JPS63150231A - Production of alkylated aromatic compound - Google Patents

Abstract

PURPOSE:To obtain the aimed compound in high selectivity and conversion ratio, by using specific hydrogen type zeolite Y as a catalyst in reacting an aromatic hydrocarbon with an alkylating agent in the presence of an aluminosilicate catalyst to produce the titled compound. CONSTITUTION:An aromatic hydrocarbon is reacted with an alkylating agent in the presence of an aluminosilicate catalyst to produce an alkylated aromatic hydrocarbon compound. In the process, hydrogen type zeolite Y, synthesized by using activated silicic acid or activated aluminosilicic acid prepared by acid treatment of a clay mineral and having an acidity of <=-5.6 expressed in terms of Hammett's acid strength function within the range of 0.5-1.0meq/g as the above-mentioned catalyst. Furthermore, when the afore-mentioned reaction is carried out in the liquid phase and batch method, an inert gas is passed through a reaction vessel to suppress formation of condensates, e.g. binaphthyls, etc., and polyalkylated substances, etc., as by-products. Selectivity and conversion ratio to monoalkylated substances are increased to afford the aimed compound in high yield with excellent catalyst life.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing alkylated aromatic compounds, and more particularly, to a method for producing an alkylated aromatic compound (herein referred to as "monoalkyl"). The expression "incorporated" means that one alkyl group is newly introduced into the polyaromatic hydrocarbon by the method of the present invention.

For example, dodecyltoluene obtained by alkylating toluene with dodecene according to the process of the present invention will conveniently be classified as monoalkylated aromatic compounds. ) is produced with high selectivity and high conversion rate by the reaction of aromatic hydrocarbons and alkylating agents.

(Prior Art and Technical Problems of the Invention) The alkylation of aromatic hydrocarbons with olefins has been known for a long time, and the catalysts used include AtCl3. B
Lewis acids such as F3, protonic acids such as sulfuric acid, and solid acids such as aluminosilicate are known.

The use of hydrogen type zeolite X, zeolite Y, etc. as a solid acid catalyst is already known from Japanese Patent Publication No. 3298/1983.

Among hydrogen-type zeolites, those using zeolite Y as a precursor have a high S102/At20s ratio, excellent heat resistance, acid resistance, hydrothermal resistance, etc., and have a bore size within a range suitable for the reaction. It also has excellent coking resistance, making it particularly suitable for the alkylation catalyst.

A known method for producing hydrogen-type zeolite Y is to prepare a composition in which the silicic acid content, alumina content, sodium content, and water content are within the zeolite Y production range, and if necessary, produce zeolite Y in the presence of a mineralizing agent. A step of bringing the zeolite Y into contact with an ammonium salt to produce an ammonium-type zeolite, and a step of converting the ammonium-type zeolite into a hydrogen-type zeolite by calcining it.

Hydrogen type zeolite Y produced by a known method is still not satisfactory in terms of reaction selectivity and conversion rate.

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

(Gist and Objectives of the Invention) The present inventors have developed hydrogen-type zeolite Y, which has a certain acidity and is synthesized from activated silicic acid or activated aluminosilicate obtained by acid treatment of clay minerals, by aromatic carbonization. It has been found that when used as a hydrogen alkylation catalyst, the desired monoalkylated aromatic hydrocarbon can be obtained with high selectivity and conversion.

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

Another object of the present invention is to obtain the target monoalkylated aromatic hydrocarbons while maintaining a small level of formation of by-products such as condensates of aromatic hydrocarbons such as binaphthyl and polyalkylated aromatic hydrocarbons. The object of the present invention is to provide a method for producing group hydrocarbons in high yield.

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

(Structure of the Invention) According to the present invention, in a method for producing an alkylated aromatic compound comprising reacting an aromatic hydrocarbon and an alkylating agent in the presence of an aluminosilicate catalyst, clay minerals are used as the aluminosilicate catalyst. It is synthesized using activated silicic acid or activated aluminosilicic acid obtained by acid treatment as a silica raw material, and has an acidity of -5.6 or less according to the Nomet acid strength function of 0.5 to 1. A method is provided, characterized in that it uses a hydrogen-type zeolite Y in the range of Oms q/g.

Furthermore, based on the above method, there is provided a method for producing an alkylated aromatic compound, which is characterized in that an inert gas is passed through the reaction vessel when reacting an aromatic hydrocarbon and an alkylating agent in a liquid phase, batch method. 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, and the activity obtained by acid treatment of clay mineral is It must be synthesized from silicic acid or activated aluminosilicic acid as a silica raw material; the acidity of hydrogen-type zeolite Y is 0.5 to 1.0 me, assuming that it is -5.6 or less according to the Nomet acid strength function.
q/! It is characterized by the combination of being controlled within a range of 9.

Conventionally, it is already known that 61 types of zeolites, including zeolite Y, can be synthesized using acid-treated clay minerals having a layered structure as silica raw materials (for example, British Patent No. 1,062,064). Specification, U.S. Patent No. 3,393,045, JP-A-52-6231
Publication No. 4). However, to the best of the knowledge of the present inventors, there is no known example of producing hydrogen-type zeolite Y from zeolite Y using a clay acid-treated material as a raw material.

