JP3009249B2 - Method for producing mono- and / or dialkylnaphthalene - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing mono- and / or dialkylnaphthalene by contacting naphthalene and / or monoalkylnaphthalene with an alkylating agent with zeolite as a catalyst.

[0002]

[Prior art]

<Zeolite> There are a wide variety of zeolites, including faujasite-type zeolites, a kind of crystalline aluminosilicate, and ZSM-5, a kind of crystalline silicate.

<Faujasite-type zeolite> Faujasite-type zeolite, which is a kind of crystalline aluminosilicate, has a three-dimensional pore structure and has pores through which aromatic compound molecules can be easily removed. It is known that it can be used as an alkylation catalyst for aromatic hydrocarbons such as naphthalene and monoalkylnaphthalene. (For example, JP-A-63-14739, JP-A-63-230645, and JP-A-1-24
No. 5855, JP-A-1-246230)

Japanese Patent Application Laid-Open No. Sho 63-14738 discloses that naphthalene or monoalkylnaphthalene is alkylated using a faujasite-type zeolite that has been subjected to a dealumination treatment.

Some studies have been made on a method of modifying a faujasite-type zeolite (particularly, a Y-type zeolite) with a metal.

For example, JP-A-63-8344 discloses HY type, dealuminated HY type, alkali metal Y type, alkaline earth metal Y type, rare earth metal Y type or 8 type.
A method for producing a dialkylnaphthalene from a monoalkylnaphthalene and a lower alcohol by using a group Y metal Y-type zeolite is disclosed. According to the description in the lower left column of page 2 of this publication, HY type or dealuminated H
Type Y is prepared by acid treatment of type Y zeolite, and alkaline earth metal Y, rare earth metal Y or group VIII metal Y is prepared by ion exchange or impregnation with ions of these metals. In Example 3, the rare earth metal-exchanged Y-type zeolite was used. In Example 4, H-type zeolite was used.
The Y-type zeolite is vacuum impregnated with nickel nitrate and then dried and calcined. In Comparative Examples 4 and 5, rare-earth metal exchanged X-type zeolite is used.

[0007] Proceedings of the symposium "Catalyst research, exploring contact points between industry and academia", pages 18 to 19, show that Na of Y type zeolite belonging to faujasite type zeolite is La, Ce,
It is disclosed that a material whose pore size has been adjusted by ion exchange with a rare earth metal such as Nd or an alkaline earth metal is used for the alkylation reaction of naphthalene.

[0008] Also, one of "CHEMISTRY LETTERS, 1986"
On page 213, (a) HY-type zeolite is converted to iron (III) nitrate.
Iron zeolite loaded with Fe while dealuminizing by treating with an aqueous solution; (b) iron ion-exchanged zeolite loaded with iron at an ion exchange site by treating with an aqueous iron (II) nitrate solution; The results of examining the catalytic activity in the disproportionation reaction of toluene using each of the iron zeolites obtained by depositing iron hydroxide on the zeolite are shown.In particular, in a mixed gas stream of hydrogen sulfide and hydrogen, (a ) Significantly improves the disproportionation activity of iron zeolite with respect to toluene.

The X-type zeolite belonging to the faujasite-type zeolite typically has a composition of Na ₂ O / Al ₂ O ₃ /2.5SiO ₂ / 6H ₂ O (Si / Al atomic ratio is 1.25 ), Si at the time of its synthesis
The O ₂ / Al ₂ O ₃ molar ratio is 3-5, and the crystallization reaction temperature is around 100 ° C.

The Y-type zeolite, which also belongs to the faujasite-type zeolite, typically has a composition of Na ₂ O / Al ₂ O ₃ /4.8SiO ₂ / 8H ₂ O (Si / Al atomic ratio: 2.4), Si at the time of its synthesis
O ₂ / Al ₂ O ₃ molar ratio is 8 to 20, the crystallization reaction temperature is 100 ° C.
Before and after.

In the description of the conventional method in Japanese Patent Application Laid-Open No. 61-21911, faujasite-type zeolites generally have an oxide molar composition of (0.9 ± 0.2) M ₂ O / Al ₂ O ₃ / xSiO _2. / wH ₂ O (M is an alkali metal cation here, x is 2.5-6,
It is shown that w is represented by 6-9).

