JP2943266B2 - Method for producing tertiary olefin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a tertiary olefin corresponding to a side chain by dealkylating an aromatic hydrocarbon having an alkyl group in the side chain. .

Tertiary olefins are useful as intermediate materials for agricultural chemicals and chemical products.

[Problems to be solved by conventional technology and invention]

As a method for producing a tertiary olefin, for example, 2,3-dimethyl-2-butene, a method for dimerizing propylene with a nickel catalyst system is known (Japanese Patent Application Laid-Open No. 54-39004).

However, in this method, not only is the catalyst unstable in air, but also the cost of the catalyst is high.

Further, when performing a reaction for producing a tertiary olefin by dealkylation of an aromatic hydrocarbon substituted with a tertiary alkyl group, the present inventors have found that ZS is a known dealkylation catalyst.
As a result of a gas-phase flow method using M-5 zeolite (JP-A-61-47424, etc.), skeletal isomerization of the desired tertiary olefin occurred, and a large amount of by-products was produced. As described above, there is a problem that the selectivity of the target tertiary olefin is low when a known dealkylation catalyst is used.

[Means for Solving the Problems] In view of such circumstances, the present inventors dealkylate an aromatic hydrocarbon having an alkyl group in a side chain to produce a tertiary olefin corresponding to the alkyl group in the side chain. As a result of diligent studies as a dealkylation catalyst, the use of a specific catalyst suppresses by-products of skeletal isomers and enables the highly selective production of the desired tertiary olefin. The present invention was also found to be easy, and the present invention was completed through various studies.

That is, the present invention produces a tertiary olefin represented by the general formula (II) and / or (III) by dealkylating an aromatic hydrocarbon represented by the general formula (I) having an alkyl group in a side chain. The method according to the third aspect, wherein at least one catalyst selected from the group consisting of modified silica obtained by supporting an aluminum compound on silica and calcined, ion-exchanged X zeolite, ion-exchanged mordenite, and heteropolyacid is used as a catalyst. The present invention provides a method for producing a grade olefin.

((I), (II) , (III) formula R _1, R _2, R ₄ each represents a hydrogen atom or a lower alkyl group, R _2, R ₄ is not simultaneously hydrogen atoms .R ₃ Represents a lower alkyl group, R ₅ represents a hydrogen atom or a lower alkyl group.) Hereinafter, the present invention will be described in detail.

Examples of the catalyst used in the present invention include ion-exchanged X zeolite, ion-exchanged mordenite, heteropolyacid,
Alternatively, at least one kind of a modified silica obtained by supporting an aluminum compound on silica and calcining the same is exemplified.

As the ion-exchanged X zeolite or mordenite, sodium cation type X zeolite or mordenite may be used. Those ion-exchanged with cations such as protons may be mentioned. Among them, X zeolite or mordenite ion-exchanged with a cation of proton, lanthanum, lithium, magnesium or cerium is preferable.

The method of ion-exchanging X zeolite or mordenite is not particularly limited, and a known method can be employed.

Examples of the heteropolyacid include one or a mixture of two or more of tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, molybdosilicic acid, vanadophosphoric acid, and vanadosilicic acid.

Of these, tungstophosphoric acid and tungstosilicic acid are preferred. In the present invention, those in which these heteropoly acids are supported on a commonly used carrier such as silica or activated carbon can also be used.

The method for supporting the heteropolyacid on the carrier is not particularly limited, and a known method such as an impregnation method can be employed.

Next, the modified silica used in the present invention is preferably obtained by supporting an aluminum compound on silica and calcining the aluminum compound at a temperature from the temperature at which the aluminum compound normally decomposes to 1500 ° C.

As a method of supporting the aluminum compound, known methods, for example, a method of impregnating a silica carrier with an aluminum compound (equilibrium adsorption method, evaporation to dryness method, spray method, etc.),
Various methods such as a method in which silica powder and an aluminum compound are sufficiently mixed and molded, and a method in which silica and an aluminum compound are kneaded in a slurry state and molded, can be employed.

The firing time depends on the firing temperature, but usually 0.1 to 24 hours,
Preferably, it is about 0.5 to 10 hours.

The amount of the aluminum compound supported on the silica depends on the carrier 10
0 to 100 parts by weight, usually 0.1 to 100 parts by weight, preferably 1 to 5 parts by weight.
0 parts by weight.

As the aluminum compound used in the present invention, a compound which decomposes usually at 1500 ° C. or lower is used, and examples thereof include aluminum sulfate, nitrate, halide, organic acid salt and hydroxide. Of these, sulfates are preferred.

