JPS6045536A - Trans-methylation of methyl-substituted naphthalene - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for transmethylating methyl-substituted naphthalenes. More specifically, it relates to a so-called transmethylation method in which a methyl-substituted naphthalene or a methyl-substituted naphthalene is brought into contact with naphthalene to transfer a methyl group between naphthalene rings.

Conventionally, methods for transmethylating methyl-substituted naphthalenes, such as transmethylating monomethylnaphthalene to obtain naphthalene and dimethylnaphthalene, or transmethylating dimethylnaphthalene and naphthalene to obtain dimethylnaphthalene, are known.

However, these known methods are unsatisfactory for industrial implementation. Furthermore, according to a known method, when monomethylnaphthalene is transmethylated, industrially useful 2.6-
Another disadvantage is that the proportion of 2,7-dimethylnaphthalene in dimethylnaphthalene is relatively low.

Therefore, an object of the present invention is to provide a method for transmethylating methyl-substituted naphthalenes with high transmethylation activity using a catalyst containing a zeolite as described below.

Another object of the present invention is to provide a method for transmethylating methyl-substituted naphthalenes under relatively mild reaction conditions and with excellent equipment efficiency.

Still another object of the present invention is to selectively carry out the desired reaction with fewer secondary reactions and side reactions.
An object of the present invention is to provide a method for transmethylating 111% naphthalenes.

Still another object of the present invention is a method for obtaining industrially useful dimethylnaphthalenes containing 2,6-dimethylnaphthalene and/or 2,7-dimethylnaphthalene in a high a degree from monomethylnaphthalene. Our goal is to provide the following.

2.6-Dimethylnaphthalene and 2.7-dimethylnaphthalene are industrially useful components as raw materials for polyester, but these useful isomers can be separated by distillation from a mixture containing them. The isomer mixture remaining after cryogenic separation or extractive separation with complex-forming compounds is itself of low value. Therefore, if this isomer mixture can be converted to monomethylnaphthalene, this monomethylnaphthalene can be used again as a useful 2.6- and/or 2.7-
- Since it is possible to isomerize to dimethylnaphthalene, the overall effectiveness of the raw material is increased.

A further object of the present invention is to provide a method for transmethylating dimethylnaphthalenes and naphthalene to obtain monomethylnaphthalene with high conversion and high selectivity.

Further objects of the invention will become clear from the description below.

According to the research conducted by the present inventors, the objects and advantages of the present invention are to provide a method for transmethylating methyl-substituted naphthalenes or 7-talenes;
Presence of a catalyst containing a crystalline aluminosilicate zeolite having a molar ratio of %/A'tOs of 10 to 100 and an X-ray lattice spacing shown in Table A.
It has been found that this can be achieved by a method characterized by 'VL11.

According to the present invention, by using a catalyst containing crystalline aluminosilicate zeolite, which will be described later, transmethylation of methyl-substituted naphthalenes can be carried out under relatively mild conditions and with a small number of catalyst tubes due to the high activity of the zeolite. be able to. In addition, it is possible to carry out the desired transmethylation reaction advantageously with few secondary reactions and side reactions.
The method of the present invention can be very advantageously applied to the reaction to obtain dimethylnaphthalene, and the reaction of dimethylnaphthalenes with naphthalene to produce monomethylnaphthalene.

The method of the present invention will be explained in more detail below, but first the catalyst of the present invention and then the transmethylation method will be explained.

[1] Catalyst used in the method of the present invention and its manufacturing method and preparation The crystalline aluminosilicate zeolite used as an active component of the catalyst in the method of the present invention is as described above (
11Sin, /AJ, 03 (Motb ratio) is lθ~10
0, and the fiil X-ray pole spacing has the characteristics shown in Table 8 below.

This zeolite has a high SiOt/A40s (molar ratio) composition similar to that of the conventionally known zeolite ZSM-5, but has a higher X-ray diffraction lattice spacing (di) than ZSM-5.
It is clearly distinguished from that of No. 5.

Hereinafter, the crystalline aluminosilicate zeolite may be abbreviated as "mono-IC" zeolite.

The zeolite of the present invention has a high SiO, /A/'70. C molar ratio),
The proportion ranges from 10 to 100, preferably from 15 to 70
, more preferably from 20 to 50.

In addition, the zeolite of the present invention has the characteristics of the Xa lattice spacing shown in Table 8 below.According to the analysis of the present inventors, the X-ray diffraction chart of the B4lite of the present invention is
A detailed comparison with that of -5 revealed that there were some differences. One major difference is ZS
According to US Pat. No. 3,702,886, the X-ray lattice spacing d(2) giving the strongest beam of M-5 is dlXl
= 3.85 (211 = 23.14), but the strongest peak of the zeolite of the present invention is branched, and d (A
) = 3.116 and 3.83 (2θ = 23.05
and 23.25).

Another major difference is that d(5)23.00 (2θ=29.76) is observed in zsM-5.
In the zeolite of the present invention, one peak of
This is observed as a branched concave peak at 3.00 (2θ=29.75). Although this latter concave peak is not observed in all zeolites of the invention, it is observed in most cases. Next, the X-ray lattice spacing d (Al and its relative intensity) of the zeolite of the present invention is shown. This relative intensity (I/'Io) is d (3) = 3.8
Relative intensity of each peak r I/Io ('1) when the intensity (10) of 6 (2θ = 23.05) is taken as 100
] 100-60 is VS (very strong), 60-40
is S (strong), 40-20 is M (medium), and 20-10 is W (weak).

Furthermore, d(
5) = 3.86 and 3.83 two 1 very strong''
The peak is generally d-3,86 (2θ = 23.05
) when the peak intensity (Io) of d(
The relative intensity (I/Io) of the peak of Al=3.113 (2θ=23.25) is at least 70, preferably at least 75, more conservatively 77-80.
The correlation is within the range of .