The invention disclosed in Japanese Patent Application Laid-Open No. 61-21911 discloses a method in which a raw material mixture comprising a silica source, an alumina source and an alkali source is heated and crystallized to produce a faujasite-type zeolite. , An aqueous solution of an alkali aluminate and an aqueous solution of an alkali hydroxide are mixed and aged, and a transparent liquid phase substance is obtained in the raw material mixture.

<ZSM-5> On the other hand, ZSM-5, which is a kind of crystalline silicate, typically has a composition of (0-20) M ₂ O / (0-20) Al ₂ O ₃ / 100SiO ₂ . (Si / Al atomic ratio is 15 or more), the SiO ₂ / Al ₂ O ₃ molar ratio at the time of its synthesis is, for example, 180, and the crystallization reaction temperature is around 150 ° C.

JP-A-57-196719 discloses a reaction mixture containing a silica source, a transition metal and / or alumina source, an alkali source, water and diglycolamine, and the mixture is used to form a crystalline silicate. There is disclosed a method for producing a crystalline silicate comprising heating at a time and a temperature until the transition metal is reached. For transition metals, Fe, Ni, Co, Rh, Ru, Pd, La, and Ce are disclosed.
, Ti, V, Cr, Nb, and Ta are used. The use of diglycolamine is for increasing the degree of crystallinity and improving the catalytic activity regardless of the type of the transition metal. In Example 1, a solution B composed of a mixture of water and hydrochloric acid in which ferric chloride and aluminum sulfate were dissolved was added to a solution A composed of water glass, and diglycolamine was further added to form a reaction mixture. This mixture was reacted with stirring to produce a crystalline silicate having a composition of 0.6Na ₂ O / 0.45Fe ₂ O ₃ /0.55Al ₂ O ₃ / 77SiO ₂ excluding organic compounds and water of crystallization. It is shown.

[0015]

As described above, as described above,
Faujasite-type zeolites are known as catalysts for the alkylation of aromatic hydrocarbons such as naphthalene and monoalkylnaphthalene, but the selectivity of the target product is not so high because of the large gauge in the crystal. In this gauge, coke is precipitated or molecules having a large molecular diameter are adsorbed in the gauge, and the reaction activity is apt to deteriorate.

The method of subsequently modifying the Y-type zeolite with a metal is to reduce the above-mentioned large gauge and improve the selectivity.
No. 4 and the symposium "Searching for Contact between Catalyst Research and Industry-Academia", a method described in the proceedings, that is, ion exchange of Y-type or X-type zeolite using alkaline earth metal or rare earth metal, or nitric acid conversion to HY-type zeolite The method of vacuum impregnation of nickel has a limitation in improving selectivity, and there is still room for improvement in industrialization. In addition, when the ion exchange is performed with an alkaline earth metal, the metal introduced by the ion exchange is converted into BaCO3 or the like when the catalyst is regenerated, so that there is a problem that it cannot be reused.

Further, the methods (a), (b) and (c) described in "CHEMISTRY LETTERS, 1986" involve the disproportionation reaction of toluene having a small molecular weight, so that the method can be applied to other organic compounds. On the other hand, it is not possible to determine what effect it has, and in a hydrogen sulfide / hydrogen mixed gas, the conversion rate of the disproportionation reaction of toluene is large, but the conversion rate under a hydrogen gas stream is small. Alternatively, it is not known whether the compound exhibits favorable conversion and selectivity to other organic compounds when hydrogen is not used.

Japanese Patent Application Laid-Open No. 57-196719 discloses a method in which a transition metal is previously mixed in a reaction mixture to cause a reaction.
The present invention relates to SM-5 and has no direct relation to the present invention for obtaining a faujasite-type zeolite that is crystalline "aluminosilicate". Further, when a crystalline silicate is used, even if a transition metal is introduced, selectivity in the alkylation reaction of an aromatic hydrocarbon such as naphthalene or monoalkylnaphthalene is small.

Under such a background, the present invention provides industrially advantageous mono- and / or mono- and / or mono-alkyl naphthalenes and alkylating agents by using a specific metal-containing faujasite-type zeolite. It is an object of the present invention to provide a method for producing dialkylnaphthalene.