The present invention is a method for dealkylating an aromatic hydrocarbon having an alkyl group in a side chain using such a catalyst. As the aromatic hydrocarbon, a monocyclic aromatic hydrocarbon represented by the general formula (I) is usually used.

In the formula, R ₁ , R ₂ , and R ₄ each usually represent a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, or a propyl group, and R ₂ and R ₄ are not simultaneously hydrogen atoms. R ₃ usually includes a lower alkyl group such as a methyl group, an ethyl group, and a propyl group. The total carbon number of the side chain alkyl group including R ₁ , R ₂ , R ₃ , and R ₄ is 5 to 10. R ₅ is usually a hydrogen atom or a methyl group, an ethyl group, a normal propyl group, an isopropyl group,
A lower alkyl group such as a normal butyl group is exemplified.

Further, as the aromatic hydrocarbon, specifically, (1,1,
(2-trimethylpropyl) benzene, (1,1-dimethylpropyl) benzene, (1,1,2-trimethylbutyl) benzene, (1,2-dimethylpropyl) benzene, (1,2-dimethylbutyl) benzene, ( 1-ethyl-2-methylpropyl) benzene, (1-ethyl-1,2-dimethylpropyl) benzene, 1- (1,1,2-trimethylpropyl)
-4-methylbenzene, (1,2-dimethylhexyl) benzene, (1,2-dimethyloctyl) benzene, 1-
(1,1,2-trimethylpropyl) -4-isopropylbenzene and the like.

The tertiary olefin obtained by the present invention is a compound represented by the general formula (II) and / or (III),
An olefin having a total of 5 to 10 carbon atoms.

(Wherein R ₁ , R ₂ , R ₃ , and R ₄ have the same meaning as in the general formula (I).) The tertiary olefin represented by the general formula (II) is
Also included are the cis and trans isomers where R ₃ and R ₄ are interchanged.

Specific examples of the tertiary olefin include 2,3-dimethyl-2-butene, 2,3-dimethyl-1-butene, 2-methyl-2-butene, 2-methyl-1-butene, and 2,3-dimethylene. Dimethyl-2-pentene, 2,3-dimethyl-1-pentene,
3-methyl-2-pentene, 2-methyl-2-pentene, 3-methyl-2-heptene, 3-methylnonene and the like.

As a method for carrying out the present invention, any of a gas phase method and a liquid phase method can be adopted. In addition, any of a distribution system using a fluidized bed or a fixed bed and a batch system can be adopted. Among them, the liquid phase method is preferable because the desired tertiary olefin can be obtained with good selectivity. Further, the distribution system by the liquid phase method is more preferable as an industrial system.

The reaction temperature of the method of the present invention is usually from 100C to 450C, preferably from 200C to 350C. The reaction pressure of the method of the present invention is usually from atmospheric pressure to 20 kg / cm ² , preferably from atmospheric pressure to 10 kg / cm ² .

The amount of the catalyst used in the process of the present invention is usually 2 to 50% by weight, preferably 5 to 30% by weight based on the aromatic hydrocarbon in the batch mode.
% By weight.

Also, the weight ratio of catalyst to aromatic hydrocarbon in the distribution system
W / F is usually 0.05 to 100, preferably 0.1 to 80.

Although the reaction time of the present invention is not particularly limited,
It is usually 1 to 50 hours, preferably 2 to 25 hours.

〔The invention's effect〕

As described in detail above, the present invention can produce the desired tertiary olefin with good selectivity, and the catalyst used is easy to handle.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Catalyst preparation method) Reference example 1 (Preparation of La ³⁺ type mordenite) 40 g of synthetic mordenite (Na ⁺ type, SiO ₂ / Al ₂ O ₃ = 10) was added to 0.1 g of 0.1%.
It was immersed in 490 ml of a 05N aqueous ammonium chloride solution and stirred at 25 ° C. for 12 hours. This operation was repeated five times. Next, it was washed with 2000 ml of water and dried at 120 ° C. for 10 hours. By the above operation, NH ₄ ⁺ type mordenite was obtained. This NH ₄ ⁺ type mordenite
Immerse 15 g in 75 ml of 2.5 wt% lanthanum acetate aqueous solution,
For 1 hour. This operation was repeated three times. Then 10
Washed with 00 ml of water and dried at 120 ° C. for 10 hours. Then 400 ℃
For 3.5 hours to obtain La ³⁺ type mordenite.