However, the present inventors have found that among hydrogen-type zeolite Y synthesized from clay acid-treated products using silica raw materials, those whose acidity is within a specific range of -5.6 or less according to Hammett's acid strength function are conventionally known. It has been discovered that this hydrogen-type zeolite Y has novel characteristics not found in known hydrogen-type zeolites, and also provides high selectivity and high conversion rate as an alkylation catalyst for aromatic hydrocarbons.

The drawbacks that occur when hydrogen-type zeolite Y synthesized from synthetic silicic acid or alkali silicate as a silica raw material are used as alkylation catalysts have already been pointed out, but the most serious drawback is that the amount of by-products that cannot be ignored in practice is It is the production of living things.

For example, when naphthalene is alkylated, a condensation product of aromatic hydrocarbons such as binaphthyl is produced as a by-product. Such condensates are solids with high melting points, and their contamination with the alkylated aromatic hydrocarbon product is completely unacceptable because it will adversely affect the quality of the product.
On the other hand, it is very difficult to separate this by-product from the product by means such as distillation because the condensate has a high melting point and has sublimation properties.

On the other hand, the specific hydrogen-type zeolite Y used in the present invention has extremely little tendency to form condensates of aromatic hydrocarbons, so the resulting alkylated aromatic hydrocarbon products have high purity. At the same time, there is an advantage that product separation and purification operations can be performed very easily.

Also, during the alkylation reaction, the condensation reaction between aromatic hydrocarbons is suppressed, so the reaction can be carried out by maintaining a higher molar ratio of aromatic hydrocarbon to alkylating agent than in conventional methods. As a result, it becomes possible to improve the conversion rate while suppressing the formation of dialkylated products more significantly.

Table A below shows typical hydrogen-type zeolite Y conventionally used for alkylation of aromatic hydrocarbons and hydrogen-type zeolite Y used in the method of the present invention using acid-treated smectite clay as raw material. , shows the relationship between various properties, ie, specific surface area, pore volume, acidity, and the selectivity and conversion rate obtained during alkylation of naphthalene with an α-olefin (20 carbon atoms).

A table specific surface area (normal 2/!j) 400-600
600-800 Pore volume (Mutsu', F) 0.20-0
．． 30 0.30-0.35 acidity (meq/,!
i') Ho≦-6,50,5-1,01,5-2,5 conversion rate (
To) Note 1) 96 or more 85-90 selectivity (Inquiry Note 1) 92 or more 82-87 Note 1) Same conditions as Example 1-3 After 6 hours of reaction, according to the results in Table A, the hydrogen type used in the present invention Zeolite Y is inferior to conventionally known hydrogen-type zeolite Y in terms of specific surface area, pore volume, and acidity, and is therefore predicted to have inferior performance as a solid acid catalyst. be done. However, according to the present invention, contrary to such predictions, far superior selectivity and conversion rate can be obtained compared to the conventional ones, and this is due to the unexpected effects of the present invention. It is.

Although the exact reason for this is unknown, it is assumed as follows. In other words, while the conventional hydrogen-type zeolite Y has too high acidity and causes side reactions, in the hydrogen-type zeolite Y used in the present invention, the acidity is suppressed to an appropriate range, and this causes side reactions. It is presumed that this has a favorable effect on suppressing the reaction and improving the conversion rate.

The alkylation reaction based on the method of the invention described above proceeds at a rate sufficient to be commercially viable. However, the present inventors have discovered that when carrying out this alkylation reaction in a liquid phase or batch mode, the reaction rate can be increased by flowing an inert gas such as nitrogen gas into the reaction vessel, for example, in the space above the reaction liquid. We found that it is possible to further speed up the process. It was also found that the selectivity to the monoalkylated aromatic compound in this case is no different from that in the case where no inert gas is passed when compared at the same conversion rate. For example, using hydrogen-type zeolite Y as a catalyst, α of naphthalene can be produced in a liquid phase or batch process.
- When alkylation with an olefin (carbon number 2.0) is carried out, when nitrogen gas is passed, the conversion rate is high in half the reaction time compared to when no nitrogen gas is passed under the same conditions. I was able to achieve this. In addition, the olefin conversion rate is 95
When compared at 96 or higher, the selectivity to monoalkylnaphthalene was as good as about 92, regardless of whether nitrogen gas was flowing or not, and no difference could be found.

(Description of preferred embodiments of the invention) The present invention will be explained in detail below.

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

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

Smectite-type clay minerals generally have a three-layer structure in which two 8104 tetrahedral layers are sandwiched with an A/, 06 octahedral layer sandwiched between them, and this basic three-layer structure is further multilayered in the C-axis direction. It has a stacked multilayer 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 or a combination of two or more types of beidellite, sabonite, nontronite, etc. are used. These clay minerals may be, for example, in the form of a mixture of smectite clay minerals and other clay minerals, or may be clay minerals in which smectite clay minerals are naturally slightly modified, such as crystals in which the multilayer structure of smectite is slightly destroyed. Clay produced by Sanko, Shibata City, Niigata Prefecture, etc., which exhibits a structure, can be used for the purpose of the present invention.