[0020]

The process for producing mono- and / or dialkylnaphthalenes according to the present invention comprises contacting naphthalene or / and / or monoalkylnaphthalene with an alkylating agent with zeolite as a catalyst to produce mono- and / or dialkylnaphthalene. In the production of, a metal-containing faujasite-type zeolite containing both an iron group metal or a titanium group metal (A) and a platinum group metal (B) is used as the zeolite.

Hereinafter, the present invention will be described in detail.

Raw Materials In the present invention, naphthalene or / and / or
And monoalkylnaphthalene. Among them, examples of the monoalkylnaphthalene include lower monoalkylnaphthalenes having a linear or branched alkyl group having 1 to 4 carbon atoms, such as methylnaphthalene, ethylnaphthalene, propylnaphthalene, and butylnaphthalene, and monomethylnaphthalene is particularly important. .

Examples of the alkylating agent include those having 1 to 4 carbon atoms such as methanol, ethanol, propanol and butanol.
And lower olefins having 1 to 4 carbon atoms such as ethylene, propylene and butylene. The lower alcohol is more practical when both are compared.

[0024] In the catalyst and the invention, as a catalyst for reacting the naphthalene and / or monoalkyl naphthalene with an alkylating agent, containing both iron group or titanium group of metals (A) and a platinum group metal (B) A metal-containing faujasite-type zeolite is used. Examples of iron group metals are Fe, Co, N
i, examples of titanium group metals are Zr, examples of platinum group metals are Pt,
Pd, Ru, and Rh. Of these, it is particularly important that the iron or titanium group metal (A) is Fe and the platinum group metal (B) is Pt.

In the metal-containing faujasite-type zeolite containing both the iron group or titanium group metal (A) and the platinum group metal (B), the iron group or titanium group metal
(A) is desirably contained in such a manner that part of Al constituting the crystal skeleton of zeolite is substituted.
(B) is desirably introduced into the ion exchange site of zeolite by ion exchange. Such a metal-containing faujasite-type zeolite is produced, for example, by the method described below.

One of them is that a part of Al constituting the crystal skeleton of a separately prepared faujasite-type zeolite or a commercially available faujasite-type zeolite is subsequently replaced with an iron group or titanium group metal (A). At the same time as the substitution operation or at an appropriate stage after the substitution operation, a platinum group metal (B) is further introduced into the ion exchange site of the zeolite by ion exchange.

In this method, the faujasite-type zeolite is suspended in an aqueous solution of a compound of the metal (A) of the iron group or the titanium group (for example, a water-soluble salt such as nitrate, sulfate or chloride) and heated. After that, the mixture is separated into solid and liquid by means such as centrifugation, and then sufficiently washed with water, and then dried and fired. As a result, part of Al constituting the crystal skeleton is replaced with the iron group or titanium group metal (A). When the zeolite is suspended in an aqueous solution of the metal (A) compound, a water-soluble compound of the platinum group metal (B) (for example, an amine complex salt) is allowed to coexist with the aqueous solution. Can be achieved simultaneously. The ion exchange with the platinum group metal (B) can be performed at any stage of the step of substituting a part of Al constituting the crystal skeleton with the iron group or titanium group metal (A). It can also be carried out after firing.

Another one is that a compound of an iron group or titanium group metal (A) is blended at the beginning of the zeolite production process so that a part of Al constituting a crystal skeleton is an iron group or titanium group metal (A). This is a method in which a faujasite-type zeolite substituted with A) is obtained, and then a platinum group metal (B) is introduced into the ion-exchange site of the zeolite by ion exchange.

In this method, first, a compound of a metal (A) of the iron group or titanium group (for example, a water-soluble salt such as a nitrate, a sulfate or a chloride) is used together with a silica source, an alumina source and an alkali source. A blended mixture is prepared. As the silica source, those used for zeolite synthesis, for example, silica powder, colloidal silica, water glass, silica sand, hydrated solid silicic acid, and the like are used. As the alumina source, aluminum sulfate, sodium aluminate, potassium aluminate, aluminum chloride, activated alumina and the like are used. As the alkali source, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, and the like are used.When an alkali metal salt is used as a silica source or an alumina source, the alkali metal may be used as the alkali source. it can.