Furthermore, the more preferred zeolite of the present invention also exhibits unique properties in terms of chemical activity; for example, the zeolite in an activated state is .78 1 3.05 Weak 5.61 15.80 Weak 5.41 16.40 Weak 3.61 24.65 Weak 2.98 29.95 Weak to Moderate 2.96 30.20 Weak The cyclohexane decomposition index ratio as determined by the definition below is at least 1.1, preferably at least 1.5.
, more preferably 1.7 or more.

As used herein, the term "activated state" means that most of the alkali metal ions contained in the zeolite of the present invention immediately after synthesis are replaced with hydrogen ions according to a known method. It is something to do. That is, 7 of the alumina-based cation exchange sites of the zeolite.
This means that 0 or more, preferably 90 or more, are substantially occupied by hydrogen ions, and this means that zeolite in an activated state (zeolite in such a state is sometimes referred to as H-type zeolite) is obtained.

In general, zeolite has its S i 01/Ajt's (
(molar ratio) K, its activity, especially acidity, has approximately a fixed value. However, one feature of the zeolite of the present invention is that it exhibits a high activity compared to that of ZSM-5, which has approximately the same S io,/Aj*Os (molar ratio). In other words, if the cyclohexane decomposition activity of the standard ZSM-5 is 1, it is almost the same as 5ift/A.
The cyclohexane decomposition activity of the zeolite of the present invention having ltos (molar ratio) is 1.1 or more, preferably 1.5 or more, expressed as a cyclohexane decomposition index ratio, as described above.

The present inventors believe that this is due to the fact that the zeolite of the present invention has a higher acid strength within its pores than ZSM-5. The upper limit of the cyclohexane decomposition index ratio of the zeolite of the present invention is generally 3, preferably 2.5 or less.
*/A'tOs (molar ratio) and has the characteristics of the X-ray lattice spacing described above, and is not particularly influenced by the type of synthesis method. Among them, preferred zeolites have the cyclohexane decomposition index ratio of at least 1.
1, preferably at least 1.5, and more preferred is a zeolite synthesized by the following method, but the synthesis method shown below is only an example, and the zeolite of the present invention is limited to them. Not that it will be done.

Method A Method A is a method previously proposed by the present inventors, and its details will be explained below.

That is, this method uses a crystalline aluminosilicate zeolite ZSM-5 having a S10y/A110g (molar ratio) of 20 to 300, and containing 0.1 to 1 g of alkali metal hydroxide per 1 g of the zeolite ZSM-5. This is a method of heating in an aqueous solution to a temperature between 80 and 250°C.

This method is specifically and in detail explained in the specification IFC invention title: [Novel crystalline aluminosilicate zeolite and its manufacturing method]) filed by the present inventors on June 17, 1982.

ZSM-5, which is the raw material for this method, is
It can be manufactured by the method described in Publication No. 064, and it can also be used because it is manufactured by Mobil Oil Tuboration. 5i02/A(,0,
The molar ratio is in the range of 20 = 300, preferably 3
A range of 0 to 200 is advantageously used to produce the zeolite of method A. ZSM-5 with a 5i01/1toa molar ratio of less than 20 is not only extremely difficult to produce, but also not easy to obtain. However, according to method A, 5i02/AA', 0. 8 layers using ZSM-5 as a raw material with a molar ratio of 20 or more, preferably 30
．． It is not only possible to easily produce a zeolite having a /A/,09 molar ratio of 20 or less, but also that such a zeolite exhibits the above-mentioned unique activity.

The alkali metal hydroxides used in the treatment of the above raw material zeolite (ZSM-s) include, for example, water-clarified sodium, potassium hydroxide, lithium hydroxide, etc.
Among these, sodium hydroxide is particularly suitable. The amount of alkali gold tetrahydroxide used is determined based on the i of ZSM-5 used.
0.19 to sg per p, preferably 0.29 to 0
．． It can be in the range of 7g, more preferably in the range of 0.3g to 0.5g.

The alkali metal hydroxide is generally brought into contact with the raw zeolite (ZSM-5) particles in the form of an aqueous solution. In this case, the amount of water is not critical and can be varied widely depending on the type and amount of ZSM-5 and/or alkali metal hydroxide used, but usually the total amount of ZSM-5 supplied is It is sufficient that the amount is sufficient to be immersed in the aqueous solution under sufficient pressure. The concentration of the alkali metal hydroxide in the aqueous solution is not limited and can be varied over a wide range, but is generally in the range of 1 to 10% by weight, preferably 2 to 7% by weight.

The reaction is carried out at 80°C to 250°C, preferably 1o.

This is done by heating to a temperature in the range from .degree. C. to 200.degree.

The reaction can be carried out until a zeolite having the above characteristics is substantially produced, and the weight ratio of the formed zeolite/raw material zeolite (ZSM-s) can be used as a measure of the production. That is, the reaction takes place when the weight ratio is 10
-80%, preferably in the range of 20 to 70 inches, more preferably in the range of 30 to 60 inches.

The zeolite thus obtained has the characteristics of III.
The chemical composition is represented by the following formula.

xM2/no-Al,O,・ySiO,・−・−・−
(1) Here, M is alkali gold 1 for the zeolite just produced by method A! A especially refers to sodium, which can be converted into hydrogen ions, hydrogen ions,
ammonium ion.

Can be exchanged for cations such as other metal ions. Of course, even if the zeolite is exchanged with cations other than sodium ions, it essentially meets the requirements of the zeolite of the present invention.

Further, in the above formula (I), X is an index of the amount of ions bonded to the zeolite, and in the case of the zeolite of the present invention, it is within the range of 0.5 to 4, preferably 0.9 to 3. can be.