On the other hand, clay minerals with a two-layer structure are basically two-layer structures consisting of the aforementioned 5i04 tetrahedral layer and AAO6 octahedral layer, and have a layered structure in which this basic structure is laminated in the C-axis direction. . Suitable examples are halloysite and kaolin; the former can be directly treated with acid to produce active silicic acid or active aluminosilicate, while the latter is difficult to be treated with acid directly, but can be processed by grinding. If the crystal structure is destroyed by and/or firing treatment, it becomes possible to produce active silicic acid or active aluminosilicic acid by acid treatment.

Other examples of clay minerals with a layered structure include atta thurgite, -yarigorskite, and sepiolite, and these clay minerals have A, ω6, Alternatively, it has a structure in which Mg06 octahedral layers are inserted intermittently and alternately.

All of these clay minerals have a tetrahedral layer of 5lo4, and have in common that they give active silicic acid or active aluminosilicic acid having layered silica as a skeleton by acid treatment.

11. Acid treatment First, the above clay mineral is treated with an acid under conditions where the X-ray diffraction peak of surface index [001] disappears, that is, at least under conditions where the multilayered structure of the clay is destroyed.

The acid treatment of smectite group clay minerals can be carried out 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 with the acid may also be any method.
゜29-112.29-2169.32-2960.4
5-11208.45-11209.47-44154
The acid treatment of clay minerals disclosed in et al. is particularly suitable for the present invention.
A so-called granular activation method involving liquid contact, a so-called dry activation method involving dry reaction (granules) of a mixture of clay and acid, and then extraction of a basic salt can be applied to the acid treatment of the present invention.

The acid concentration, treatment temperature and treatment time used for acid treatment are as follows:
It varies depending on the type of clay mineral and the acid treatment method, and it is difficult to specify generally, but for example, when dry acid treatment is performed, the smectite group clay mineral and the basic component in the clay mineral 0.3 to 1.5 equivalents, especially 0
．． 4 to 0.95 equivalents of the acid or its aqueous solution are uniformly mixed in a ratio such that the acid or its aqueous solution is 0.3 to 2.5 parts by weight per 1 part by weight of the clay, based on the dry matter of the clay. to directly form a plastic to solid reaction product, which is then treated with PL (1 or less) in an aqueous medium to extract the basic metal components in the product. The basic metal component to be removed in the clay means the amount of all basic components such as alkali metals, alkaline earth metals, iron, and aluminum contained in the clay.Clay By maintaining the liquid ratio of the acid and the acid or its aqueous solution within the above range, the mixture becomes solid or creamy, and the mixture is heated to a temperature in the range of 60 to 300°C for a period of 10 to 600 minutes. Among them, the surface index [0
The reaction is completed by maintaining conditions under which the X-ray diffraction peak of [01] substantially disappears.

The soluble base component in this reaction product is then extracted and removed by treatment in an aqueous medium of -1 or less, preferably -0.5 or less. At this time, it is important to perform extraction and removal of the soluble base component in the reaction product under the above-mentioned conditions in order to prevent hydrolysis of the base component. When colloidal iron is contained, the yield or crystallinity of synthetic zeolite appears to be considerably reduced.

In order to produce an acid-treated aluminosilicate raw material by bringing granulated clay into solid-liquid contact with mineral acids, 1.
Mineral acids at a concentration of 0 to 98 ton, 1:0 on a clay dry basis.
．． 0.01 to 1:0.1 in a weight ratio to produce non-disintegrating granules under subsequent acid treatment conditions. The non-collapsible clay granules are then immersed in an aqueous mineral acid solution of 5 to 72 g, especially 10 to 50 g, at room temperature to the boiling point of the solution and for 0.5 to 100 hours.
The treatment is carried out under conditions such that the X-ray diffraction peak of the [001] plane in the clay substantially disappears.

Acid treatment of clay minerals can also be carried out wet by dispersing the clay in slurry form in a mineral acid such as 5 to 98% sulfuric acid. In this case, the acid treatment conditions should be similar to the granular acid treatment described above. I can do it.

In this way, activated silicic acid or activated aluminosilicate can be obtained by acid treatment of the clay used in the synthesis of the catalyst of the present invention.
Particle size below μ is 20% by weight or more of the total, especially 30% by weight.
% by weight or more, particles larger than 20μ account for 3 of the total.
In order to facilitate the synthesis of zeolite Y, it is desirable to adjust the particle size so that it is smaller than 0% by weight, especially smaller than 10% by weight.

111. Synthesis of Zeolite Y Mix the above-mentioned activated silicic acid or activated aluminosilicate, an additional amount of alumina component, Na) IJium component and water,
Aged to form a homogeneous composition in which each component is in the zeolite Y forming range.

Examples of the alumina component include amorphous alumina such as aluminum hydroxide hydrogel and xerogel; alumina monohydrate such as boehmite and pseudoboehmite; alumina trihydrate such as pialite, gibbsite, and nordstrandite; e.g., γ, η. , δ, fine powder of activated alumina such as θ, χ, and ρ type alumina can be used.

Moreover, as the sodium component, sodium hydroxide is particularly preferably used. The alumina component and sodium component are
They may be used in combination in the form of compounds or mixtures, and are particularly preferably used in the form of sodium aluminate. Of course, at this time, if excess alumina component or sodium component is required, these components can be supplied to the reaction system in the form of a mixture with sodium aluminate.

According to the invention, the active aluminosilicate component, additional alumina component, sodium component and water are mixed in component ratios known per se. According to conventionally known methods, zeolite? The forming components are used in the following component ratios (based on oxides).

