JPS601140A - Production of p-ethyltoluene - Google Patents

Abstract

PURPOSE:To produce the titled compound useful as a raw material of p-methylstyrene useful as a hardener and a raw material of resins, in high selectivity, yield and efficiency, with a simple process, by reacting toluene with ethylene using a crystalline borosilicate as a catalyst. CONSTITUTION:Toluene is made to react with ethylene at a molar ratio of 1/10-20/1 at 200-600 deg.C, under normal pressure -30kg/cm<2>G and a space weight velocity of 0.1-100hr<-1> in the presence of a crystalline borosilicate which may support amorphous or crystalline silicon oxide. The crystalline borosilicate can be prepared by adding a silica source such as sodium silicate, a boron source such as boric acid, and a crystallizing agent such as tetrapropyl ammonium bromide, etc. to an aqueous medium, subjecting to the hydrothermal reaction, and if necessary, calcining at 600-1,000 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing para-ethyltoluene. Concerning a method for efficiently producing para-ethyltoluene with high selectivity by reacting toluene and ethylene in the presence of a catalyst. It can be converted to paramethylstyrene, which is useful as an unsaturated polyester curing agent. Therefore, various methods for producing para-ethyltoluene have been known for a long time, and one of them is a method for producing toluent ethylene Karahara ethyl toluene using a zeolite catalyst such as Z8M-5 (Japanese Patent Application Laid-open No. 53-1979-1). 12816) has been developed. However, in this case, para-ethertoluene can only be obtained at a production ratio of about 33%, which is close to the equilibrium composition, and if the production ratio of bulk bodies is low, the ortho-isomer becomes cyclized during the 1-methylstyrene trap conversion. , there was a problem that it caused a decrease in productivity.

The inventors of the present invention have conducted extensive research in order to overcome the problems of the prior art described above and develop a method for producing para-ethyltoluene with high selectivity. As a result, it was discovered that the object could be achieved by using crystalline borosilicate or crystalline borosilicate supporting Fi or rR silicon as a catalyst, and the present invention was completed. That is, in the present invention, when toluene and ethylene are reacted in the presence of a catalyst to produce para-ethyltoluene, one loaf! The present invention provides a method for producing paraethyltoluene, characterized in that crystalline borosilicate or crystalline η111 silicic acid supporting silicon oxide is used as a medium.

Various types of crystalline borosilicate can be used in the present invention, such as those disclosed in JP-A-53-55500, JP-A-55-7598, JP-A-56-84313, Publication No. 57-123817, Japanese Unexamined Patent Publication No. 57-1
Examples include crystalline borosilicate described in Japanese Patent No. 29820 and the like. There are various methods for preparing these crystalline borosilicic acids, but generally they can be prepared by adding various silica sources, boron sources, and crystallizing agents to an aqueous medium and carrying out a hydrothermal reaction.

For example, ammonium type crystalline borosilicate is as follows? S
J is made. That is, first, an aqueous solution containing boric acid, concentrated sulfuric acid, and tetrabrobylammonium bromide (f
tJ solution A), an aqueous solution of water glass (solution B) consisting of silicon oxide, sodium oxide and water, and an aqueous sodium chloride solution (solution C) are respectively prepared, and solutions A and B are added dropwise to solution C, and as needed. Adjust the FI■ of the mixed liquid using
Heat this in an autoclave. Thereafter, crystalline sodium borosilicate is obtained through the processes of cooling, washing, drying and firing. Further, the obtained crystalline sodium borosilicate is treated with an aqueous ammonium nitrate solution to obtain ammonium-type borosilicate. The borosilicate obtained by pressing in this manner is in powder form, but it can also be molded by adding a binder such as alumina sol to it.

In the method of the present invention, the crystalline borosilicate thus prepared is used as a catalyst either as it is or after being calcined at 600 to 1000°C, so that toluene and ethylene or raha ethyl toluene can be mixed with high selectivity. Manufacture.

Furthermore, in the method of the present invention, it is also effective to use crystalline borosilicate carrying silicon oxide as a catalyst instead of the above-mentioned crystalline borosilicate. In order to prepare crystalline borosilicate carrying silicon oxide, silicon oxide may be supported on the above-mentioned crystalline borosilicate by various methods. For example, tetraethyl silicate.

Crystalline borosilicate is impregnated into silicon compounds such as alkyl silicates such as tetramethylsilicate, organosilanes such as trimethylchlorosilane and dimethyldichlorosilane, or silicones such as diphenyl silicone, methylphenyl silicone, and dimethyl silicone. If this is then fired, crystalline borosilicate on which amorphous silicon oxide is supported can be obtained.There are various methods for impregnating crystalline borosilicate with these organosilicon compounds, but in general, the above-mentioned organosilicon compound is A method may be used in which the compound is dissolved in an inert organic solvent such as n-hexane, and the crystalline borosilicate is immersed in this solution.

