ₂ O)
A solution obtained by diluting and with 154 g of water was mixed and stirred until uniform. The reaction mixture was allowed to stand at room temperature for 20 hours, 11.6 g of sodium chloride was added, and the mixture was stirred in a water bath at 95 ° C for 20 hours for crystallization. After suctioning, washing was carried out with water until the pH of the washing solution became 10.5. The obtained product was analyzed by X-ray diffraction and chemical composition analysis to obtain Na- with a SiO ₂ / Al ₂ O ₃ molar ratio of 4.20.
It was confirmed to be Y zeolite.

The Na-Y zeolite was converted to an HY zeolite using the methods shown in the third and fourth steps of producing zeolite No.2.

Zeolite No. 4 and No. 5-Comparative Example Test Samples Using the Na—Y zeolite obtained in the second step of producing zeolite No. 2, zeolite having different ion exchange conditions from No. 2 was produced.

In zeolite No. 4, 50 g of Na-Y zeolite (110 ° C dry matter equivalent) was dispersed in 1000 ml of ammonium chloride solution with a concentration of 26.8 g / l, and the ion exchange operation of stirring at room temperature for 20 hours, suction, and washing was performed only once. Performed with zeolite No.5, Na-Y
50 g of zeolite (converted to 110 ° C. dry matter) was dispersed in 1000 ml of an ammonium chloride solution having a concentration of 53.5 g / l, and the ion exchange operations of stirring at 80 ° C. for 3 hours, suction, and washing were repeated 5 times. In each case, washing with water was performed until chlorine ions were not detected in the washing solution, and the resulting NH ₄ -Y zeolite was washed with 1
After drying at 10 ℃ for 20 hours, 30g in an electric furnace at 450 ℃ 5
It was calcined for hours and converted to HY zeolite.

Manufacture of Zeolite No. 6 and No. 7-Comparative Test Samples Using the NH ₄ -Y zeolite obtained in the third step of zeolite No. 2 manufacture, zeolite was manufactured under firing conditions different from those of No. 2. . Put 30 g of NH ₄ -Y zeolite in an alumina dish, 350 ° C for zeolite No. 6 and 6 for zeolite No. 7.
It was calcined in an electric furnace at 00 ° C for 5 hours to be converted into HY zeolite.

Manufacture of Zeolite No. 8-Comparative Example Test Sample A zeolite was manufactured using sodium silicate as a silicic acid raw material. A solution prepared by diluting 512 g of No. 3 sodium silicate solution (containing 21.5% by weight of SiO _{2 and} 7.0% by weight of Na ₂ O) in 1060 g of water was added to a solution of sodium aluminate (22.9% by weight of Al ₂ O ₃ and N 2
54.2 g of a ₂ O containing 18.4% by weight) and sodium hydroxide solution (Na
And ₂ O37.0 wt% content) 236 g by mixing a solution obtained by diluting in water 1093 g, sealed reaction vessel after standing for 24 hours at room temperature, 95
Crystallization was performed by standing still in a water bath at ℃ for 40 hours. After suctioning, washing was carried out with water until the pH of the washing solution became 10.5. The obtained product was analyzed by X-ray diffraction and chemical composition analysis to obtain Si
It was confirmed that the O ₂ / Al ₂ O ₃ molar ratio Na-Y zeolite 3.65. This Na-Y zeolite was converted into H by using the method shown in the third and fourth steps of producing zeolite No.2.
-Converted to Y zeolite.

Preparation of Zeolite No. 9-Comparative Example Test Sample Zeolite was prepared using an aqueous colloidal silica sol as a silicic acid raw material.