In addition to the characteristics described above, the zeolite obtained by this method A also has the following characteristics in comparison with the known zeolite ZSM-s and other similar zeolites. One of its characteristics is that the (cyclohexane/n-hexane) adsorption ratio is abnormally high. Zeolites according to this method AK have an adsorption ratio of at least 0.7, preferably at least 0.8, more preferably at least 0.9. (Cyclohexane/n-hexane) adsorption ratio is a value measured according to the definition described below, but Z
All values of SM-5 are lower than 0.7, and as far as the present inventors know, there are no values higher than 0.7.

This adsorption ratio is a value indicating the adsorption ratio of cyclohexane to n-hexane, and the higher this value is, the larger the diameter (-)ζ of the pores in the zeolite is. The upper limit of the adsorption ratio of zeolite according to this method AK is generally about 1.3, typically about 1.2, and this zeolite has an appropriate pore size.

Next, the "(cyclohexane+7/n-hexane) adsorption ratio" and the "cyclohexane decomposition index ratio" are indicators representing the characteristics of the zeolite obtained by this method A.
The definition and measurement method will be explained in detail.

This (cyclohexane/n-hexane) adsorption ratio represents the weight ratio of cyclohexane to the weight f of n-hexane adsorbed per xi of the zeolite, and is a parameter that defines the pore diameter of the zeolite. The dog-lip shape means that molecules with a large cross-sectional area, such as cyclohexane, can more easily diffuse into the pores.

The amount of adsorption per unit weight of zeolite is measured as follows. That is, a pellet-shaped zeolite calcined in an electric furnace at 45,000 ℃ for 8 hours is refined using a spring balance of an adsorption device. Next, after evacuating the inside of the adsorption tube, cyclohexane and n-hexane were introduced in gaseous form until the vacuum reached 60±2 mm.

Hold at 20±I'C for 2 hours. The amount of cyclohexane or n-hexane adsorbed on zeolite can be determined from the difference in spring balance length before and after adsorption.

The cyclohexane decomposition index ratio is the same as that of HffZSM- in the activated state with the same non-liquid/alumina (molar ratio).
It is defined as the ratio of the cyclohexane decomposition index of type I (type zeolite) that was not obtained in the present invention to 5.

Cyclo-\keyn decomposition index is 50MM percent r
- After calcining 10 to 20 mesh pellet-shaped zeolite containing alumina at 450°C for 8 hours in an electric furnace, a certain weight of the zeolite was charged into a fixed bed reactor,
℃, -atmospheric pressure (weight unit hourly space velocity WH5V
= 2HR' (total weight basis of cyclohexane and hydrogen/cyclohexane = 2/) (molar ratio) of water is measured. This is called the Lean Decomposition Index.

In addition, wusv is expressed by the following formula and is a direct line.

Catalyst mold needle method B This method B has also been proposed by Nagisa et al.
8! This method was devised, and the application was filed on July 6, 1981 under the title of ``Process for producing crystalline arsinosilicate zeolite and novel crystalline arsinosilicate zeolite.'' Although the contents are not specifically and detailedly explained in the specification of the application, the gist thereof will be explained below.

This method B uses silica source, alumina source and zeolite)
A zeolite selected from ZSM-5 and zeolites having the characteristics shown below is added at a concentration of 1 to 200% per 1 g of the zeolite.
In an aqueous solution containing millimoles of alkali metal hydroxide,
maintained under temperature, pressure and time conditions such that a crystalline aluminosilicate zeolite is formed, characterized in that: (a) the silica/alumina molar ratio is in the range of 10 to 100; b) The X-ray lattice spacing d is as shown in Table 8 of the specification, and (c) the amount of chemical deposition of n-hexane is at least o, o7
．． ! 7/l. This is a method for producing crystalline aluminosilicate zeolite.

This method B does not require substantial use of organic amines as in the conventional production of ZSM-5, in other words, under conditions where organic cations derived from such organic amines are substantially absent, ZSM-5 is produced. The essential feature is that the zeolite is produced in the presence of the zeolite previously produced by -5 or method B.

This method B uses as raw materials an aqueous solution of a silica source, an alumina source, and an alkali metal hydroxide, which are usually used in the synthesis of zeolites, and a starting zeolite selected from zeolite ZSM-5 and the zeolite produced by method B. By simply doing this, it is possible to synthesize zeolite at an extremely high yield, several times that of the starting zeolite used as a raw material, and under suitable conditions, several times as much.

In this method B, any silica source that is commonly used for zeolite production can be used,
For example, silica powder.

Examples include colloidal silica, water-soluble silicon compounds, and silicic acid. To explain these specific examples in detail, suitable silica powders include precipitated silica produced by a precipitation method from alkali metal silicate such as di-rosylsilica fuming silica and silica gel, and colloidal silicas include: Various particle sizes can be advantageously used, for example particle sizes from 10 to 50 microns. Examples of water-soluble silicon compounds include alkali metal silicates such as water glass, sodium silicate, potassium silicate, etc. containing 0.1 to 5 moles, especially 2 to 4 moles of Si per mole of alkali metal oxide. It will be done. Colloidal silica or water glass is particularly preferred as the silica source.

On the other hand, any alumina source that is generally used in the production of zeolite can be used, such as alumina, aluminum mineral salts, aluminates, etc. Specifically, colloidal sources can be used. Alumina, punidoboehmite, boehmite, γ-alumina.

Hydrated or hydrateable alumina such as α-alumina and β-alumina trihydrate; aluminum chloride, aluminum nitrate, aluminum sulfate; sodium aluminate, potassium aluminate, etc. Among these, sodium aluminate or aluminum mineral acid salts are preferred.