The composition of the mixture is SiO ₂ / Al ₂ O ₃ = 9-15 M ′ ₂ O / Al ₂ O ₃ = 1.5-5 H ₂ O / M ′ ₂ O = 30-55 M _m O _n / SiO ₂ = 0.001-0.15 (However, M 'is an alkali metal, M is iron group or titanium group of metals, M _m O _n is m and n an oxide of a metal M a positive integer) When the composition is out of this range, the desired metal-containing faujasite-type zeolite cannot be obtained.

In preparing the mixture, a method of mixing an aqueous solution of an alumina source and a compound of a metal (A) of an iron group or titanium group with stirring in an aqueous solution of a mixture of a silica source and an alkali source; Alumina source under stirring,
A method of mixing an aqueous solution of an alkali source and an aqueous solution of a compound of the iron group or titanium group metal (A) is preferably employed.

By heating and crystallizing the above mixture under conditions that produce faujasite-type zeolite, the desired faujasite-type zeolite is obtained.

In this case, first, the main raw material mixture is heated and reacted to form a slurry-like substance, and then centrifuged and washed with water to obtain a gel-like substance. This gel-like substance is ground to form a fine gel-like substance. Therefore, it is also preferable to form a slurry by adding water, and mix the slurry with a separately prepared crystallization accelerator to provide crystallization. Here, as the crystallization accelerator, those obtained by aging the mixed aqueous solution comprising the above-mentioned silica source, alumina source and alkali source are particularly preferable. In addition, fine powder solid silica, fine powder zeolite and the like can also be used. When a crystallization accelerator is used, the composition of the main raw material mixture should be determined in consideration of its incorporation into the final zeolite.

The temperature at the time of preparing the mixture is preferably about 30 to 80 ° C. When the crystallization accelerator is a mixed aqueous solution comprising a silica source, an alumina source and an alkali source, the temperature of the crystallization preparation is also preferably about 30 to 80 ° C.

The crystallization reaction temperature is desirably about 70 to 110 ° C., particularly preferably about 90 to 100 ° C. If the temperature is too high, the crystallization reaction is too fast, so that the iron group or titanium group metal (A) is reduced. In some cases, the desired skeleton position may not be reached, whereas when the temperature is too low, crystallization does not proceed smoothly. Also,
The crystallization reaction time is suitably about 8 to 48 hours. If the reaction time is too short, the crystallization becomes insufficient, and if the reaction time is too long, the metal (A) once entering the skeleton is expelled. In some cases, it is disadvantageous in terms of productivity.

After the crystals are formed, solid-liquid separation is performed, and the resultant is sufficiently washed with water and then dried. As a result, a target crystal is obtained.

The obtained crystal is fired in an air atmosphere at a temperature of about 300 to 700 ° C., particularly about 350 to 600 ° C., for about 20 minutes to 5 hours. This allows
Oxide composition _{(0.1-0.15) Al 2 O 3 /(0.6-0.8)SiO} 2 /(0.1-0.2)M '2 O / (0.001-0.1) M m O n ( however, M' is an alkali metal, M is iron group or titanium group of metals, M _m O _n m and n an oxide of the metal M is a positive integer, the metal-containing faujasite zeolite numbers in parenthesis are molar composition) is can get.

Usually, the calcined product is subjected to an acid treatment to obtain a hydrogen type or an NH ₄ type and then calcined in air to obtain a hydrogen type, or ion exchange is performed on the calcined product. And converted to NH ₄ type, and then further added under steam atmosphere.
By firing at a temperature of about 00 to 900 ° C. in a steam atmosphere for about 10 minutes to 3 hours, a hydrogen type is obtained. Firing in a steam atmosphere is preferable from the viewpoint of alkylation of naphthalene and / or monoalkylnaphthalene, since slight removal of Al occurs to slightly deform the crystals.

When the above-mentioned calcined product or zeolite in the hydrogen form is subjected to ion exchange with the platinum group metal (B), the desired metal-containing zeolite is obtained.

Reaction Conditions The alkylation reaction can be carried out in either a gas phase or a liquid phase, but is usually carried out in a liquid phase. Reaction
If the operation is performed under a hydrogen pressure of 0.5 kg / cm ² G or more, the life of the catalyst tends to be improved. At the time of the reaction, a fluidized bed reactor or a moving bed reactor can be used in addition to a fixed bed reactor using a reaction tube, a pressurized fixed bed reactor or the like.