667 g of commercially available aqueous colloidal silica sol (Snowtex 30, SiO ₂ 30.0 wt% content manufactured by Nissan Chemical Industries, Ltd.), sodium aluminate solution (Al ₂ O ₃ 22.9 wt%, Na ₂ O 18.4
52.4 g (containing wt%) and sodium hydroxide solution (Na ₂ O 37.0
(Containing wt.%) 250 g and a solution diluted with 346 g of water are mixed,
After stirring at room temperature for 48 hours, the reaction vessel was sealed and left standing in a water bath at 95 ° C for 24 hours for crystallization. After suctioning, washing was carried out with water until the pH of the washing solution became 10.5. The obtained product was analyzed by X-ray diffraction and chemical composition analysis to obtain SiO ₂ / Al ₂ O.
It ₃ is Na-Y zeolite in a molar ratio 3.97 was confirmed. This Na-Y zeolite is the third product of zeolite No.2 production.
It was converted to an HY zeolite using the method shown in step as well as step 4.

Production of Zeolite No. 10 and No. 11-Comparative Example Similar to Test No. 9, an aqueous colloidal silica sol was used as a silicic acid raw material.

667 g of commercially available aqueous colloidal silica sol (Snowtex 30, SiO ₂ 30.0 wt% content manufactured by Nissan Chemical Industries, Ltd.), sodium aluminate solution (Al ₂ O ₃ 22.9 wt%, Na ₂ O 18.4
Wt%) 55.0g and sodium hydroxide solution (Na ₂ O 37.0
(Containing wt.%) 200 g and a solution of 188 g diluted with water are mixed,
After stirring at room temperature for 48 hours, the reaction vessel was sealed and left standing in a water bath at 95 ° C for 24 hours for crystallization. After suctioning, washing was carried out with water until the pH of the washing solution became 10.5. The obtained product was analyzed by X-ray diffraction and chemical composition analysis to obtain SiO ₂ / Al ₂ O.
It ₃ is Na-Y zeolite in a molar ratio 4.76 was confirmed. 50 g of this Na-Y zeolite (converted to 110 ° C dry matter)
Disperse in 1000 ml of ammonium chloride solution of 3.5 g / l concentration,
Zeolite No. 10 has only one ion exchange operation such as stirring, suction, and washing at room temperature for 20 hours.
The ion exchange operation of stirring at 0 ° C. for 3 hours, suction, and washing with water was repeated 5 times. In each case, the product was finally washed with water until no chlorine ions were detected in the washing solution, and the obtained NH ₄ -Y
After drying the zeolite at 110 ℃ for 20 hours, 30 g of 550 ℃
In an electric furnace for 3 hours for conversion into HY zeolite.

HY zeolite samples No. 1 to No. 1 produced as described above
The physical properties of 1 are listed in Table F. The physical properties were measured by the test methods described below.

Test Method The test method for each item in this specification was as follows.

(1) Na ₂ O / Al ₂ O ₃ molar ratio and SiO ₂ / Al ₂ O ₃ molar ratio Determined by chemical composition analysis. However, the quantification of Al ₂ O ₃ and SiO ₂ is performed by the gravimetric method, and the quantification of Na ₂ O is performed by the atomic absorption method.

(2) Specific surface area and pore volume BET surface area measuring device (P
-600 type) is used for nitrogen gas adsorption measurement. The specific surface area is obtained by the BET one-point method, and the pore volume is obtained from the adsorption amount at saturated vapor pressure.

However, the sample is heated and degassed at 10 ^-2 to 10 ^-3 mmHg and 200 ° C for 2 hours, and then adsorption measurement is performed.

(3) Acidity The acidity of -5.6 or less is measured by the Benesi method with Hammett's acid strength function. All reagents used for the measurement are manufactured by Wako Pure Chemical Industries, Ltd.

(A) Grind in 7 aerial flasks with stoppers of 50 ml, which were weighed in advance, into 200 amesh (opening 74
Micron) through a sieve, take about 0.1g each, 20
After drying in a constant temperature oven at 0 ° C for 2 hours, let stand for 15 minutes in a desiccator and weigh. The dry sample weight W (g) is determined from the difference with the weight of the empty Erlenmeyer flask.

(B) Reagent n-butylamine and reagent special grade benzene are 0.
A 1N n-butylamine benzene solution is prepared and standardized using a 0.1N oxalic acid solution for volumetric analysis to determine the factor f.

(C) Amount of 0.1N n-butylamine benzene solution to be added V
(Ml) is calculated by the following formula.