Nh20/5in2=0.2~1.4SIO2/
At203 = 6 to 40 H2O/Na2O = 12 to 90 Generally, an aqueous slurry of activated silicic acid or activated aluminosilicate and an aqueous solution containing sodium aluminate and sodium are mixed to form a slurry having the above composition ratio. is desirable.

In the present invention, when these samples are mixed, the components in the mixture are glued to form a heterogeneous slurry. The glued slurry is thoroughly stirred to obtain a homogenized slurry, and then aged. The temperature and time of ripening are
There is no particular limit, but generally at a temperature of 0 to 50°C, especially 10 to 30°C, for 0.1 to 100 hours, especially 1 to 5
It is desirable to carry out the aging in the range of 0 hours.

Zeolite crystallization is carried out by maintaining the homogeneous composition described above at the zeolite crystallization temperature.

In general, the lower the temperature, the longer it will take for crystallization, and the higher the temperature, the larger the secondary particle size and the difficulty of normal pressure treatment. A crystallization treatment at a temperature of 1 to 100 hours is advantageous.

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

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

IV. Ammonium exchange treatment The produced zeolite Y is brought into contact with an aqueous solution of ammonium salt, and the final hydrogen type zeolite is Nh20/At205.
The molar ratio is 0.10 to 0.40. Especially 0.15 to 0.
Ammonium is exchanged so that it becomes 35.

When the NIL20 /A t20 s molar ratio is outside 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 can also be carried out using other ammonium salts such as ammonium sulfate. The concentration of ammonium chloride used is generally desirably in the range of 5 to 1501/l, and the contact between the zeolite and the ammonium chloride solution can be carried out in one step or in multiple steps.
Alternatively, it can be carried out by a continuous method in which both are brought into contact in a countercurrent manner, or by a method in which the ammonium chloride solution is passed through a column packed with zeolite.

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

After ammonium exchange, the zeolite is washed with water to remove by-product salts and to obtain ammonium-type zeolite.

(2) Calcining treatment In preparing the catalyst of the present invention, ammonium type zeolite is calcined to convert it into hydrogen type zeolite.

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

The conditions for ammonium exchange have already been explained, and the calcination treatment is carried out at a temperature of 380 to 580°C, particularly 400 to 550°C, for a time period of 0.5 to 20 hours, and for a period of 1 to 1 hour.
It is best to do this for 0 hours. That is, if the temperature and time are within the above ranges, ammonium groups are almost completely decomposed and converted into hydrogen type zeolite. However, if the temperature is higher than the above range and/or the time is longer than the above range, the activity of the solid acid catalyst tends to decrease. On the other hand, if the temperature is lower than the above range and/or the time is shorter than the above range, the ammonium group tends to remain without being decomposed into the hydrogen form, and effective acid sites may not be formed. be.

■1 Characteristics of the catalyst The specific surface area of the hydrogen-type zeolite Y used in the present invention by the BET method is generally 400 to 600 m2/
within the range of g.

This hydrogen-type zeolite Y can be generally used in the form of powder with an average particle size of 0.1 to 100 μm by the sedimentation method, or can be formed into pellets, tablets, and spheres with a particle size of 1 to 10 μm using various clay binders. It can be used in the reaction in the form of granules, columnar extrusion granules, etc.

Alkylation Reaction of Aromatic Hydrocarbons The method for producing alkylated aromatic hydrocarbons 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. However, the present invention is suitable for alkylation of naphthalene, which tends to cause condensation between aromatic hydrocarbons. It is highly effective.

As the alkylating agent, olefins having 2 to 28 carbon atoms, corresponding alkyl halides, alcohols, etc. are used, but olefins are preferred from the viewpoint of cost. Examples of olefins include ethylene, hexene, decene, hexadecene, and icosene. The alkyl chains of these olefins may have branches.

Moreover, a mixture of two or more of these olefins may be used.

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

The reaction temperature and pressure are generally known per se;
Generally Zoo to 300°C, especially Zo.

Temperatures between 250°C and 250°C are preferred. Further, although normal pressure is sufficient, pressure may be increased if necessary.

The reaction can be carried out either batchwise or continuously.

In the former case, both raw materials and hydrogen type zeolite Y can be charged at once and reacted, or at least one of them can be added in portions or dropped to react.

The amount of catalyst added is 1 to 30% based on the alkylating agent.
A range by weight, especially from 1 to 15% by weight, is suitable. Furthermore, the molar ratio of aromatic hydrocarbon to alkylating agent is generally 1.
A suitable range is from 1:1 to 10:1@- and from 1:1 to 4:1. The reaction time is suitably in the range of 1 to 10 hours, and unreacted aromatic hydrocarbons or alkylating agents can be separated from the product and used again for the reaction.

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 liquid, in order to increase the reaction rate. Examples of the inert gas include nitrogen, hydrogen, and helium. If even a small amount of inert gas is distributed, the reaction will be accelerated, but if the amount is too small, no substantial benefit can be expected, and if it is too large, the necessary reactants will be transported out of the system. Therefore, although it depends on the reaction charge amount, a flow rate of 0.5 to 51 per hour of reaction liquid head space is generally appropriate.