Reference Example 2 (Preparation of Ce ³⁺ type mordenite) 10 g of NH ₄ ⁺ type mordenite was immersed in 50 ml of a 2.0% by weight cerium acetate aqueous solution, and stirred at 60 ° C for 1 hour. This operation 3
Repeated times. Hereinafter, the same operation as that of the La ³⁺ type mordenite was performed to obtain Ce ³⁺ type mordenite.

Reference Example 3 (Preparation of H ⁺ type X zeolite) 100 g of synthetic 13X zeolite (Na ⁺ type X zeolite, Molecular Sieve 13X manufactured by Union Showa Co., Ltd.) was immersed in 500 ml of 0.05N ammonium chloride aqueous solution and stirred at 25 ° C. for 12 hours. . This operation was repeated five times. Next, it was washed with 5000 ml of water and dried at 120 ° C. for 10 hours. By the above operation, NH ₄ ⁺
Type X zeolite was obtained. This NH ₄ ⁺ type X zeolite is 500
Calcination at 3 ° C. for 3 hours gave an H ⁺ type X zeolite.

Reference Example 4 (Preparation of Li ⁺ type X zeolite) 15 g of NH ₄ ⁺ type X zeolite was immersed in 75 ml of a 5.0% by weight aqueous lithium acetate solution, and stirred at 60 ° C. for 1 hour. This operation 2
Repeated times. Next, it was washed with 2000 ml of water and dried at 120 ° C. for 10 hours. Next, it was calcined at 350 ° C. for 3 hours to obtain Li ⁺ type X zeolite.

Reference Example 5 (Preparation of Mg ²⁺ type X zeolite) 15 g of NH ₄ ⁺ type X zeolite was immersed in 75 ml of a 5.0% by weight aqueous magnesium chloride solution and stirred at 60 ° C. for 1 hour. This operation was repeated twice. Thereafter, the same operation as that of the Li ⁺ type X zeolite was performed to obtain Mg 2 ⁺ type X zeolite.

Reference Example 6 (Preparation of La ³⁺ type X zeolite) 15 g of NH ₄ ⁺ type X zeolite was immersed in 75 ml of a 5.0% by weight aqueous lanthanum acetate solution, and stirred at 60 ° C. for 1 hour. This operation 2
Repeated times. Hereinafter, the same operation as that of the Li ⁺ type X zeolite was performed to obtain the La ^{3 +} type X zeolite.

0.05N Reference Example 7 (H ⁺ -type Preparation of Y zeolite) Synthesis Y zeolite (Na ⁺ type Y zeolite) 100 g
It was immersed in 500 ml of ammonium chloride aqueous solution and stirred at 25 ° C. for 12 hours. This operation was repeated five times. Next, it was washed with 5000 ml of water and dried at 120 ° C. for 10 hours. By the above operation, N
H ₄ ⁺ type Y zeolite was obtained. This NH ₄ ⁺ type Y zeolite is
Calcination at 50 ° C. for 3 hours gave an H ⁺ type Y zeolite.

Reference Example 8 (Preparation of Ca ²⁺ type Y zeolite) 15 g of NH ₄ ⁺ type Y zeolite was immersed in 75 ml of a 5.0% by weight aqueous solution of calcium chloride and stirred at 60 ° C. for 1 hour. This operation was repeated twice. Then wash with 1000 ml of water,
Dried for hours. Next, calcining was performed at 350 ° C. for 3 hours to obtain a Ca ²⁺ type Y zeolite.

Reference Example 9 (Preparation of Mg ²⁺ type Y zeolite) 15 g of NH ₄ ⁺ type Y zeolite was immersed in 75 ml of a 5.0% by weight aqueous magnesium chloride solution and stirred at 60 ° C. for 1 hour. This operation was repeated twice. Thereafter, the same operation as that of the Ca ²⁺ type zeolite was performed to obtain the Mg ²⁺ type zeolite.

Reference Example 10 (Preparation of H ⁺ type A zeolite) 100 g of synthetic A zeolite (Molecular sieve 4A manufactured by Union Showa Co., Ltd.) was added to a 0.05N ammonium chloride aqueous solution in 1200 ml.
And stirred at 20 ° C. for 12 hours. This operation was repeated five times. Next, it was washed with 600 ml of water and dried at 120 ° C. for 10 hours. By the above operation, NH ₄ ⁺ type A zeolite was obtained. The NH ₄ ⁺ type A zeolite is calcined at 350 ° C. for 3 hours to obtain an H ⁺ type A zeolite.
A zeolite was obtained.

