JPS6019725A - Preparation of aromatic hydrocarbon - Google Patents

Abstract

PURPOSE:To obtain an alkylated and/or dealkylated aromatic hydrocarbon efficiently, by subjecting an aromatic hydrocarbon to alkylation and/or trans-alkylation in the presence of a catalyst comprising crystalline gallosilicate as a main component. CONSTITUTION:An alkylated and/or dealkylated aromatic hydrocarbon (e.g., xylene is prepared from benzene or toluene) is prepared by using a catalyst comprising crystalline gallosilicate(crystallized compound with Si-Ga composition) as a main component. When alkylation is carried out, or the alkylation and trans-alkylation are simultaneously carried out, it is necessary to add an alkylation agent to the reaction system. The reation conditions are 400-600 deg.C, normal pressure -10kg/cm<2>G, and 0.5-10/hr weight space velocity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aromatic hydrocarbons, and more specifically, by alkylating or transalkylating aromatic hydrocarbons such as benzene and toluene in the presence of a specific catalyst. This invention relates to a method for efficiently producing aromatic hydrocarbons of high value.

Conventionally, a method using crystalline aluminone licade as a catalyst has been known for alkylating benzene and toluene to produce aromatic hydrocarbons with high utility value such as xylene (Japanese Patent Laid-Open No. 57688/1983). , same 5
2-120292).

However, this method has a problem in that it involves a dealkylation reaction.

Therefore, the present inventors conducted intensive studies to solve the problems of the conventional method described above, and found that using crystalline gallosilicate as a catalyst can effectively alkylate or transalkylate aromatic hydrocarbons as raw materials. Moreover, this alkylation and transalkylation can be performed freely with KFI4.
I discovered that it is possible to The present invention was completed based on this knowledge.

That is, the present invention provides an alkylation and/or de-alkylation process characterized by carrying out an alkylation reaction and/or a d-nidoranthyl alkylation reaction of aromatic hydrocarbons in the presence of a catalyst containing crystalline gallosilicate as a main component. Z provides a method for producing algylated aromatic hydrocarbons.

The catalyst used in the method of the present invention has crystalline gallosilicate as its main component, as described above.

There are no particular restrictions on the crystalline gallosilicate, and various types may be mentioned, and in short, any crystallized product having a 5i-Ga composition may be used. Specifically, those described in JP-A-56-129608 or JP-A-57-158730 are preferably used.

There are various methods for preparing these crystalline gallosilicates, but generally they can be prepared by adding various silica sources, gallium sources, and crystallizing agents to an aqueous medium and carrying out a hydrothermal reaction. For example, ammonium type crystalline gallosilicate is prepared as follows. That is, first, an aqueous solution containing a gallium salt such as gallium nitrate, a crystallizing agent such as concentrated sulfuric acid and tetrapropylammonium bromide (solution A), an aqueous solution of water glass consisting of silicon oxide, sodium oxide and water (solution B), and sodium chloride. Prepare aqueous solutions (solutions ()), respectively, and prepare these solutions A and J.
and 13 are added dropwise to solution C, the volume of the mixed solution is adjusted as necessary, and this is heated in an autoclave. Thereafter, a sodium type crystalline gallosilicate is obtained through a process of cooling, washing, drying and calcination. Further, the obtained sodium type crystalline gallosilicate is treated with an aqueous ammonium nitrate solution in step 1 to obtain an ammonium type crystalline gallosilicate. The crystalline gallosilicate powder obtained by L7 can be molded by adding a binder such as alumina sol.

In the method of the present invention, the crystalline gallocrylate prepared in this way is used as a catalyst either as it is or after being calcined at 600 to 1000°C, thereby facilitating the alkylation or transalkylation reaction of aromatic hydrocarbons. By proceeding, the desired aromatic hydrocarbons such as xylene, ethylbenzene, and other highly useful aromatic hydrocarbons can be produced with good selectivity f.

The raw material compound used in the method of the present invention is not particularly limited as long as it is an aromatic hydrocarbon, and may be appropriately selected depending on the target compound to be produced. Specifically, benzene, toluene, xylene, and ethylbenzene.

Although there are various types such as naphthalene and methylnaphthalene, benzene and toluene are particularly preferably used.

In the method of the present invention, an alkylation or transalkylation reaction of aromatic hydrocarbons such as benzene and toluene is carried out using a catalyst containing the above-mentioned crystalline gallosilicate as a main component. Either the alkylation reaction or the transalkylation reaction may proceed depending on the selected reaction conditions, or both reactions may proceed simultaneously.

If the alkylation reaction or the alkylation reaction and the transalkylation reaction of the two reactions proceed simultaneously, it is necessary to add an alkylating agent to the reaction system, but if only the transalkylation reaction is carried out, , the reaction proceeds without adding an alkylating agent.

The alkylating agent that can be used here differs from K in terms of the raw material compound used, the desired product, etc., and cannot be unambiguously defined, but if the alkylation is a methylation reaction, a methylating agent such as methanol or dimethyl ether is used. In the case of the ethylation reaction, ethylene, ethanol, etc. are preferably used, and in the case of the propylation reaction, propylene, isopropanol, etc. are preferably used. The amount of alkylating agent used varies depending on the raw material compound, target product, other reaction conditions, etc., but generally alkylating agent/raw material compound = 0 to 1.
0 (molar ratio), preferably #i1/20 to 10 (molar ratio), more preferably l;j115 to 2 (molar ratio).