In the case of using a fixed bed reactor, a reaction tube is filled with a metal-containing faujasite type zeolite as a catalyst and, if necessary, is placed in a stream of air, nitrogen or the like.
Stabilize the catalyst by heating at a temperature of about 500 ° C., and then add a naphthalene or / and a monoalkylnaphthalene and an alkylating agent, and if necessary, a saturated alicyclic hydrocarbon such as decalin or bicyclohexyl. The resulting mixture is supplied to the above-mentioned reaction tube, and brought into contact with a catalyst to cause an alkylation reaction. The addition of a saturated alicyclic hydrocarbon is effective in preventing the activity of the catalyst from decreasing.

The supply amount of the naphthalene and / or monoalkyl naphthalene, in terms of catalyst per unit weight (WHSV) 0.5~20hr ^-1, is especially to the 1～15Hr ^-1 is usually.

The amount of the alkylating agent to be supplied is about 1 to 10 parts by weight, especially about 1 to 3 parts by weight, per 1 part by weight of naphthalene and / or monoalkylnaphthalene. If the proportion of the alkylating agent is too small, the degree of alkylation becomes insufficient, while if it is too large, by-products such as trialkylnaphthalene increase.

The reaction temperature is between 150 and 500 ° C., preferably between 200 and 400 ° C., in particular between 250 and 350 ° C. The reaction pressure may be any of normal pressure, reduced pressure, and increased pressure, but it is advantageous from the viewpoint of operation and equipment to carry out the reaction at normal pressure or under a pressure of up to 10 kg / cm ² G.

[0045]

Function and Effect of the Invention There are various isomers of dimethylnaphthalene, and among them, 2,6-dimethylnaphthalene is useful. Oxidation of 2,6-dimethylnaphthalene gives naphthalene-2,6-dicarboxylic acid. Polyesters obtained from this dicarboxylic acid have a wide range of uses in synthetic fibers and films.

In the present invention, a metal-containing faujasite type zeolite containing both an iron group or titanium group metal (A) and a platinum group metal (B) is used as a catalyst. Is that the large gauge of general faujasite-type zeolite is reduced by the above metal (A), and the ion exchange site is a platinum group metal.
(B), when used as an alkylation catalyst for naphthalene and / or monoalkylnaphthalene, the conversion rate (reaction rate) of the raw material is high, and the target substance (for example, 2,6- Is also high. In addition, it is possible to carry out highly active alkylation reaction using easily available naphthalene (Naphthalene production in Japan is 250,000 tons / year, methyl naphthalene production is 2-3,000 tons / year) as raw material. When recycling of a by-product (β-methylnaphthalene or α-methylnaphthalene) is considered, the alkylation can be performed on the by-product with high activity. In addition, the effect of being able to regenerate the catalyst at a low temperature so as not to destroy the zeolite structure is exhibited, which is suitable for industrialization.

In addition, the present invention provides that the raw material supply weight per unit weight of catalyst (WHSV) can be increased,
That the reaction conditions (temperature, pressure) are relaxed, that the catalyst is solid (granular), so that a fixed-bed flow reactor can be used, and that there is no need to separate the reaction product and the catalyst;
Even when the saturated alicyclic hydrocarbon is not added, the deterioration of the catalyst is small, the oxide of the target metal remains in the pores,
There is also an effect that there is little possibility that coke is deposited in the zeolite gauge.

[0048]

The present invention will be further described with reference to the following examples. All the water used is ion exchange water.

<Production of Catalyst> Catalyst Production Example 1 Ultra-stable Y-type zeolite (HSZ-
330HUA) was suspended in a mixed solution 300ml of tetraamine platinum chloride to 10 g 0.05 N (II) and 0.3N of Fe (NO _{3) 3.} This was stirred at 80 ° C. for 1 hour, centrifuged, and sufficiently washed with ion-exchanged water. Next, after drying all day and night at 100 ° C., it was calcined in air at 540 ° C. for 3 hours to obtain a platinum ion exchanged-iron-containing zeolite. This was adjusted to a particle size of 26 to 42 mesh.