It is also possible to use aluminosilicate compounds as a common source of silica and alumina, such as naturally occurring feldspars, kaolin, acid clay, bentonite, montmorillonite, etc. The silica source and/or a part or all of the silica source may be replaced.

The amount of silica source in the raw material mixture of the present invention is generally 0 iOy per 1 g of starting zeolite as raw material.
．． In the range 1-200 mmol, preferably 1-100E
Advantageously, the amount of the alumina source is in the range of 5 to 80 mmol, more preferably in the range of 5 to 80 mmol, and the amount of the alumina source is
J20. Generally calculated as 0 per gram of starting zeolite.
．． The amount is preferably within the range of 0.01 to 20 mmol, preferably 0.1 to 10 mmol, and more preferably 0.5 to 5 mmol. The mixing ratio of the silica source and the alumina source is not limited, but is generally 5i02 and A1.0. Convert to S i O,/A
l, 02 molar ratio is in the range of 1 to 200, preferably 5 to 1
It is preferable to set it within the range of 00. If this molar ratio is less than 1, the desired zeolite cannot be obtained, and if it exceeds 200, the ratio of modification will be similar.

As the alkali metal hydroxide, sodium hydroxide and potassium hydroxide are particularly suitable, and each of the stiffeners can be used alone or together with silk.

Such alkali metal hydroxide is present in an amount of 1 to 200 mmol per starting zeolite mill, preferably 5 to 100 mmol,
More preferably it is used in an amount ranging from 10 to 80 mmol.

Further, the alkali metal hydroxide for the silica source and alumina source is alkali metal hydroxide/(SiO, +
AJ, O,) in terms of molar ratio, generally 0.1 to 10,
It is preferably used in a range of 0.2 to 5, more preferably 0.3 to 1.

The above-mentioned alkali metal hydroxide is usually used in the form of an aqueous solution, and the concentration of the alkali metal hydroxide in the aqueous solution is generally based on the total amount of water in the reaction system K L, and the water 1
1 to 100, -11 moles per mole, preferably 5 to 50
Conveniently, it is 10 mmol, more preferably 10 to 40 mmol.

Furthermore, in this method B, the starting ZSM-5 that can serve as the crystal matrix of the produced zeolite is a known one, which is combined with a specific organic cation consisting of an alkali metal left-handed ion, and is hydrothermally heated in an alkaline aqueous solution together with a silica source and an alumina source. It can be obtained according to known methods for synthesis under synthetic conditions (for example, Japanese Patent Publication No. 46-1
(See Publication No. 0064).

Zeolite (ZSM-5) synthesized by this known method is usually thoroughly washed with water and then calcined at a temperature in the range of, for example, 300 to 700°C, preferably 400 to 600°C, to remove organic cations. However, the ZSM-5 used in this method B may be the one obtained by incinerating such organic compounds or the one remaining.

In addition, ZSM-5 zeolite, which is a raw material mixture, is prepared by converting some or all of the ions originally present in the zeolite into other cations such as lithium, steel, monovalent ammonium oxide, etc., according to a known method after the above-mentioned calcination operation. Divalent alkaline earth elements such as iron, calcium, and barium: Cobalt.

Group II metal cations such as nickel, platinum, palladium;
The zeolite may be ion-exchanged with a valent cation such as a rare earth metal. Furthermore, in this method B, the 90% zeolite obtained in this method B is used as the starting zeolite instead of the 28M-5 zeolite described above. The object of the present invention can also be achieved. The form of such zeolite may be in the form of slurry immediately after Soft 1 is synthesized,
It may be separated from the filtrate and subjected to a drying and calcination process. Furthermore, it is completely acceptable even if the zeolite is ion-exchanged with the metal cations, like the 28M-5 zeolite.

In method B, a silica source, an alumina source, an alkali metal hydroxide, a zeolite, and water are mixed in the ratios as described above, and the mixture is heated to a sufficient level to form crystalline zeolite. Zeolite synthesis is carried out by maintaining temperature, pressure and time conditions.

In addition to keeping the silica source, alumina source, alkali metal hydroxide, and water in the proportions mentioned above, the silica source, alumina source, and alkali metal hydroxide in the raw material mixture were each -5+
S rot/AllOs = 1 to 200, preferably 5 to 100, more preferably 10 to 8゛0, OH'7/' (S j Ox +Az, o3) =
0, 1 to lO1 preferably 1° or 0.2 to 5, more preferably 0.3 to 1, OH/'H, O= 0, u 01 to 0. l.

It is more advantageous to use it in a ratio that satisfies the following, preferably o, o's to 6.05, more preferably 0.011 to 0.04.

The temperature for the above zeolite synthesis reaction is not limited and can be within the same range as the temperature conditions used in conventional ZSM-5 production, usually 90°C or higher, preferably 10°C or higher.
Temperatures in the range from 0 to 250°C, more preferably from 120 to 200°C are advantageously used.

Furthermore, if this method B is used, the reaction rate is significantly accelerated compared to the conventional method, and as a result, the reaction time is usually 3.
0 minutes to 7 days, preferably 1 hour to 2 days, particularly preferably 2 hours to 1 day are sufficient. The pressure applied is the autoclave's autogenous pressure or higher pressure, and it is generally carried out under autogenous pressure, and may be carried out under an inert gas atmosphere such as nitrogen gas.

When synthesizing zeolite 4 according to this method, a raw material method can be used in which all of the above-mentioned raw material components are charged as a mixture into a reaction vessel and the reaction is carried out under the above-mentioned conditions. Alternatively, a slurry of silica source,
A continuous method may be used in which the reaction is carried out in stages while continuously feeding the alumina source.