The method of the present invention uses aromatic hydrocarbons such as benzene and toluene as raw material compounds, and also uses aromatic hydrocarbons such as benzene and toluene as raw materials. The reaction may be carried out using an appropriate alkylating agent depending on the conditions, and the above-mentioned catalyst containing crystalline gallosilicate as a main component, and other conditions are not particularly limited.

General conditions include reaction temperature: 350-650°C, preferably 400-600°C, reaction pressure: normal pressure - 10 kg.
/cm” G s weight space velocity (wnsv) 0.1~
20M! .

Preferably it is 0.5 to 10 hr"".

According to the method of the present invention as described above, the alkylation or transalkylation of the aromatic hydrocarbon as a raw material compound proceeds rapidly under pressure, and industrially useful aromatic hydrocarbons can be obtained in high yield. For example, if you perform a methylation reaction using benzene as a raw material and a methylating agent, toluene and xylene can be obtained.However, if you perform a methylation reaction and a transmethylation reaction using toluene as a raw material and a methylating agent, you can obtain xylene and benzene. is obtained, and the yield of xylene is particularly high.

Furthermore, xylene and benzene can be obtained by transalkylating only toluene as a raw material. In addition, ethylbenzene and ethyltoluene can be obtained by performing an ethylation reaction using an ethylating agent such as ethylene using benzene or toluene as a raw material, and propylating reaction can also be performed using a propylating agent such as propylene using benzene as a raw material. Bakumen et al.

Therefore, the method of the present invention can be widely and effectively used as an industrial method for producing aromatic hydrocarbons of high utility value such as xylene.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) Preparation of catalyst Solution A in which 2.34 g of gallium nitrate, 4.42 g of concentrated sulfuric acid and 6.589 g of tetra-n-propylammonium bromide were dissolved in 62 ml of water, water glass (J Sodium silicate No. 3: Nihon Kagaku Kogyo Co., Ltd.) 52.78.9 with water 6
Solution B dissolved in 2rtrl and solution C in which IJum I 9.75, V was dissolved in water 3(ltK)
was prepared. Solutions A and B were then added dropwise to Kffi solution C simultaneously. This mixed solution was placed in an autoclave and reacted for 24 hours at a reaction humidity of 170°C. After cooling, the contents were filtered, washed with water, dried at 120°C for 12 hours, and further heated to 600°C.
C. for 6 hours to obtain 9.6 g of monosodium type crystalline gallosilicate.

The obtained gallon liquor was placed in a 1N ammonium nitrate solution of 5 times its weight, heated at 80° C. for 8 hours, cooled, and then filtered. The solid substance was further heated and filtered three times, washed with water, and dried at 120°C for 16 hours to obtain ammonium type crystalline gallosilicate. This ammonium type crystalline Gallon Licade is SiO, /Ga208=
75.5 (solar ratio), and by X-ray diffraction it is 28
It was found that it had an M-5 structure.

Alumina sol was added to this ammonium type crystalline gallosilicate so that the alumina content after firing was 20% by weight, and it was molded, dried at 120°C for 16 hours, and then heated to 60% by weight.
By firing at 0° C. for 6 hours, a molded product of proton type crystalline gallosilicate was obtained.

(2) Alkylation reaction of benzene A normal pressure fixed bed flow type reaction tube was filled with 2 g of the above molded product as a catalyst, the reaction temperature was maintained at 450°C, and WH8V 4
Benzene and ethylene were fed at a feed ratio of cabenzene/ethylene to 3/1 (molar ratio) to carry out the ethylation reaction of benzene. Table 1 shows the reaction results 2 hours after the start of the reaction.

Example 2 In Example 1 (2), the ethyl benzene A chemical reaction was carried out. Table 1 shows the reaction results 2 hours after the start of the reaction.

Table 1 Example 3 Example 1 (1) was added as a catalyst to a normal pressure fixed bed flow reaction tube.
The molded product 29 obtained in step 29 was filled, the reaction temperature was maintained at 500° C., and only WH8V 2 br' toluene was supplied to carry out the transalkylation reaction of toluene. The reaction results 6 hours after the start of the reaction are shown in Table 2.0 Example 4 Example 1 (1) with one catalyst in a normal pressure fixed bed flow reaction tube
Filled with molded #J2g obtained in step 1, the reaction temperature was maintained at 500°C, and the reaction temperature was maintained at 500°C.
Methylation and transmethylation of toluene were simultaneously performed by supplying ene and methanol at a feed ratio of toluene/methanol-471 (molar ratio). Table 2 shows the reaction results 6 hours after the start of the reaction.

Table 2 Special pestle applicant: Idemitsu Kosan 1 Co., Ltd. 11-

Claims (3)

[Claims] (1) Alkylation and/or dealkylation characterized by carrying out an alkylation reaction and/or an l-lanth alkylation reaction of aromatic hydrocarbons in the presence of a catalyst containing crystalline gallosilicate as a main component. A method for producing aromatic hydrocarbons. (2) The method according to claim 1, wherein the aromatic hydrocarbon as the raw material compound is toluene or benzene. (3) The method according to claim 1, in which an alkylating agent is added to the reaction system.