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

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

Therefore, the alkylated aromatic hydrocarbons, especially alkylnaphthalenes, according to the present invention have excellent purity and can be used in synthetic lubricating oils, heat transfer oils, diffusion oils, etc. It is useful for applications such as cleaning oil.

The present invention will be explained below with examples. First, the production method and physical properties of hydrogen type zeolite Y (hereinafter referred to as H-Y zeolite) used in Examples and Comparative Examples will be shown, and then the aromatic The results of alkylation of group hydrocarbons are shown.

Production Example of Zeolite AI H-Y zeolite was produced using acidic clay produced in Nakajo Town, Niigata Prefecture as a clay mineral having a layered structure.

The acidic clay used from Nakajo Town, Niigata Prefecture has a moisture content of 4% in its natural state.
Contains 5% by weight, its main component is % by weight on a dry matter basis.
(110℃ dry) 5in272.1, At20314
．． 2, F・20,3.87, MgO3,25, CaO1
, 06, and the ignition loss was 3.15. This raw acid clay is 5W in diameter! ×Mold into a cylindrical shape with a length of 5 to 20 m, collect an amount equivalent to 76.59 in terms of dry matter into a 5001 nl conical beaker, add 200 mJ of 50 wt% sulfuric acid solution, and heat to 90 ° C. After acid treatment for 20 hours, the mother liquor was separated using a decant take method, followed by washing with water until the sulfuric acid groups disappeared to obtain a granular acid-treated product consisting of activated aluminosilicate. Next, the obtained granules were wet-pulverized in an aqueous medium using a galmill, and
Coarse particles were removed through a mesh sieve (opening = 74 microns) to obtain a homogeneous activated aluminosilicate slurry having an average particle size of 5.7 microns and a concentration of 28.1% by weight. (
1st step) The chemical composition of the obtained activated aluminosilicate on a dry basis at 110°C is shown in Table B, and the particle size distribution determined by the sedimentation method is shown in Table 0.

A sodium aluminate solution (ht2o323.2% by weight) was added to 378 g of the above activated aluminosilicate slurry.

Na2O1B-7M content) 96.51 and sodium hydroxide solution (Na2O3 containing 7.0% by weight) 90.8#
A solution of diluted with 140 liters of water was mixed, and the solution was heated to 48 ml at room temperature.
After stirring for an hour, the reaction vessel was sealed and placed in a 95°C water bath for 4 hours.
The mixture was kept quiet for 8 hours to perform crystallization. Subsequently, the solid was separated by suction filtration and washed with water until the - of the washing liquid became 10.5. The obtained product was confirmed by X@ diffraction and chemical composition analysis to be sodium type zeolite Y (hereinafter referred to as Na-Y zeolite) with a 5in2/At203 molar ratio of 3.79. (Second step) The above Na-Y zeolite 50# (110℃ dry matter equivalent)
Ammonium chloride solution with a concentration of 53.5 #/no 1010
The mixture was dispersed in 0O and stirred for 3 hours at 80°C, filtered under suction, and washed with 1000ml of water.

53.5117A! After repeating the ion exchange operation three times with a concentrated ammonium chloride solution, the washing solution was washed with water until no chloride ions were detected, and the obtained ammonium-type zeolite Y (hereinafter referred to as NH4-Y zeolite) was It was dried at ℃ for 20 hours. (Third step) Finally, the NH4-Y zeolite 30.9 was placed in an alumina dish and fired in an electric furnace at 450°C for 5 hours.
It was converted into Y zeolite. (Fourth step) H-Y zeolite was produced using acid clay from Odo, Shibata City, Niigata Prefecture.

The main components of the suspended acidic clay from Odo, Shibata City, Niigata Prefecture are 510274.6% by dry weight (drying at 110°C).
At20314.1 *Fe2O32,99, MgO
1,84, CaO 1,77, and loss on ignition 4.65.

This raw acid clay was treated by the method shown in the first step of Zeolite 1 production, and the average particle size was 5.9 microns.
An activated aluminosilicate slurry having a concentration of 4% by weight was obtained.

(First step) The chemical composition of the obtained activated aluminosilicate on a dry basis at 110° C. is shown in Table D, and the particle size distribution determined by the sedimentation method is shown in Table E.

Table D Table E A sodium aluminate solution (A/, 20323.2% by weight) was added to the above activated aluminosilicate slurry 3901.

18.7% by weight of Na2O) 79.411 and sodium hydroxide solution (containing 7.0% by weight of Na2O3) 113.
A solution prepared by diluting 9 with 210 g of water was mixed and stirred at room temperature for 5 hours, then sodium chloride 12.2.9 was added.
Crystallization was carried out by stirring in a 5°C water bath for 20 hours. After suction filtration, water washing was performed until the - of the washing liquid became 10.5. The obtained product was determined by X-ray diffraction and chemical composition analysis to have a 5i02/A/203 molar ratio of 3.90ONa.
-I confirmed that it is Y zeolite. (Second step) 50g of the above Na-Y zeolite (calculated as dry matter at 110°C) was dissolved in ammonium chloride at a concentration of 53.511713*x
o o oat, stirred at room temperature for 20 hours, filtered with suction, and 10001! Washed with Ll water.