Here, A is the amount of n-butylamine per 1 g of dried sample (meq /
g) and A = 0.5n (n = 0,1,2,3,4,5,6).

(D) Benzene reagent grade benzene is added to an Erlenmeyer flask so that the total amount with V (ml) calculated in (d) and (c) is 10 ml, and after stoppering, the sample is dispersed using an ultrasonic cleaner.

(E) Add the V (ml) 0.1N n-butylamine solution calculated in (c) to the Erlenmeyer flask and hold it down with vinyl tape so that the stopper does not come off, then shake the figure 8 (Tokyo Rika Kikai Co., Ltd.). Fix it to SS-80 (made by SS) and shake at room temperature for 24 hours.

(F) Using a 0.1% benzalacetophenonebenzene solution prepared with the reagent benzalacetophenone and reagent grade benzene as an indicator for pKa-5.6, add 3 drops to the Erlenmeyer flask after shaking. After plugging and shaking gently, observe the color of the sample surface.

(G) The highest value of A (meq / g) among the samples whose surface is colored yellow, which is the acidic color of the indicator, is A ₁ (meq /
g).

(H) Set the number of Erlenmeyer flasks in (a) to 10,
A in (c) is A = A ₁ + 0.05n (n = 0,1,2,3,4,5,
Repeat steps (a) to (f) with exactly the same contents, except for 6,7,8,9).

(I) The largest value of A (meq / g) among the samples whose surface is colored yellow is A ₂ (meq / g), and the acidity of the sample is -5.6 or less (meq / g) ) Is A _{2 to} A ₂ +0.05 (meq /
g).

Examples 1 to 3 224 g (0.8 mol) of 1-icosene, 205 g (1.6 mol) of purified naphthalene (melting point 79.8 ° C.) and HY zeolite were placed in a four-necked flask equipped with a thermometer, a stirring blade and an air cooling tube. 11.2g was charged and set on the mantle heater. While stirring, the temperature was raised from room temperature to 210 ° C in about 30 minutes. At this point, the reaction temperature is set to 21
The reaction was kept at 0 to 215 ° C. The reaction mixture sampled at regular intervals was centrifuged at 80 ° C. or higher, and the obtained supernatant was used as a sample for analysis. The unreacted naphthalene content, unreacted olefin content, and monoalkylnaphthalene content in the sample were quantified by gas chromatography, and the olefin conversion rate and the monoalkylnaphthalene selectivity were calculated based on the results. The content of binaphthyl in the sample was separately quantified by thin layer chromatography.

In the above-mentioned reaction method, the cases where Zeolite Nos. 1 to 3 in Table F are used as the HY zeolite are Examples 1 to 3 respectively, and the cases where Zeolite Nos. 4 to 11 are used are Comparative Examples 1 to 8 respectively. As a result, those reaction results are shown in Table G. According to the results of Examples 1 to 3, both the conversion rate of olefin and the selectivity to monoalkylnaphthalene are high,
Moreover, the production of an alkylated aromatic compound according to the present invention using a zeolite having suitable physical properties with almost no formation of binaphthyl is well exemplified. Comparative Examples 1 to 4 correspond to the cases of using Zeolite Nos. 4 to 7 shown in Table F, respectively, but it is understood that the acidity is low and the catalytic activity is low because the ion exchange conditions and the firing conditions are not properly selected. To be done.

Further, Comparative Examples 5 to 8 are zeolite N shown in Table F, respectively.
Although it corresponds to the case where o.8 to 11 are used, the physical properties of the produced HY zeolite are different when the silicic acid raw materials are different, even though the apparently similar Na—Y zeolite is used as the precursor. It is understood that it varies significantly and does not exhibit favorable catalytic activity. In particular, when using No. 9-11 zeolite with high acidity, an unacceptable amount of binaphthyl was produced.

Further, when the method of the present invention is applied to a method for producing an alkylnaphthalene, there are advantages that an oxidation stability is excellent and an alkylnaphthalene having an α-substitution / B-substitution ratio of 1.0 or more can be obtained.