At this time, the amount of the organosilicon compound to be impregnated into the crystalline borosilicate is not particularly limited as it may be adjusted appropriately according to various conditions, but usually the amount of supported silicon oxide after firing is 0.05 to 50 (weight ratio), preferably 1
~25 (weight ratio).

Another possible method for supporting silicon oxide on crystalline borosilicate is to cover crystalline borosilicate with an outer shell of crystalline silicon oxide. Specifically, this method is as follows: 1. First, the above-mentioned crystalline borosilicate is used as the inner core part, and this is used as sodium silicate and silica sol.

Silicic anhydride (e.g. Aerosil) 1 is added to an aqueous solution containing a silicon compound such as quartz, and if necessary, a crystallizing agent such as tetraalkylammonium halide is added to carry out a hydrothermal reaction, followed by drying and firing in the usual manner. If carried out, the desired crystalline borosilicate, that is, crystalline borosilicate on which crystalline silicon oxide is supported, can be obtained.

According to the method of the present invention, para-ethyltoluene is produced using toluene and ethylene as raw materials, using the above-mentioned crystalline borosilicate or crystalline borosilicate supporting silicon oxide as a catalyst. The conditions for this reaction are not particularly limited and may be adjusted appropriately depending on various circumstances, but for example, the reaction temperature is 200 to 600''C.

Preferably 300 to 500°C, reaction pressure normal pressure to 30°C]
<y/1yn2Gs preferably normal pressure to 10 ky/c
m” G 1m Space velocity (WH8V) 0.1~10
0 hr-', preferably tl, <l]: 1 to 20 hr. Also, the ratio of toluene and ethylene, which are raw material compounds, is toluene/ethylene (molar ratio) = 1710 to 20/1.
, preferably 1/2 to 5/1.

According to the method of the present invention such as the combination L, ethyltoluene can be produced at a high efficiency of 177 IR, and the selectivity of para-ethyltoluene is extremely high. Therefore, the method of the present invention has high industrial utility value as an efficient method for producing para-ethyltoluene, which is a raw material for producing para-methylstyrene useful as a resin raw material and a curing agent.

Next, the present invention will be explained in more detail based on examples.

Example 1 (1) Preparation of catalyst 1.34 g of boron oxide was dissolved in 250 m/m of water, and concentrated sulfur ffZ17.68 m/m was dissolved. ? and tetra-n-propylammonium bromide 26.329 were dissolved to obtain liquid A, and water glass (J Sodium Silicate No. 3 Nippon Kagaku Kogyo Co., Ltd.) 211.1! ! was dissolved in 250 ml of water to obtain liquid B, and further 79.0 p of sodium chloride was dissolved in 122 ml of water to obtain liquid C.

Next, solutions A and B were simultaneously added dropwise to solution C at room temperature for 10 minutes. The resulting mixed solution was placed in an autoclave and heat-treated at a reaction temperature of 170° C. for 20 hours. The contents of the autoclave were then filtered, and the solids were washed and dried at 120° C. for 12 hours. 56g of IJum type crystalline borosilicate
Obtained.

Next, 30 g of the obtained sodium-type crystalline borosilicate was added to a 1N aqueous ammonium nitrate solution weighing 5 times its weight, and the mixture was refluxed for 8 hours. Thereafter, the mixture was cooled and allowed to stand, and the supernatant was removed by decantation. After repeating the reflux and decantation operation three times, the mixture was filtered, washed, and dried at 120° C. for 12 hours to obtain 29.59 ammonium-type crystalline borosilicate powder.

Furthermore, a binder alumina sol was added to this ammonium-type crystalline borosilicate so that the alumina content after firing was 20% by weight, and the pellet was formed, dried at 120°C for 16 hours, and heated at 550'C in Mitsui. A catalyst was obtained by firing for 6 hours.

f2)) Reaction of luene and ethylene 2g of the catalyst obtained in the above (1) was simply charged in a normal pressure fixed bed flow type reaction at a reaction flow rate of 450°C and 1" Wf of luene.
The reaction was carried out using JSV 7 br-' and the feed ratio of raw materials was toluene/ethylene = 3.88/1 (molar ratio) and t. The results of the reaction are shown in Table 1.

Example 2 (1) Catalyst f, :Id η The catalyst obtained in Example 1 (1) was calcined at 900'C for 2 hours, and this calcined product was used as a catalyst.

(27) Example 1 except that in the actual reaction of toluene and ethylene Mti B'111 f21, the catalyst obtained in (1) above was used.
The reaction was carried out in the same manner as in (2). The results of the reaction are shown in Table 1.