After repeating the ion exchange operation three times using an ammonium chloride solution with a concentration of 53.5 g/min, the washing solution was washed with water until no chlorine ions were detected, and the resulting NH4
-Y zeolite was dried at 110°C for 20 hours. (3rd
Process) Finally, 30g of the above NH4-Y zeolite was placed in an alumina dish and calcined for 5 hours in an electric furnace at 450°C.
Converted to zeolite. (Fourth Step) Production of Zeolite A3 - Example The activated aluminosilicate slurry obtained in the first step of the production of Zeolide Cliff 2 was added to the raw material, and H-Y zeolite was produced by another method.

A sodium aluminate solution (At20323.2% by weight, Na2O1
A solution prepared by diluting 61.3F (containing 8.71Jit%) and 136F sodium hydroxide solution (NJL2037.ON content) in 154g of water was mixed and stirred until uniform. After the reaction mixture was kept quiet at room temperature for 20 hours, sodium chloride 11.6. ! i' was added and stirred for 20 hours in a 95°C water bath to perform crystallization.

After suction filtration, water washing was performed until the - of the washing liquid became 10.5. The obtained product was determined to be 5102/A/! by X-ray diffraction and chemical composition analysis. , 203 and a molar ratio of 420.

The above Na-Y zeolite was converted to H-Y zeolite using the method shown in the third and fourth steps of Zeolitem 2 production.

Using the Na-Y zeolite obtained in the second step of Zeolite Tom 2 production, a zeolite with different ion exchange conditions from Ya 2 was produced.

For Zeolite & 4, Na-Y Zeolite 50II (1
10℃ dry matter conversion) is 26.81! Zeolite & 5 was dispersed in 10,001 nl of ammonium chloride solution with a concentration of /l, stirred at room temperature for 20 hours, suction filtrated, and washed with water.
9' (calculated as dry matter at 110℃) was dispersed in 1000ml of ammonium chloride solution with a concentration of 53.51/l, and
The ion exchange operations of stirring for hours, suction filtration, and washing with water were repeated 5 times. Finally, the washing solution was washed with water until no chlorine ions were detected, and the obtained NH4-Y zeolite was dried at 110°C for 20 hours, and 30I was
It was calcined in an electric furnace at 0°C for 5 hours and converted into H-Y zeolite.

Using the Mζ-Y zeolite obtained in the third step of producing zeolite A2, zeolite was produced under different firing conditions than in Example 42. NH4-Y zeolite 30.9 was placed in an alumina dish and zeolite A6 was calcined at 350°C and zeolite A7 at 600°C for 5 hours in an electric furnace to convert it into H-Y zeolite.

Zeolite was manufactured using sodium silicate as a silicic acid raw material. No. 3 sodium silicate solution (5in22
1.5% by weight, NIL207.0% by weight) 512g
A sodium aluminate solution (At20.22.9% by weight, Na2O1B,
4% by weight) 54.2.9 and sodium hydroxide solution (
Na2O3 (containing 7.0% by weight) 236.9 and water 109
The solutions diluted to 3.9% were mixed, allowed to stand for 24 hours at room temperature, and then the reaction vessel was sealed and allowed to stand in a 95°C water bath for 40 hours to effect crystallization. After suction filtration, the - of the cleaning solution is 10
．． Washing with water was continued until the temperature reached 5. The obtained product was determined to be 5IO2/At203 by X-ray diffraction and chemical composition analysis.
It was confirmed that the zeolite was Na-Y zeolite with a molar ratio of 3.65. This Na-Y zeolite was produced using H-
It was converted into Y zeolite.

Manufacture of Zeolite A9 - Comparative Example A zeolite was manufactured using an aqueous colloidal silica sol as a silicic acid component raw material.

Commercially available aqueous colloidal silica sol (Snowtex 30.5in, 230.0% by weight, manufactured by Nissan Chemical Industries, Ltd.)
667#, sodium aluminate solution (At20.2
2.9% by weight, containing 18.4% by weight of Na2O) 52.4
．． 9 and sodium hydroxide solution (Na2037.0% by weight
A solution prepared by diluting 25011 and 346I of water was mixed, stirred at room temperature for 48 hours, and then the reaction vessel was sealed.
The mixture was allowed to stand for 24 hours in a water bath at 0.degree. C. for crystallization. After suction filtration, water washing was performed until the - of the washing liquid became 10.5. The obtained product was determined to be 8102/At20. by X-ray diffraction and chemical composition analysis. It was confirmed that the zeolite was Na-Y zeolite with a molar ratio of 3.97. This Na-Y zeolite was converted to H-Y zeolite using the method shown in the third and fourth steps of zeolite A2 production.

Similar to Flat 9, aqueous colloidal silica sol was suspended as the silicic acid raw material.

Commercially available aqueous colloidal silica sol (contains Snowtex 30.810230.0% by weight manufactured by Nissan Chemical Industries, Ltd.)
66719, sodium aluminate solution (At203
22.9% by weight, Na2O1B, 4% by weight) 55.
(l and sodium hydroxide solution (Na2037.0% by weight)
Contains) 200. ! i+ and diluted with water 188II were mixed, stirred at room temperature for 48 hours, the reaction vessel was sealed, and left standing in a 95°C water bath for 24 hours to effect crystallization. After suction filtration, water washing was performed until the pH of the washing solution reached 10.5. The obtained product was determined by X-ray diffraction and chemical composition analysis to contain Na with a 5102At203 molar ratio of 4.76.
-Y zeolite was confirmed. This Na-Y
Zeolite 50.9 (110℃ dry matter conversion) 53. !
Disperse in 1000 ml of ammonium chloride solution with a concentration of M'/l, and for Zeolite AIO, perform ion exchange operations of stirring at room temperature for 20 hours, suction filtration, and washing with water only once, and for Zeolite Flat 11, stir at 80°C for 3 hours, and perform suction filtration. The ion exchange operation of washing with water was repeated 5 times. In both cases, the washing solution was finally washed with water until no chloride ions were detected, and the obtained NH4-Y zeolite was dried at 110°C for 20 hours, and then 30.9 was calcined in an electric furnace at 550°C for 3 hours to obtain H -Y was converted to zeolite.