Furthermore, a part of the product obtained by the above method is taken out,
It is also possible to carry out the reaction by newly feeding an aqueous solution of alkali metal hydroxide, a pulverizing source, and an alumina source in a bunch manner or continuously.

The zeolite formation reaction is continued by heating the raw material mixture to the desired temperature, with stirring if necessary, until the zeolite is formed.

After crystals have formed, the reaction mixture is cooled to room temperature and filtered, e.g.
Wash with water until the crystals are separated. Furthermore, in order to dry the crystals, it is necessary to keep them at 50°C or higher under normal pressure or reduced pressure.
It is held for 5 to 24 hours.

Thus, according to the above method B, in addition to the silica source, alumina source, and alkali metal aqueous solution normally used for zeolite synthesis, zeolite ZSM-5 or the zeolite obtained by method B is used as the raw material. Compared to the zeolite used as
Under suitable conditions, it is possible to synthesize zeolite in an amount equivalent to several times as much, and in a continuous system, it is also possible to synthesize zeolite in an amount of 100 times or more.

The zeolite thus obtained contains an alkali metal ion as a cation, and can be ion-exchanged by a method known per se, for example, by treating it with an aqueous ammonium chloride solution to replace the cation sites with ammonium ions. If this is further fired, ammonium ions can be converted to hydrogen ions in an activated state.

Furthermore, part or all of the alkali metal ions in the obtained zeolite can be exchanged with other cells A). Examples of ion-exchangeable cations include monovalent metal cations such as lithium, potassium, and silver; alkaline earth metal cations such as magnesium, calcium, and barium; and divalent transitions such as manganese, iron, cobalt, nickel, copper, and zinc. Metal cations; cations containing noble metals such as rhodium, palladium, and platinum; and rare earth metal cations such as lanthanum and cerium.

In the case of exchanging with the various cations mentioned above, it may be carried out according to a known method, and the zeolite may be contacted with a water-soluble or water-insoluble medium containing an aqueous solution containing the desired cation. Such contact processing can be accomplished in either a batch or continuous manner.

The zeolite thus obtained may be calcined at a temperature of 100 to 600°C, preferably 300 to 500°C, for 5 to 40 hours, preferably 8 to 24 hours, and this calcined product can also be used as the zeolite of the present invention. Ru.

The zeolite obtained by this method B) has the following characteristics in comparison with the known zeolite ZSM-5 and other similar zeolites. One of its characteristics is that the conversion deposition amount of n-to-V-sun has a very high value of at least o, orll/l.

The amount of chemical conversion deposition of 11-hexane is a value measured according to the following definition. The amount of chemical deposition of n-hexane is a factor related to the pore volume of zeolite, and a large value indicates that the zeolite channels.
This means that the pore volume is large. However, there is naturally an upper limit to the amount of chemical deposition of n-hexane, and the upper limit of the amount of chemical deposition of hexane on the zeolite produced by method B is generally o, 1 g/I! degree, typically O, Oag
/g, preferably 0.07-0.0911/I
It has a specific adsorption amount of n-hexane in the range of I.

Yet another zeolite produced by the above method B
One characteristic is the (2-methylmenthane/cyclohexane) adsorption ratio. This adsorption ratio is a value measured by the method described below, but this zeolite is generally 1
．． 1 to 6, preferably 1.2 to 1.5, more preferably 1.25 to 1.45.

This (2-methylpentane/cyclohexane) adsorption ratio is a factor related to the pore diameter of the zeolite channel, and a large value means that molecules with large cross sections, such as cyclohexane molecules, are absorbed into the zeolite channel. On the other hand, its cross section is smaller than that of cyclohexane2
-Means that methylpentane molecules can easily enter the channel.

Therefore, when a zeolite having a pore diameter of 1,000 yen and having an adsorption ratio in the above range is used as a catalyst, it exhibits unique shape selectivity and becomes a novel catalyst of high industrial value.

Next is an index expressing the characteristics of the zeolite of method B [n
- amount of chemical conversion of hexane] and “(2-methylpentane/
The definition and measurement method of ``cyclohexane adsorption ratio'' will be explained in detail.

Amount of chemical deposition of n-hexane This index is defined as the weight of n-hexane gently adsorbed by 1 g of zeolite under the following constant conditions, and is measured as follows. That is, at 450°C in an electric Matsufuru furnace.
The pelleted zeolite calcined for 8 hours is accurately weighed using the spring balance of the adsorption device. Next, after evacuating the inside of the adsorption tube for 1 hour (OmJg), the inside of the adsorption tube became 50±1-
1! ? Introducing n-hexane in gaseous form until reaching
The weight of adsorbed n-hexane maintained at room temperature (20±1° C.) for 2 hours can be calculated from the difference in spring balance length before and after adsorption.

(Ill (2-methylpentane/cyclohexane) adsorption ratio This index is expressed as the weight ratio of 2-methylpentane to the weight of cyclohexane adsorbed per gram of zeolite under conditions of constant H. Measurement of the amount of adsorption of each component The method is exactly the same as the above item (1).

Note that the chemical composition of the zeolite obtained by the method B UC is almost the same as that of the zeolite obtained by the method A, so a description thereof will be omitted here.

Method C1 Obtained by the method described in JP-A-56-17926 4
The zeolite L method was used.

The zeolites obtained by the method described in JP-A-57-123815 have the characteristics specified in the present invention, but they also contain (cyclohexane/n
-hexane) adsorption ratio is less than 0.7, generally 0.
One of the characteristics is that it is 4 to 0.7. Another feature is that the amount of chemical conversion of n-hexane is 0.03 to 0.06 g/
It has a relatively small value of g.

Among the specific examples of the zeolite synthesis methods described above, when zeolites obtained by method A and method B are used,
This method is more preferable since it is possible to obtain a catalyst which has higher transmethylation activity for methyl-substituted naphthalenes, which is the object of the present invention, and which can cause more selective polarization.

