JPH05194283A - Production of alkylnaphthalene - Google Patents

Abstract

PURPOSE:To produce alkylnaphthalenes by alkylating naphthalene and/or monoalkylnaphthalene. CONSTITUTION:Naphthalene and/or monoalkylnaphthalene is reacted with 1 to 10 times molar lower olefin in the presence of beta-zeolite. Alkylnaphthalenes, especially dialkylnaphthalenes can be high selectively produced in high yields.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to a method for producing alkylnaphthalenes. More specifically, it relates to a method for producing an alkylnaphthalene by contacting naphthalene with a lower olefin in the presence of β-type zeolite.

[0002]

2. Description of the Related Art Alkylnaphthalenes are generally useful compounds as intermediates for dyes, pharmaceuticals, agricultural chemicals and the like, and also have a wide range of uses as precursors of polymer raw materials.
For example, 2,6-diisopropylnaphthalene is converted into 2,6-naphthalenedicarboxylic acid by oxidation of an alkyl group, and by condensation-polymerizing this with a polyhydric alcohol such as ethylene glycol, a polyester that can be molded into a synthetic fiber or a film is produced. Can be synthesized.

As a method for producing these alkylnaphthalenes, a method of alkylating naphthalene with an alkylating agent using an acid catalyst (Friedel-Crafts reaction) has been conventionally known. For example, a method in which a Lewis acid such as anhydrous aluminum chloride, boron trifluoride, or iron chloride is used as an acid catalyst to carry out the reaction in a homogeneous system at a low temperature, or a solid acid such as silica-alumina is used as an acid catalyst in a reaction at a high temperature The method is a typical example.

A method of using zeolite as one of the solid acids is also known. For example, a method of alkylating isopropylnaphthalene with propylene using Y-type zeolite to produce diisopropylnaphthalene (JP-A-1-24).
No. 6230), a method for producing diisopropylnaphthalene by alkylating 2-isopropylnaphthalene with propylene using mordenite (JP-A-2-2959).
No. 36), a method of alkylating naphthalene with ethylene using ZSM-5 (Japanese Patent Laid-Open No. 61-362232), etc., and a method of using Y-type, mordenite, ZSM-5 as a catalyst. Are known.
Also known is a method of alkylating mainly monocyclic aromatics using β-type zeolite (JP-A 3-1).
No. 81424).

[0005]

Generally, in the alkylation (Friedel-Crafts) reaction of naphthalene, a large amount of a high boiling point compound (polyalkylnaphthalene) is produced as a reaction by-product, and the alkylnaphthalene produced is introduced into the reaction. It has a drawback that the number of alkyl groups and regioselectivity are low. From an industrial point of view, when a Lewis acid catalyst is used in a homogeneous system, it is necessary to perform complicated decomposition and removal operations of the catalyst such as neutralization and washing with water after the reaction. There is a problem that it cannot be reused. Further, the method using a solid acid catalyst solves the problems such as separation from the catalyst and treatment of waste liquid, but any of the conventionally proposed catalysts has a problem that the activity and selectivity are insufficient and the yield of the target product is low. There is.

The object of the present invention is to obtain a high selectivity and a high yield of alkylnaphthalenes, especially dialkylnaphthalenes, by a process which does not cause a problem of waste liquid treatment after the reaction, facilitates separation of the catalyst, and can reuse the catalyst. It is to provide a method of manufacturing.

[0007]

Means for Solving the Problems That is, the inventors of the present invention have made earnest studies to solve the above problems, and as a result, by using β-type zeolite as an alkylation catalyst for naphthalene and / or monoalkylnaphthalene, a high yield was obtained. It has been found that alkylnaphthalenes, especially dialkylnaphthalenes can be produced with high selectivity.

The β-type zeolite used in the present invention is a crystalline aluminosilicate described in US Pat. No. 3,308,069 and can be identified by its characteristic X-ray diffraction pattern. The important d values (angstrom, radiation: copper Kα doublet, Geiger counter analyzer) of this diffraction pattern are shown in Table 1. The β ₂ -type zeolite used in the present invention has a SiO ₂ / Al ₂ O ₃ molar ratio of 10 to 300, preferably _{30 to 200} , and this value is obtained by using a hydrothermal synthetic formulation or a hydrothermal synthetic product with an acid such as nitric acid. It can be controlled by a known method such as treatment.