The platinum ion exchanged iron-containing zeolite
The Fe ₂ O ₃ content was 11.6% by weight and the Pt content was 1.4% by weight.

Catalyst Production Example 2 The procedure of Catalyst Production Example 1 was repeated except that a 0.3 N—Zr (NO ₃ ) ₂ aqueous solution was used instead of the 0.3 N—Fe (NO ₃ ) ₃ aqueous solution, and a platinum ion exchanged zirconium-containing zeolite was used. Obtained. The platinum ion-exchanged zirconium-containing zeolite had a Zr ₂ O ₄ content of 5.3% by weight and a Pt content of 1.2% by weight.

Catalyst Production Example 3 A solution was prepared by mixing an aqueous solution in which 51 g of aluminum sulfate was dissolved in 100 g of water and an aqueous solution in which 18.6 g of iron nitrate was dissolved in 40 g of water. 207 g of an aqueous solution of sodium silicate (water glass No. 3) and 5.8 g of sodium hydroxide were added to water 15
The resultant was mixed with an aqueous solution dissolved in 2 g to obtain a solution B. The solution A and the solution B were heated to 60 ° C., and the solution A was added thereto while stirring the solution B with a homogenizer stirrer to start the reaction. Stirring was continued for 30 minutes after the start of the reaction to obtain a slurry-like substance. This slurry-like substance is separated into a gel-like substance and water using a centrifugal separator, water is added to the separated gel-like substance, centrifugation is performed again, and SO ₄ ^2- is not detected in the washing solution. Washing was repeated. Next, the obtained gel-like substance was ground by using a grinder to obtain a fine gel-like substance.

On the other hand, 8 g of sodium aluminate was added to water 22
g of an aqueous solution and 28 g of sodium hydroxide in water 4
An aqueous solution dissolved in 4 g was mixed and kept at 30 ° C. 82.8 g of an aqueous solution of sodium silicate (water glass No. 3) also kept at 30 ° C. was added to this mixed solution, and the temperature was raised to 40 ° C. with slow stirring, kept at this temperature for 60 minutes, and aged. An aqueous solution (solution C) was prepared as an accelerator.

100 g of the previously obtained fine gel-like substance (water 7
(1.4% by weight), 63 g of water was added thereto, and while sufficiently stirring with a homogenizer stirrer, 53 g of the liquid C prepared above was added, followed by stirring for 30 minutes to obtain a slurry for crystallization. This slurry for crystallization is placed in a sealed container made of fluororesin, and 9
It was allowed to stand in a thermostat at 5 ° C. for 24 hours to be crystallized. After the crystallization was completed, the solid-liquid was separated by a centrifuge, washed sufficiently with water, and dried at 110 ° C. The composition of the mixture, including the crystallization promoter, is, by molar ratio, SiO ₂ / Al ₂ O ₃ = 10 Na ₂ O / Al ₂ O ₃ = 3.3 H ₂ O / Na ₂ O = 43 Fe ₂ O ₃ / SiO ₂ = 0.017.

From the X-ray diffraction diagram of the obtained crystal, it was confirmed that the crystal was a faujasite-type zeolite.

Next, the crystal obtained above was calcined at 540 ° C. for 3 hours in an air atmosphere. Oxide composition after calcination was _{0.122Al 2 O 3 /0.719SiO 2 /0.143Na 2} O / 0.017Fe 2 O 3.

The calcined product was subjected to ion exchange twice at 80 ° C. using a 1N—NH ₄ NO ₃ solution, and then subjected to solid-liquid separation with a centrifuge and dried at 110 ° C.

After sintering the obtained NH ₄ type crystal at 700 ° C. for 1 hour under a steam atmosphere, 1N—NH ₄ NO
After performing ion exchange using the _three solutions under the same conditions as above, calcination was performed under the same conditions as above under a steam atmosphere. Thus, a hydrogen-type iron-containing zeolite was obtained.

The iron-containing zeolite had a SiO ₂ / Al ₂ O ₃ molar ratio of 4.9, a Na ₂ O content of 0.8% by weight, and a Fe ₂ O ₃ content of 4.8.
% By weight.

As a result of ESR (electron spin resonance) spectrum analysis of the obtained iron-containing zeolite, it was found that the iron-containing zeolite was substantially free of free Fe ₂ O ₃ .