Reference Example 11 (Preparation of H ⁺ -type ZSM-5 zeolite) First, raw material liquids having the following compositions were prepared.

A liquid water _{160g H 2 SO 4 7.3g Al 2} (SO 4) 3 · 17H 2 O 21.6g (n-Pr) 4 NBr 20.2g B liquid water 120 g 3 sodium silicate 186 g C liquid water 282 g NaCl 71 g Part C The solution A and the solution B were simultaneously dropped and mixed into the solution. At this time, the mixture was vigorously stirred while maintaining the pH in the system at 9 to 11 (a 48% by weight aqueous sodium hydroxide solution was added for pH adjustment). The pH at the end of mixing was 9.5. The mixture was charged into a stainless steel autoclave and heated at 160 ° C for 2 hours.
Hydrothermal synthesis was performed with stirring at 120 rpm for 0 hours. After cooling, the mixture was filtered, sufficiently washed with about 7 distilled water, and the filtration was repeated. After drying at 120 ° C. for 15 hours, the mixture was calcined at 530 ° C. for 3 hours under flowing air to obtain 49 g of white powdery crystals. This was identified as ZSM-5 as a result of X-ray diffraction measurement. As a result of composition analysis by fluorescent X-ray, the molar ratio of SiO ₂ / Al ₂ O ₃ was 12. Next, the Na / H type ZSM-5 obtained above was ion-exchanged at 65 ° C. for 2 hours with 200 g of a 5% by weight aqueous solution of ammonium chloride for 3 hours.
Turn, and further add 25 g of 5% by weight aqueous ammonium chloride solution to 25 g.
After ion exchange at 0 ° C overnight, the mixture was filtered. After repeating washing and filtration with 200 g of distilled water a total of 5 times, the resultant was dried at 120 ° C. for 10 hours to obtain NH ₄ ⁺ type ZSM-5.

Next, NH ₄ ⁺ type ZSM-5 is calcined at 530 ° C. for 3 hours to obtain H ⁺ type ZSM.
-5 was obtained.

Reference Example 12 (Preparation of MgO / Li ⁺ type ZSM-5 zeolite) NH ₄ ⁺ type ZS obtained in Reference Example 11 having a SiO ₂ / Al ₂ O ₃ molar ratio of 12
140m of an ion exchange liquid consisting of 2 parts by weight of M-54.0 g of a 0.1 M / L aqueous solution of lithium chloride and 1 part by weight of an aqueous 0.1N lithium hydroxide solution
and stirred at 20 ° C. for 1 hour to carry out ion exchange treatment. After filtration, it was sufficiently washed with distilled water and dried at 120 ° C. for 2 hours to obtain Li ⁺ type ZSM-5.

Next, 28 ml of an 8% by weight aqueous magnesium acetate solution was added to 52.5 g of the obtained Li ⁺ -type ZSM-52.5 g, and the mixture was stirred and concentrated to dryness at 80 ° C. using a rotary evaporator. Subsequently, after drying at 120 ° C. for 10 hours, it is calcined at 530 ° C. for 3 hours under an air stream to obtain MgO / Li ⁺
3.1 g of type ZSM-5 (MgO supported amount = 2.0% by weight) was obtained.

Reference Example 13 (Preparation of Modified Silica) Commercially available silica carrier (trade name: Silica N, Nikki Chemical Co., Ltd.)
-608) was ground to 10 to 24 mesh. The silica 100
Aluminum sulfate was supported by an impregnation method so as to be 10 parts by weight of aluminum sulfate with respect to parts by weight. 130 ° C in air
After drying at 350 ° C. for 3 hours and at 350 ° C. for 3 hours, respectively, the resultant was calcined at 900 ° C. for 5 hours in a nitrogen gas to obtain a modified silica.

Reference Example 14 (Preparation of 10% by weight tungstophosphoric acid supported on silica) 100 g of a 2% by weight aqueous solution of tungstophosphoric acid (Nacalai Tesque Co., Ltd., reagent grade) was mixed with silica (Fujidevison Chemical Co., Ltd.
# 57) Soak 20 g and use a rotary evaporator for 60
After stirring at ℃ for 1 hour, it was dried. In addition, this is 120
After drying at 10 ° C. for 10 hours, 10% by weight of tungstophosphoric acid supported on silica was obtained.

Example 1 In a 100 ml flask, 4 g of the La ³⁺ type mordenite prepared in Reference Example 1 and 20 g of (1,1,2-trimethylpropyl) benzene (hereinafter abbreviated as TMPB) were placed, and stirred at 214 ° C.
The temperature rose. Further, the reaction was carried out for 3 hours while blowing nitrogen at 50 ml / min into the liquid, and the distilled components were cooled and collected.