Β-type zeolite is H, Na, K, Rb, C
Alkali metal cations such as s, Mg, Ca, Sr, B
Alkaline earth metal cations such as a, Fe, Co, N
It is possible to use cations of transition metals such as i and Cu, cations of rare earth elements such as La and Ce, and various cations such as ammonium ions, but preferably those containing protons. Further, in the present invention, the catalyst can be molded and used by using an inorganic oxide binder such as silica, alumina, silica-alumina and clay.

As the naphthalene used in the present invention,
Naphthalene may be used alone, monoalkylnaphthalene having one alkyl group may be used alone, or a mixture of both may be used. The monoalkylnaphthalene is preferably one having an alkyl group having 1 to 4 carbon atoms, and examples thereof include methylnaphthalene, ethylnaphthalene, normal propyl naphthalene, isopropyl naphthalene, normal butyl naphthalene, isobutyl naphthalene, and tert-butyl naphthalene. ..

The alkylating agent used in the present invention is a lower olefin having 2 to 4 carbon atoms, such as ethylene,
Examples thereof include propylene and butene. Further, when they are classified by the number of carbons that can be introduced, they can be listed as an ethylating agent, a propylating agent and a butylating agent. In the present invention, the reaction of alkylating naphthalene with an alkylating agent to produce alkylnaphthalene may be a flow reaction or a batch reaction.

The reaction temperature is usually 20 in the gas phase reaction.
0-500 ° C, preferably 250-400 ° C, 100-350 ° C, preferably 200-300 ° C in liquid phase reaction
However, regarding the reaction time, in the batch reaction format,
20 hr, preferably 0.5 to 10 hr, and 0.1 to 20 as weight hourly space velocity (WHSV) in the flow reaction mode.
hr ^-1, is preferably 0.2～10Hr ^-1, the amount of the alkylating agent is 1 to 10 mol per mol of naphthalene, preferably 1 to 5 moles are employed.

The reaction can also be carried out in the presence of a solvent. As the solvent, any solvent may be used as long as it does not react with any of naphthalene compounds and alkylating agents under these conditions. However, it is preferably a high-boiling organic compound in general, and is inert to alkylation reactions of cyclic and chain saturated hydrocarbons such as decalin, decane, undecane, and cyclododecane, halogen-substituted benzene, nitrobenzene, and benzonitrile. Examples thereof include aromatics, carbonyl compounds having no α hydrogen such as benzophenone, and the like. A hydrate of the alkylating agent used can also be used as a solvent. For example, when propylene is used as the alkylating agent, 2-propanol can be mentioned. From the viewpoint of suppressing the deterioration of the catalyst, it is preferable to coexist with hydrogen, particularly in the gas phase reaction.

[0014]

EXAMPLES The method of the present invention will be specifically described below based on examples. However, the reaction conditions in the examples are merely examples, and the present invention is not limited thereto. The abbreviations used in the examples are shown below. NAP ... Naphthalene, IPN ... Isopropylnaphthalene, DIPN ... Diisopropylnaphthalene In each table, the "conversion rate of raw material naphthalene" is (the number of moles of raw material naphthalene-the number of moles of unreacted naphthalene) x 100 / raw material naphthalene The isomerization product of the raw material naphthalene is included in the unreacted naphthalene. The “yield of a specific reaction product” is (the number of moles of a specific reaction product / the number of moles of raw material naphthalene) × 100. The "selectivity of 2,6-DIPN" indicates (the number of moles of 2,6-DIPN produced in the reaction / the number of moles of DIPN produced in the reaction) x 100.

[0015]

Reference Example 1 β-type zeolite was synthesized according to the method described in US Pat. No. 3,308,069. Ie 10
wt% tetraethylammonium hydroxide aqueous solution 500 g
And 250 g of water, 19.9 g of sodium aluminate, and 169 g of powdered silica were mixed and stirred to obtain a uniform state, which was then stirred in an autoclave at 150 ° C. under autogenous pressure for 6 days to obtain a white powder. For this, powder X-ray diffraction was measured (powder X-ray diffraction measuring device, manufactured by Rigaku Denki Co., Ltd., RAD-
3A), and a peak corresponding to the reflection d value in Table 1 was obtained, it was confirmed to be β-type zeolite.