10 g of the hydrogen-containing iron-containing zeolite obtained above
With 0.05N tetraammineplatinum (II) chloride and 0.3N Fe
An ion exchange operation of treating at 80 ° C. for 1 hour using 300 cc of a mixed aqueous solution of (NO ₃ ) ₃ was repeated once, followed by drying at 110 ° C. and calcination at 540 ° C. for 3 hours in an air atmosphere to obtain platinum. An ion-exchanged iron-containing zeolite was obtained. This was adjusted to 26 to 42 mesh.

The platinum ion exchanged iron-containing zeolite
The Fe ₂ O ₃ content was 18.9% by weight and the Pt content was 1.2% by weight.

Catalyst Production Example 4 (Comparative Example) Ultra-stable Y-type zeolite (HSZ-
330 HUA) was granulated to 26 to 42 mesh and used.

Catalyst Production Example 5 (Comparative Example) 0.05 N tetraammineplatinum (II) chloride and 0.3 N Fe (N
O ₃₎ instead of the mixed aqueous solution 300ml of _3, 0.3 N of Fe (NO _{3) 3}
Example 1 was repeated except that 300 ml of an aqueous solution of was used.

Catalyst Production Example 6 (Comparative Example) With respect to 10 g of the super-stable Y-type zeolite of Catalyst Production Example 4,
300 cc of an aqueous solution of 0.05 N tetraammineplatinum (II) chloride
Was repeated once, followed by drying at 110 ° C., and calcining at 540 ° C. for 3 hours in an air atmosphere to obtain a Pt content of 1.6.
% By weight of platinum ion exchanged zeolite was obtained. This is 26
４２42 mesh.

<Alkylation reaction> Examples 1 to 3 and Comparative examples 1 to 3 1.5 g of the catalyst obtained above was packed in a stainless steel pressurized fixed bed reactor, and the catalyst layer was heated to 300 ° C. in a nitrogen stream. did. After maintaining at this temperature for 2 hours, the pressure was 5 kg / cm ² G and the introduced amount was 30.
The mixture was switched to a hydrogen gas flow of ml / min, and 5.4 g of a 1: 1 mixture by weight of β-methylnaphthalene and methanol was supplied by a liquid pump to cause a reaction.

The results of analyzing the reaction products by gas chromatography (quantitative analysis by area ratio) are shown in Table 1 below.
It was as follows. N is naphthalene, MN is methylnaphthalene, DMN is dimethylnaphthalene, and 2,6-isomer selectivity is 2,6-isomer selectivity.

[0068]Table 1 During reaction β-MNProduct composition In DMN Conversion rate of catalyst used N α-MN DMN 2,6-isomer selectivity Example 1 Production Example 1 4hr 31.7% 3.6% 10.8% 58.7% 30.5% 6hr 31.3% 3.2% 10.4% 58.5% 30.1% Example 2 Production Example 2 6hr 26.5% 3.8% 10.1% 56.3% 28.6%Example 3 Production Example 3 3hr 27.2% 3.7% 11.2% 57.5% 31.8% Comparative Example 1 Production Example 4 3hr 11.1% 11.1% 11.3% 78.5% 30.5% Comparative Example 2 Production Example 5 4hr 18.6% 2.6% 9.8% 60.6% 28.2% 6hr 10.5% 2.4% 15.8% 67.8% 26.8%Comparative Example 3 Production Example 6 3hr 17.1% 10.8% 12.2% 65.3% 29.7%

From Table 1, it can be seen that the conversion of β-methylnaphthalene is significantly higher when the catalysts obtained in Catalyst Production Examples 1 to 3 are used than in the case where the catalysts obtained in Catalyst Production Examples 4 to 6 are used. Further, it is understood that the selectivity of the 2,6-form group in dimethylnaphthalene is also preferable. In addition, when the catalysts obtained in Catalyst Production Examples 4 to 6 were used, the conversion of β-methylnaphthalene was significantly reduced as the reaction time became longer, and the 2,6-form group in dimethylnaphthalene was selected. When the catalysts obtained in Catalyst Production Examples 1 to 3 were used, the conversion of β-methylnaphthalene was only slightly reduced even when the reaction time was prolonged. It can be seen that the decrease in the selectivity of the body group is negligible.