The zeolite used in the catalyst of the invention preferably has at least 50% of its total canon sites. i1. ．． < means that at least 70 cells are occupied by hydrogen cations (H+). In the case of zeolites with a lower proportion of hydrogen cations (H+) than this range, generally the 9
Zeolites with hydrogen cations in the upper R''' range are converted to rA? by methods known per se of ion exchange of 1,000 ions to hydrogen cations. '! can do. For example, the canaon site can be converted to hydrogen cations (H+
) can be converted to

Hydrogen cations other than hydrogen cations (H+) in the above range may be populated with various metal cations. For example, Be
, Mg, Ca, Sr, Ba, and lanthanide metal cations such as La and Ce.

Also Fe, Co, Ni, Ru, Rh, Pd, Os, I
The metals may be ion-exchanged with Group 8 metals such as r, Pt, etc., or these metals may be supported.

When this zeolite ion-exchanged or supported with Group 8 metal is used in the transmethylation reaction of the present invention,
This has the effect that the generation of carbonaceous substances on the catalyst surface is suppressed as the reaction progresses, and the activity can be maintained for a long time.

The zeolite of the present invention can be used in the form of powder itself, or can be used as molded products such as pellets,
It can also be used in tablet form. When used as a molded article, the content of zeolite in the molded article is advantageously in the range of 1 to 100 inches, preferably 10 to 90 inches by weight. Furthermore, in order to form zeolites, refractory inorganic oxides which are generally used as binders for zeolites, such as silica, alumina, silica-alumina, silica-magnesia, kaolin, etc., are used, with alumina being particularly preferred. If it contains a metal, it is treated under a reducing atmosphere (for example, under a hydrogen-containing gas atmosphere) before being subjected to the reaction of the present invention.
For example, 2()0 to 600°C, preferably 250 to 55
It is preferable to carry out the reduction heat treatment at a temperature of 0°C. This reduction heat treatment may be carried out before or after the catalyst is charged into the reactor.

[■] Transmethylation method of the present invention The gelite produced and prepared as described above or the catalyst containing it is used as a catalyst in the transmethylation of methyl 1θ-converted naphthalenes. As mentioned above, the zeolite of the present invention has high transmethylation activity and low activity of other secondary reactions and side reactions. It can be done with The present invention is advantageously applied to, for example, the following transmethylation reaction of methyl-substituted naphthalenes. In the present invention, the methyl-substituted naphthalenes have 1 to 5 methyl halide atoms in the hexathalene skeleton,
Preferably those having 1 to 3 substitutions are suitable.

(i) Synthesis of dimethylnaphthalene by transmethylation of monomethylnaphthalene; (it) Synthesis of monomethylnaphthalene by transmethylation of dimethylnaphthalene and naphthalene; This is carried out by heating the phase to a temperature in the range of 250 to 500° C. in the presence of the catalyst. Preferred reaction conditions differ slightly depending on the composition of the raw materials, intended transmethylation, and the like.

For example, when monomethylnaphthalene is converted into salts to obtain dimethylnaphthalene and dimethylnaphthalene, the weight of monomethylnaphthalene in the raw material mixture is at least 30%
A book containing at least 50 sections, preferably at least 80 sections, is desirable. Components other than monomethylnaphthalene include, for example, aliphatic hydrocarbons and aromatic hydrocarbons as described below.

In addition, when dimethylnaphthalene and naphthalene are transmethylated to obtain 1,000-methylnaphthalene, the total weight of dimethylnaphthalene and naphthalene in the raw material mixture is
It is desirable to have a content of at least 30%, preferably at least 70%, more preferably at least 80%. In this case, it is advantageous for the ratio (dimetal naphthalene/naphthalene mole ratio) to be in the range from 0.2 to 5, preferably from 0.5 to 2. Examples of components other than dimethylnaphthalene and naphthalene in the raw material mixture include n-paraffin and i@.

- Aliphatic hydrocarbons such as paraffin, aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, and the like.

As mentioned above, transmethylation in the present invention can be carried out in either liquid phase or gas phase.

When the reaction is carried out by a gas phase method, a temperature in the range of 250 to 500°C, particularly 300 to 450°C is advantageous, and the conversion and yield are excellent in this temperature range. Further, it is desirable that the raw material and the catalyst are brought into contact so that the weight unit hourly space velocity (WH8V) is in the range of 0.05 to 20, preferably in the range of o, i to 5. The reaction pressure is normal pressure ~ 2oky/er!
, preferably in the range from 1 to 10 kg/CI.

When carrying out the reaction by a gas phase method as described above, the reaction can also be carried out in the presence of a diluent such as hydrogen or nitrogen. In particular, the use of hydrogen is industrially advantageous because the life of the catalyst can be extended. The appropriate amount of hydrogen used in this case is 0.1 to 50 moles, preferably 1 to 20 moles, per mole of the raw material mixture. When carrying out the transmethylation reaction in the gas phase, the catalyst and the raw material mixture may be brought into contact in either a fixed bed reactor or a fluidized bed reactor, but the former is preferably used.

- When carried out in a liquid phase according to the method of Shiki invention, 200~
A temperature in the range of 450°C, preferably 250-400°C is preferred, and a weight unit hourly space velocity < WH8V
) is in the range from 0.1 to 30, preferably from 0.5 to 10, it is advantageous to contact the raw material with the catalyst. In the case of the liquid phase method, it is advantageous to increase the WH5V value compared to the gas phase because it can increase the cleaning effect of carbonaceous material (cake) on the catalyst and suppress the change in catalyst activity over time. It is. In the liquid phase method, the reaction pressure may be any pressure that can maintain the reaction mixture in a liquid phase state, generally from normal pressure to 50 ky/cn! , preferably 2-25 kg
/cdL range is desirable. Pressure can be maintained by supplying an inert gas such as hydrogen, nitrogen, or helium.