Then, this is fired and further according to a conventional method.
After treatment with 0.1N ammonium chloride solution, 500 ℃
Was fired to obtain a proton type. At this time SiO₂/
Al ₂O₃The molar ratio was 35. Hereinafter this is referred to as catalyst A
I will omit it. Alternatively, instead of using an ammonium chloride solution,
In addition, by treating with 1N nitric acid, it becomes a proton type
It was At this time SiO₂/ Al₂O₃The molar ratio is 196
It was. Hereinafter, this is abbreviated as catalyst B. The above-mentioned SiO₂/
Al₂O₃The molar ratio is EPMA [X manufactured by Hitachi, Ltd.
650].

[0017]

[Examples 1 to 4] 4 g of the catalyst A prepared in Example 1, 16 g (0.09 mol) of 2-isopropylnaphthalene, and 4 propylene were placed in an autoclave having a capacity of 200 ml.
g (0.1 mol), and the organic compound 8 described later as a solvent
0 ml was added and the reaction was carried out at 260 ° C. under autogenous pressure for 1 hour with stirring. Table 2 shows the conversion and selectivity of the reaction obtained from the results of analysis by gas chromatography when decalin, fluorobenzene, o-dichlorobenzene and 2-propanol were used as the organic solvent.
Shown in.

[0018]

Comparative Examples 1 and 2 In Example 1, instead of the catalyst A prepared in Reference Example 1, commercially available mordenite (SiO ₂ / A) was used.
l ₂ O ₃ = 20), Y-type zeolite (SiO ₂ / Al ₂
O ₃ = 14) (both are proton type)
The reaction was carried out under the same conditions as in Example 1. The results are shown in Table 2.

[0019]

Example 5 1 g of the catalyst B prepared in Reference Example 1 was pressure-molded, then crushed to 6 to 20 mesh and filled in a flow reaction tube. After heating the catalyst layer to 300 ° C., hydrogen gas was added to 10
The reaction was carried out by supplying milliliter / min, 7.4 mmol / hr of 2-isopropylnaphthalene and propylene, respectively (propylene / 2-isopropylnaphthalene = 1). The results are shown in Table 2.

[0020]

Example 6 4 g of the catalyst A prepared in Reference Example 1 and 9 g of naphthalene were placed in an autoclave having a capacity of 200 ml.
(0.07 mol), 5 g (0.12 mol) of propylene and 80 ml of 1,2,4-trichlorobenzene as a solvent were added, and the mixture was stirred at 220 ° C. under autogenous pressure with stirring 1
A time reaction was performed. The results are shown in Table 3.

[0021]

Comparative Example 3 In Example 6, instead of the catalyst A prepared in Reference Example 1, a commercially available Y-type zeolite (SiO ₂ / Al) was used.
_The reaction was performed under the same conditions as in Example 6 except that ₂ O ₃ = 14, proton type) was used. The results are shown in Table 3.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

[0025]

Industrial Applicability According to the method of the present invention, alkylnaphthalenes, especially cyalkylnaphthalenes can be synthesized with high yield and high selectivity, and their industrial significance is great.

[Procedure amendment]

[Submission date] February 4, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

The β-type zeolite is composed of proton , Na , K, R
b , cations of alkali metals such as Cs, Mg , Ca , S
cations of alkaline earth metals such as r and Ba, Fe and C
It is possible to use those containing transition metal cations such as o , Ni , and Cu, rare earth element cations such as La 2 and Ce, and various cations such as ammonium ions, but those containing protons are preferable. Further, in the present invention, the catalyst can be molded and used by using an inorganic oxide binder such as silica, alumina, silica-alumina and clay.

Claims (1)

[Claims] 1. A method for producing an alkylnaphthalene, which comprises reacting naphthalene and / or monoalkylnaphthalene with 1 to 10 times mol of a lower olefin having 2 to 4 carbon atoms in the presence of β-type zeolite. ..