Example 4, Comparative Example 4 The weight ratio of β-methylnaphthalene to methanol was 1: 1.
Examples 1 to 3 were repeated except that 5.4 g of a 1: 1 mixture by weight of naphthalene and decalin and 1.2 g of methanol were supplied to the reactor by separate liquid pumps instead of 5.4 g of the mixture of Was. Table 2 shows the results.

[0071]Table 2 At the time of reaction NProduct composition In DMN Conversion rate of catalyst used N α-MN DMN 2,6-isomer selectivity Example 4 Production Example 1 4hr 75.8% 18.5% 21.8% 34.3% 28.4% 6hr 74.1% 20.9% 22.9% 28.1% 26.1% 8hr 72.7% 21.6% 23.7% 32.4% 26.2% Comparative Example 4 Production Example 5 4hr 68.9% 24.9% 25.2% 40.9% 29.1% 6hr 56.0% 28.4% 27.3% 32.5% 24.2%

From Table 2, it can be seen that the conversion of naphthalene was clearly higher when the catalyst obtained in Catalyst Production Example 1 was used than in the case where the catalyst obtained in Catalyst Production Example 5 was used. , 6-body group is also preferable. Further, when the catalyst obtained in Catalyst Production Example 5 was used, the conversion of naphthalene was significantly reduced when the reaction time was prolonged, and the selectivity of the 2,6-isomer group in dimethylnaphthalene was considerably reduced. However, when the catalyst obtained in Catalyst Production Example 1 was used, the decrease in the conversion of naphthalene was small and the decrease in the selectivity of the 2,6-isomer group in dimethylnaphthalene was small even when the reaction time was long. .

<Regeneration of Catalyst> Example 5, Comparative Examples 5 to 6 1.5 g of the catalyst obtained in Catalyst Production Example 1, 4 or 5 was charged into a stainless steel pressurized fixed bed reactor, and the catalyst layer was formed. The temperature was raised to 300 ° C. in a nitrogen stream. After maintaining at this temperature for 2 hours, the pressure was switched to a hydrogen stream at a pressure of 5 kg / cm ² G and a flow rate of 30 ml / min, and a 1: 1 mixture by weight of naphthalene and decalin was used.
5.4 g and 1.2 g of methanol were supplied to the reactor with separate liquid pumps, and reacted for 6 hours.

The catalyst after the reaction for 6 hours was subjected to a regeneration treatment for heating coke and high-boiling substances adhering to the surface of the catalyst by heating the mixture from room temperature to 800 ° C. in air to obtain TG and DTG curves. . The results are shown in FIG. The TG curve is a weight loss curve, and the DTG curve is a differential weight loss curve. In FIG. 1, Pt-Fe USY is the catalyst obtained in Catalyst Production Example 1, USY is the catalyst obtained in Catalyst Production Example 4, and Fe USY is the catalyst obtained in Catalyst Production Example 4. This is the case where each was used.

From FIG. 1, Pt-Fe USY is 520 ° C.
e It can be seen that coke is separated at a point of 580 ° C. in USY and 640 ° C. in USY. That is, Pt-Fe US
It can be seen that Y has the lowest coke firing temperature and can be regenerated at a temperature that does not destroy the zeolite structure.

[Brief description of the drawings]

FIG. 1 is a graph showing TG and DTG curves at the time of regenerating a used catalyst.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-215647 (JP, A) JP-A-63-230645 (JP, A) JP-A-59-121115 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C07C 2/70 C07C 2/86 C07C 15/24 B01J 29/08-29/14

Claims (2)

(57) [Claims] (1) In producing mono- and / or dialkylnaphthalene by contacting naphthalene and / or monoalkylnaphthalene and an alkylating agent with zeolite as a catalyst, an iron group or titanium group metal (A) is used as the zeolite. ) And a platinum group metal (B), comprising a metal-containing faujasite-type zeolite. 2. In the metal-containing faujasite-type zeolite, the iron-group or titanium-group metal (A) is contained in such a manner that part of Al constituting the crystal skeleton of the zeolite is substituted, and the platinum-group metal is contained. 2. The method according to claim 1, wherein (B) is introduced into the ion exchange site of the zeolite by ion exchange.