As described above, according to the transmethylation of the present invention, since the above-mentioned highly active catalyst is used, the desired methyl-substituted naphthalenes can be obtained with high conversion and high selectivity, and the reaction conditions are relatively mild. In addition, reaction devices can also be used to improve moving vehicles.

The method of the present invention will be described in detail below with reference to Examples.

Example-1 fal The silica/alumina molar ratio was 71.
No. 9 ZSM-5 zeolite was synthesized. That is, during the synthesis, tjj-n-propylamine and n-propyl bromide were added as organic cation sources. The obtained composite was filtered for 4 hours, thoroughly washed with water for 7 hours, and then electrically dried in the cold for 10 hours.
It was dried at 0° C. for 16 hours, then at 200° C. for 8 hours, and then fired at 500° C. for 16 hours under air circulation.

Next, 10.9 g of the above ZSM-5 was taken and suspended in 50 ml of an aqueous solution in which 1.5 g of sodium hydroxide was dissolved in a flask. After holding this at 90°C for 3 hours with stirring, the residue was filtered, thoroughly washed with water, and then electrically dried for 10 minutes.
It was dried at 0°C for 16 hours. The weight after drying was 5.79, the silica/alumina molar ratio of this product decreased to 39.2, and the X-ray diffraction pattern obtained by irradiation with Cu Ka rays was as shown in Table A above. ZSM
d(5) obtained by -s = 3. It was observed that the strongest peak of j4 was clearly separated into d(5) = 3.86 and d(5) = 3.83 (zeolite A-1). Further, powdered zeolite A-1 was subjected to ion exchange using a 5 wt % ammonium chloride aqueous solution at 70°C for 16 hours.
Ta. The amount of ammonium chloride aqueous solution used was 5 ml per 1 g of zeolite, and this operation was repeated twice. After ion exchange, the zeolite was washed and dried as described above, and then calcined in an electric furnace at 450° C. for 8 hours under air circulation to obtain H-type zeolite (zeolite A-2).

(bl After molding the above zeolite A-1 into a size of 10 to 20 meshes, it was heated to 450°C in an electric Matsufuru furnace.
It was baked for 8 hours. Approximately f1.5. The fi+ was suspended in an adsorption tube, placed on a spring balance, and the weight of the zeolite was precisely measured from the elongation of the spring. Next, after penetrating the inside of the adsorption tube, the n-hexane filled in the gas holder introduced cycloxane into the adsorption tube.

Adsorption is 20℃, 60+nn+II! The test was carried out for 2 hours under the conditions of 9.

The adsorption negative mass μ adsorbed on the zeolite was calculated from the difference in the length of the spring balance of the adsorption mass. The adsorption MV of n-hexane and cyclohexane to the zeolite is 6 h6. swt% and 6.4 Wt%, and the adsorption ratio of cyclo-hexane to n-hexane was 0.94.

(cl) To the zeolite A-2 described above, Al-S Nagel for 0 Madograph (300 mesh or less) was added at a weight ratio of 1/1, thoroughly mixed, and molded into a size of 10 to 20 mesh. After calcining at 450°C for 8 hours in a Matsufuru furnace, 4g was charged into a fixed bed reaction tube.After setting the catalyst bed temperature to 350°C, cyclohexane BE/Hr and hydrogen/cyclohexane-2/1 (molar ratio ) when hydrogen was supplied and the cyclohexane decomposition index was measured.21.
It was 5.

The cyclohexane decomposition index of ZSM-5, which has the same silica/alumina (molar ratio) as zeolite A-2, is 11.3 from the correlation curve in Figure 1, and therefore it is
It can be seen that the cyclohexane decomposition index ratio of is 1.9.

Example-2 (al Sodium Kitori (special grade reagent made by Wako Tsumugi Pharmaceutical) 10
．． Aluminum sulfate 16-18 hydrate (
Wako Tsumugi Pharmaceutical Special Grade Reagent) 3, I J9 was added, and silica sol (Catalyst Kasei Kafroid S-30L) was added as a silica source.
Sin.

A gel was prepared by adding 69.4 g of 3Qwt%).

Next, after charging this gel into a 300yljl capacity stainless steel autoclave, Z synthesized in Example 1-(a)
SM-5 zeolite) 6.9/l was added. The composition of the feed material is expressed per 1 g of ZSM-5: SiO, = 60.0 mmo/, MtO, = 0.7
14. mmolNaOH=38.0 mmo/, and expressed in molar ratio Sio, /AI,O,, = 7o.

oH-/S iO* + A et al. Q, = 0.75.

OH/HxO=o, o 1g. The materials were reacted at 180° C. under autogenous pressure for 6 hours with gentle stirring. After taking out the reaction product and filtering it, it was thoroughly washed with pure water until the washing solution became 5oμV/'z or less, dried at 90°C overnight, and its weight was measured.
, flp, and 1 for the 25M-5 zeolite charged.
．． I got a product of 5 times the number. As a result of quantifying silica and alumina, the silica/alumina (molar ratio) was 23.8, and the X-ray diffraction pattern had characteristics similar to those shown in Rock-A, especially those obtained with ZSM-5. d(Al
The strongest peak of =3.84 is d (A+=3.86 and d
I want to show a remarkable separation in prison = 3 is 3) B-1
).

From this powdered zeolite) B-1, H-type zeolite (zeolite B-1) was prepared according to the method described in Example 1-(al).
-2) was obtained.