Example 3 (1) Made of NVd catalyst 5 g of the catalyst obtained in Example 1 (]) was mixed with silicone (manufactured by Toshi Silicone Co., Ltd.: trade name 8Ji-710, viscosity 47).
5 to 525 cst (25°C)) o, 6y was added to a solution of rBFI in 50 ml of n-hexane, and 2
It was soaked for 4 hours.

Then, it was evaporated to dryness, dried at 120°C for 14 hours, and
5 ff,) #Q *l was formed at 0°C. Furthermore, alumina sol was added as a binder to this fired powder so that the alumina content after one firing was 20% by weight, and the powder was molded.
After drying at 20°C for 16 hours, the mixture was heated at 550°C for 6 hours to obtain a catalyst.

(2)) Reaction of toluene and ethylene In Example 1 (2), the same mK reaction as in Example 1 (2) was carried out except that the catalyst obtained in (1) above was used. The results of the reaction are shown in Table 1.

Example 4 (1) Preparation of catalyst i+ Proton type crystallinity obtained by calcining the ammonium type crystalline boric acid (') powder obtained in Example I O) at 5 s o ℃ for 6 hours. 9g of borosilicate to 5g of ethyl orthosilicate
In addition to 0 g, 8rP9riIJ was refluxed. Then filter,
It was washed, dried at 120°C for 8 hours, and fired at 550°C for 6 hours. A binder, alumina sol, was added to this fired powder so that the alumina content after firing was 20% by mass, and the powder was dried at 120°C for 16 hours and then at 550°C for 6 hours.
A catalyst was obtained by firing at 00°C for 2 hours.

+21) Reaction of toluene and ethylene In Example 1 (2), the reaction was carried out in the same manner as in Example 1 (2) except that the catalyst obtained in (1) above was used. The results are shown in Table 1.

Example 5 0) R1 of the catalyst was oxidized to boron oxide 0.64. ? was dissolved in 112.5 ml of water, and 7.929 g of sulfur and 11.8 g of tetra-n-propylammonium bromide were dissolved to prepare h-liquid.
Water glass (same as Example 1) 9i5g water 112.5F
/ to make solution B, and then add sodium chloride 35.6
9 was dissolved in 55 ml of water to obtain liquid C.

These A and B solutions were mixed simultaneously at room temperature for 10 minutes.
dripped into the liquid. After boiling the resulting mixture for 1 hour,
The mixture was placed in an autoclave and heated at a reaction temperature of 170°C for 13 hours, followed by filtration to obtain a solid product.

Next, sodium hydroxide 2.05.9 and tetra-n
- 23.8 g of flobyl ammonium bromide in 1 part of water
501111 to obtain liquid D, and a silica sol aqueous solution (trade name, Snowtex-89 manufactured by Nissan Chemical Co., Ltd.)
91.6.9 was dissolved in 111 mJ of water to prepare Solution E. Solutions D and E were simultaneously dropped into 700 ml of water at room temperature over 10 minutes.

The above-mentioned solid product was added to the resulting mixed solution, placed in an autoclave, and heat-treated at a reaction humidity of 170° C. for 48 hours. Then, after filtering and washing the contents of the autoclave,
It was dried at 120°C for 12 hours. It was further calcined at 550° C. for 6 hours to obtain sodium type zeolite 52.4Ii having an inner shell of crystalline borosilicate and an outer shell of crystalline silicon oxide.

Furthermore, this sodium type zeolite 30. lir 5
In addition to the double-fill standard nitrate/monicum aqueous solution, 8
Refluxed for an hour. Next, the supernatant was cooled and left to stand, and the supernatant was removed by decantation.The reflux and decantation operations were repeated three times, and then filtered and washed.
Dry at 20°C for 12 hours to obtain one crystal of ammonium-type zeolite with an inner shell of borosilicate and an outer shell of crystalline oxidized silicic acid) 29. 'I got 7g.

This ammonium type zeolite was molded with alumina sol added as an inder so that the alumina content after firing was 20 mm, dried at 120'C for 16 hours,
The catalyst was calcined at 550°C for 6 hours and then at 900°C for 2 hours to obtain a catalyst having an inner shell of crystalline borosilicate and an outer shell of crystalline silicon oxide.

(2) Reaction of toluene and ethylene In Example 1 (2), the reaction was carried out in the same manner as in Example 1 (2) except that the catalyst obtained in (1) above was used as the catalyst. The results are shown in Table 1.

Table 1

Claims (1)

[Scope of Claims] (1) A method for producing paraethyltoluene, characterized in that crystalline borosilicate is used as a catalyst for producing paraethyltoluene by reacting toluene and ethylene in the presence of a catalyst. (2) A method for producing paraethyl toluene, which comprises using crystalline borosilicate supporting silicon oxide as a catalyst during the production of paraethyltoluene by reacting toluene and ethylene in the presence of MAY=. (1) The method according to claim 2, wherein the titted silicon is thermoformed or crystalline.