Example 4 256 g (2.0 mol) of purified naphthalene was charged into a four-necked flask equipped with a thermometer, a stirrer, an air-cooled tube and a Teflon tube for supplying olefin, and 256 g (2.0 mol) of purified naphthalene was charged and set on an oil bath of 130 ° C. The stirring was started when the naphthalene started to melt and the stirring became possible. After naphthalene is completely dissolved, raise the temperature of the oil bath to raise the temperature of naphthalene.
After 165-170 ℃, HY zeolite (No. 2 in Table F)
13.4g was added. Immediately, the liquid feed pump started feeding 1-decene through the Teflon tube, and 168 g (1.2 mol) of 1-decene was fed over 4 hours. During this time, the temperature of the reaction mixture was kept at 165-170 ° C. After continuing the reaction at the same temperature for 1 hour, the mixture was cooled to 100 ° C. The catalyst was removed from the reaction mixture by pressurization and the excess oil was subjected to gas chromatography analysis. The conversion of 1-decene was 99.1% and the selectivity to monodecylnaphthalene was 94.6%.

Example 5 167 g of 1-tetradecene was added to a reactor similar to that of Example 1-3.
(0.85 mol), 238 g (1.7 mol) of methylnaphthalene (mixture of 1-methyl and 2-methyl), and 8.4 g of HY zeolite (No. 2 in Table F) were charged. Stir, heat and heat up 21
The reaction was carried out at 5 to 220 ° C for 6 hours. As a result of analyzing the reaction mixture by gas chromatography, the olefin conversion rate was 9
6.4%, selectivity to methyltetradecylnaphthalene is 92.
It was 0%.

Example 6 Toluene 276 g (3 mol) and 1-dodecene 16 were added to a glass autoclave 1 equipped with a stirrer, a thermometer and a heater.
8 g (1 mol) and 8.4 g of HY zeolite (No. 2 in Table F) were charged. After purging the inside of the autoclave with nitrogen, the inside of the autoclave was sealed and heated to 200 ° C. in about 1.5 hours with stirring, and then kept at 195 to 205 ° C. for 2 hours. Then, after the reaction mixture was cooled, the catalyst was removed by pressurization to obtain a super oil. As a result of analysis by gas chromatography, the conversion of olefin reached 99.5% and the selectivity to dodecyltoluene reached 97.3%.

Example 7 In order to show the effect of accelerating the alkylation reaction by flowing an inert gas, naphthalene was produced under the same conditions as in Example 2 except that nitrogen gas was passed through the upper space of the reaction solution and the reaction time was 3 hours. Example 2 shows the reaction results when alkylation of
The results are shown in Table H in comparison with. The olefin conversion rate corresponding to Example 2 in the H table is different from that in the G table because the G table shows the conversion rate after 6 hours of reaction, but the H table shows the reaction acceleration effect by the inert gas flow. This is because the conversion rate after 3 hours of reaction is shown for the sake of illustration. From Table H, it is understood that the reaction is accelerated by the flow of nitrogen gas and there is no difference in the selectivity to monoalkylnaphthalene when the olefin conversion rate reaches a high rate of 95% or more. It

Claims (2)

[Claims] 1. A process for producing an alkylated aromatic compound, which comprises reacting an aromatic hydrocarbon with an alkylating agent in the presence of an aluminosilicate catalyst, which is obtained by acid treatment of a clay mineral as an aluminosilicate catalyst. A production method characterized by using hydrogen-type zeolite Y, which is synthesized by using active silicic acid or active aluminosilicic acid as a silica raw material, and has an acidity of −5.6 or less in the range of 0.5 to 1.0 meq / g in Hammett acid strength function. . 2. A process for producing an alkylated aromatic compound, which comprises reacting an aromatic hydrocarbon and an alkylating agent in a liquid phase and in a batch system in the presence of an aluminosilicate catalyst, to obtain a clay mineral as aluminosilicate catalyst. The active silicic acid or active aluminosilicic acid obtained by the acid treatment was synthesized as a silica raw material, and the hydrogen type zeolite Y whose acidity of -5.6 or less in the Hammett acid strength function is in the range of 0.5 to 1.0 meq / g is used. And a method of producing an inert gas in the reaction vessel.