Fbl The above-mentioned zeolite B-1 was molded into a size of 10 to 20 meshes, and then calcined in an electric Matsufuru furnace at 450°C for 8 hours. Approximately 0,000 s g of zeolite was placed on a spring balance suspended in an adsorption tube, and the weight of the zeolite was precisely measured from the elongation of the spring. Next, after evacuating the inside of the adsorption tube,
2-Methylpentane or cyclohexane filled in a gas holder filled with n-hexane, the inside of the adsorption tube is 50±lmm.
The introduction was continued until Hg was reached.

After holding at room temperature (20° C.±1° C.) for 2 hours, the weight of adsorbate adsorbed on the zeolite was calculated from the difference in spring balance length before and after adsorption. n-hexane to the zeolite.

The specific adsorption amounts of 2-methylpentane and cyclohexane are o, o s 7 g/g, o, o, respectively per weight of zeolite.
s 19/g and n, o 349/g, and the adsorption Kitamoto of n-hexane to cyclohexane was 1.50.

Furthermore, the nclohexane decomposition index ratio of zeolite B-2 was determined to be 2.0 in accordance with the method described and in Example 1.

Example-3 Equal weight of I (type zeolite) (A-2) K gel-like γ-alumina (300 meshes or less) synthesized in Example-1 was added, thoroughly mixed, and molded into a size of 10 to 20 meshes. .

5g of this molded material was heated in an electric Matsufuru furnace for 450 minutes in an air atmosphere.
゛Carry out calcination using Cvr and fill it into a fixed bed reaction tube. After setting the catalyst bed humidity to 375° C., an equimolar mixture of naphthalene and 1.52 methylnaphthalene was fed at a rate of 17/HR and hydrogen/(naphthalene + 1.52 methylnaphthalene) = 3/1 C molar ratio). Hydrogen was distributed. Zeolite B-2 synthesized in Example-2 using the same procedure as above
and H-type ZSM-5 (synthesized in Example-1) for comparison.
The test was also carried out on commercially available H-type mordenite (Zeolon 100B). The product composition 5 hours after the start of oil passage is listed in Table 1.

This result shows that monomethylnaphthalene can be obtained in high yield in the method of the present invention due to its high trans-alkyl activity.

Table 1 Example 4 The H-type zeolite (B-2) synthesized in Example 2 was molded and calcined by the method described in Example 3, and 5 g of it was filled into a fixed bed reaction tube.

Then, the trans-alkyl reaction of β-methylnaphthalene was carried out under the conditions of various temperatures and weight-time space velocities listed in Table 2]. Table 2 summarizes the product composition 2 hours after the start of oil passage.

WH8V in the table is based on the following definition.

These results show that the method of the present invention allows dimethylnaphthalene to be obtained from methylnaphthalene in a high yield, and that the effective concentrations of 2,6- and 2,7-dimethylnaphthalene are high.

Table 2 Methylnaphthalene conversion vehicle = 100 - Concentration of methylnaphthalene in the product Example 5 A continuous oil flow test in the liquid phase was carried out in this example. The H-type zeolite (B-2) log synthesized in Example-2 was filled in powder form into a fixed bed reaction tube lined with stainless steel. The catalyst bed temperature was set at 375°C and the inside of the reaction system was blown with nitrogen.
/cfflG pressurized extracted methylnaphthalene 10
It was fed at a rate of g/HR. Table 3 shows the duct tih.
It shows the change in composition over time. These results show that in the method of the present invention, the transalkyl reaction of methylnaphthalene occurs in a high conversion vehicle even in the liquid phase, and the activity changes little over time.

Table 3 In Example 4, H-type zeolite (A-2) was used.
I had a similar reaction. (L(, L, α-methylnaphthalene was used as the raw material instead of β-methylnaphthalene. The product composition 2 hours after the start of oil passing is summarized in Table 4. From this example, the method of the present invention It can be seen that the trans-methyl reaction proceeds even under relatively mild conditions.

Table-4

[Brief explanation of the drawing]

The attached drawing shows the cyclohexane decomposition index ratio (C, D, R)
This figure shows the correlation between the silica/alumina (molar ratio) of the H-type ZSM-s zeolite that serves as the base fabric and the cyclohegysane decomposition index for calculating the . 11K1 Applicant: Teijin Yuka Co., Ltd.

Claims (1)

[Claims] 1. A method for transmethylating methyl-substituted naphthalenes or phthalenes, the method comprising S
iO! /Aj,03 (molar ratio) is 10 to 100,
A method characterized in that it is carried out in the presence of a catalyst containing a crystalline aluminosilicate zeolite whose X-ray lattice spacing has the characteristics shown in Table A. λ The crystalline aluminosilicate zeolite has a peak intensity (Io) when the X-ray lattice spacing d is 3.86.
oo, the peak intensity at d(A) of 3.83 (ratio of 11 (1/io) has a value of at least 70. 3. The crystalline aluminosilicate. 4. The method of claim 1, wherein the zeolite has a cyclohexane decomposition index ratio of at least 1.1 in an activated state. 4. The method of claim 1, wherein the methyl-substituted naphthalene is monomethylnaphthalene. 5. The methyl-substituted naphthalene is monomethylnaphthalene. The method according to item 1, wherein the substituted naphthalenes are dimethylnaphthalenes. 6. The method according to item 1, wherein monomethylnaphthalene is transmethylated to produce dimethylnaphthalenes. 7. Dimethylnaphthalenes and 7talene are transmethylated. 8. The method according to paragraph 1, in which the method is carried out at a temperature of 250 to 500°C. 9. The method according to paragraph 1, in which the method is carried out in a gas phase. Method: 10. The method according to paragraph 1, wherein the method is carried out in the presence of hydrogen. 11. The method according to paragraph 1, wherein the method is carried out in a liquid phase.