H-Y zeolite samples produced in the above manner 1 to 1
The physical properties of No. 1 are listed in Table F. The physical properties were measured by the test method described below.

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

(1) Na2o/azzox molar ratio and 5IO2/
At203 molar ratio is determined by chemical composition analysis. however,
At203 and 5i02 were determined by gravimetric method and Na2
Quantification of O is performed using atomic absorption spectrometry.

(2) Specific surface area and pore volume Nitrogen gas adsorption measurements are performed using Shibata Kagaku Kikai Kogyo Co., Ltd.'s Rip B, E, T surface area measuring device (Model P-600). The specific surface area is determined by the B, E, and T one-point method, and the pore volume is determined by the amount of adsorption at saturated vapor pressure.

However, the sample was heated to 10 to 10 mHg at 200°C for 2
After heating and degassing for a period of time, adsorption measurements are performed.

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

(b) Grind 50 mJ of 41-mL Erlenmeyer flask cores in an agate mortar to 200 mes
The sample was passed through a sieve with a diameter of 74 microns.
．． After drying in a constant temperature dryer at 200° C. for 2 hours, the sample was left to cool in a desiccator for 15 minutes, and the weight was measured.

The dry sample weight (W) is calculated from the difference from the empty Erlenmeyer flask weight.

(→ 0 with reagent n-f thylamine and reagent special grade benzene
．． A lNn-butylamine benzene solution is prepared, and the factor f is determined by standardizing it using a 0.1 N oxalic acid solution, which is a reagent for volumetric analysis.

(c) 0,IN The amount v (mJ) of the n-butylamine benzene solution is calculated using the following formula.

Here, A is the amount of n-butylamine (m
eq/I ) and A = 0.5 n (n = Or
l, 2, 3, 4, 5, 6).

) Add reagent grade benzene to the Erlenmeyer flask so that the content with v (1 nl) calculated in ←→ becomes 10, stopper it, and disperse the sample using an ultrasonic cleaner.

(e) (V calculated in 9 (0.IN n of rfLl)
- Add the butylamine solution to an Erlenmeyer flask, cover with vinyl tape to prevent the stopper from coming off, fix it in a figure 8 shaker (ss-go manufactured by Tokyo Rikakikai Co., Ltd.), and shake at room temperature for 24 hours.

(f) Add 3 drops of a 0.1% benzalacetophenone benzene bath solution prepared with reagent benzalacetophenone and reagent special grade benzene to the shaken Erlenmeyer flask as an indicator of pKa -5,6. After capping and shaking gently, observe the color of the sample surface.

(υ The highest value of A (meq/II) among those whose surface is colored yellow, which is the acidic color of the indicator, is
1 (meq/I).

(A) The number of Erlenmeyer flasks in (A) is 10,
A in C is A=A, +〇, 05n (n ==
Or 1.

2.Return the operations from (a) to (f) with exactly the same content except for 3, 4, 5, 6.7, 8.9).

υ) The largest value of A (meq/g) among those whose surface is colored yellow is defined as A2 (meq/, 9), and the acidity (meq /
,? ) is expressed as A2-A2+0.05 (meq/g).

Examples 1 to 3 In a four-bottle flask equipped with a thermometer, a stirring blade, and an air-cooled tube, 224.9 (0.8 mol) of 1-icosene and 205.9 (melting point 79.8°C) of purified naphthalene (melting point 79.8°C) were added. 1.6 mol)
and H-Y zeolite 11.211 were charged and set on a mantle heater. While stirring, the temperature was raised from room temperature to 210° C. in about 30 minutes. This time point was taken as the starting point of the reaction, and the reaction temperature was kept at 21.0 to 215°C and the reaction was continued. The reaction mixture sampled at regular intervals was centrifuged at 80°C or higher, and the resulting supernatant was used as a sample for analysis. unreacted naphthalene content in the sample,
The unreacted olefin content and monoalkylnaphthalene content were determined by gas chromatography, and based on the results, the olefin conversion rate and the selectivity to monoalkylnaphthalene were calculated. The binaphthyl content in the sample was separately determined by thin layer chromatography.

In the above reaction method, Examples 1 to 3 are cases in which F-listed Olide Yas 1 to 3 are used as H-Y zeolite, and Comparative Examples 1 to 8 are cases in which zeolite A4-11 is used, respectively. The reaction results are shown in Table G. According to the results of Examples 1 to 3, both the olefin conversion rate and the selectivity to monoalkylnaphthalene were high;
Furthermore, there is almost no formation of binaphthyl, and the method for producing alkylated aromatic compounds according to the present invention using a zeolite having suitable physical properties is well exemplified. Comparative Examples 1 to 4 correspond to cases where zeolites &4 to 7 shown in Table F are used, but it is understood that the acidity is low and the catalytic activity is low because the ion exchange conditions and calcination conditions were not selected appropriately. Ru.

In addition, Comparative Examples 5 to 8Fi correspond to cases in which zeolite plates 8 to 11 shown in Table F are used, but if the silicic acid content raw material is different, the precursor is Na-Y zeolite, which is similar in appearance. Nevertheless, it is understood that the physical properties of the H-Y zeolite produced vary greatly and do not exhibit desirable catalytic activity.

In particular, when a zeolite with a high acidity of 1n49 to 11 was used, an unacceptable amount of binaphthyl was produced.

Further, when the method of the present invention is applied to a method for producing alkylnaphthalene, an alkylnaphthalene having excellent oxidation stability and an α-substituted product/β-substituted product ratio of 1.0 or more can be obtained.
It has the advantage of

Example 4 Purified naphthalene (256.12.0 mol) was charged into a 1104-round flask equipped with a thermometer, stirring blade, cold tube, and Teflon tube for supplying olefin, and the oil temperature was set at 130°C.
was placed on an oil bath.

Naphthalene began to dissolve and stirring was started when stirring became possible. When the naphthalene is completely dissolved, raise the temperature of the oil bath to bring the temperature of the naphthalene to 165-170℃, and then
Added y. Immediately, the supply of 1-decene was started through a Teflon tube using a liquid pump, and 168 g (1.2 moles) of 1-decene was supplied over a period of 4 hours.

During this time, the temperature of the reaction mixture was maintained at 165-170°C.

The reaction was further continued at the same temperature for 1 hour, and then cooled to 100°C. The catalyst was removed from the reaction mixture by pressure filtration, and the filter was subjected to gas chromatography analysis. The conversion rate of 1-decene was 99.1%, and the selectivity to monodecylnaphthalene was 94.6%.

Example 5 1-tetradecene 16 was added to the same reactor as in Example 1-3.
7.9 (0.85 mol), methylnaphthalene (mixture of 1-methyl and 2-methyl) 238.9 (1.7 mol),
8.4 g of H-Y zeolite (F Omotenoya 2) was charged.

The reaction mixture was stirred, heated, and heated to 215 to 220°C for 6 hours. Analysis of the reaction mixture by gas chromatography revealed that the olefin conversion rate was 96.4% and the selectivity to methyltetradecylnaphthalene was 92.0%.

Example 6 276 g (3 mol) of toluene, 168.9 (1 mol) 1-dodecene, H-Y zeolite (A in Table F) were placed in an 11 glass autoclave equipped with a stirrer, thermometer, and heater.
2) 8.4g was charged. After purging the inside of the autoclave with nitrogen, the autoclave was sealed, and the temperature was raised to 200°C in about 1.5 hours while stirring, and then maintained at 195 to 205°C for 2 hours. Then, after cooling the reaction mixture, the catalyst was removed by pressure filtration to obtain a filter pond. As a result of analysis by gas chromatography, the olefin conversion rate reached 99.5% and the selectivity to dodecyltoluene reached 97.3%.

Example 7 In order to demonstrate 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
A comparison is shown in Table H. The reason why the olefin conversion rate corresponding to Example 2 in Table H is different from Table G is that Table G shows the conversion rate after 6 hours of reaction, whereas Table H shows the reaction acceleration effect due to 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 that there is no difference in the selectivity to monoalkylnaphthalene when the olefin conversion rate reaches a high rate of 95% or more. be done.

Table H Note 1) After 3 hours of reaction Note 2) After 6 hours of reaction (at olefin conversion rate of 99.1%)
Procedural amendment (spontaneous) September 21, 1985 Kunio Ogawa, Commissioner of the Patent Office1, Indication of the case application, Patent Application No. 294949, filed in 19882, Name of the invention Process for producing alkylated aromatic compounds 3, Amendment Relationship with the case of a person who does
On stock company 4, agent 〒105 5, no date of amendment order 6, column for detailed description of invention in specification subject to amendment? , Contents of the amendment (1) In the fourth line from the bottom of page 9 of the specification, the statement "rHo≦-6,5" is corrected to FHo≦-5,6j.

Claims (2)

[Claims] (1) In a method for producing an alkylated aromatic compound, which comprises reacting an aromatic hydrocarbon and an alkylating agent in the presence of an aluminosilicate catalyst, activated silicon obtained by acid treatment of clay minerals is used as the aluminosilicate catalyst. Synthesized using acid or activated aluminosilicate as a silica raw material,
Hammett's acid strength function: -5.6 or less acidity is 0.5
Hydrogen type zeolite Y in the range of 1.0 meq/g
A manufacturing method characterized by using. (2) A method for producing an alkylated aromatic compound comprising reacting an aromatic hydrocarbon and an alkylating agent in the presence of an aluminosilicate catalyst in a liquid phase and in a batch process, in which acid treatment of clay minerals is used as an aluminosilicate catalyst. The activated silicic acid or activated aluminosilicate obtained by
A production method characterized by using hydrogen type zeolite Y having the following acidity in the range of 0.5 to 1.0 meq/g and flowing an inert gas into the reaction vessel.