As a result of analyzing the collected components by gas chromatography, the conversion of TMPB was 20.1%, the selectivity for 2,3-dimethyl-2-butene (hereinafter abbreviated as 2,3-DM2B) was 65.1%, and the Selectivity of 1-butene (hereinafter abbreviated as 2,3-DM1B) 23.4%, total selectivity of target tertiary olefin
88.5%.

The selectivity of 2,3-DM2B and 2,3-DM1B was calculated by the following equation.

However, in both of the above formulas, hydrocarbons having 6 carbon atoms do not include benzene.

Example 2 A reaction was carried out according to Example 1, except that the La ³⁺ type X zeolite prepared in Reference Example 6 was used as a catalyst.

As a result of the reaction, the conversion of TMPB was 14.8% and the selectivity of 2,3-DM2B was 6%.
The selectivity of 8.2%, the selectivity of 2,3-DM1B was 26.1%, and the selectivity of the target tertiary olefin was 94.3% in total.

Example 3 Mg ²⁺ type zeolite prepared in Reference Example 5 was used as a catalyst, liquid paraffin was used as a solvent, and the reaction temperature was 24.
Example 1 except that the reaction was carried out at 0 ° C. for a reaction time of 6 hours.
The reaction was carried out according to.

As a result of the reaction, the conversion of TMPB was 25.5% and the selectivity of 2,3-DM2B was 5%.
The selectivity of 9.2%, 2,3-DM1B was 22.8%, and the total selectivity of the target tertiary olefin was 82.0%.

Example 4 Tungstosilicic acid (Nakarai Tex Co., Ltd. reagent special grade)
The reaction was carried out according to Example 1, except that was used as a catalyst.

As a result of the reaction, the conversion of TMPB was 25.9% and the selectivity of 2,3-DM2B was 6
The selectivity for 3.9%, 2,3-DM1B was 22.2%, and the selectivity for the target tertiary olefin was 86.1%.

Example 5 Tungstophosphoric acid (Nacalai Tesque Co., Ltd. reagent special grade)
The reaction was carried out according to Example 1, except that was used as a catalyst.

As a result of the reaction, the conversion of TMPB was 35.1% and the selectivity of 2,3-DM2B was 6%.
The selectivity of 4.5%, the selectivity of 2,3-DM1B was 21.4%, and the selectivity of the target tertiary olefin was 85.9% in total.

Example 6 A reaction was carried out in the same manner as in Example 1 except that the Ce ³⁺ type mordenite prepared in Reference Example 2 was used as a catalyst.

As a result of the reaction, the conversion of TMPB was 29.1% and the selectivity of 2,3-DM2B was 5%.
The selectivity for 2,3-DM1B was 21.4%, and the selectivity for the target tertiary olefin was 73.8% in total.

Comparative Example 1 Using the Ca ²⁺ type zeolite prepared in Reference Example 8 as a catalyst, liquid paraffin as a solvent, and a reaction temperature of 24.
Example 1 except that the reaction was carried out at 0 ° C. for a reaction time of 6 hours.
The reaction was carried out according to.

As a result of the reaction, the conversion of TMPB was 49.4% and the selectivity of 2,3-DM2B was 3
The selectivity of 7.7%, the selectivity of 2,3-DM1B was 14.5%, and the selectivity of the target tertiary olefin was 52.2%.

Example 7 A 500 ml flask was charged with 7 g of the La ³⁺ type mordenite prepared in Reference Example 1 and 35 g of TMPB, and stirred at 210 ° C.
The temperature rose. While blowing nitrogen at 50 ml / min into the liquid
TMPB was supplied at 3.44 g / h, and after reacting for 200 hours, the distilled components were cooled and collected for 4.5 hours.

The collected components were analyzed by gas chromatography. As a result, the conversion of TMPB per hour was 35.2%, the selectivity of 2,3-DM2B was 66.4%, the selectivity of 2,3-DM1B was 20.3%, The total selectivity for grade olefins was 86.7%.

Example 8 10 g of the La ³⁺ type zeolite prepared in Reference Example 6 and 35 g of TMPB were placed in a 500 ml flask, and stirred.
The temperature was raised to ° C. Supplying TMPB at 3.44 g / h while blowing nitrogen at 50 ml / min into the liquid, and after reacting for 112 hours, for 4.5 hours,
The distilled components were cooled and collected.

As a result of analyzing the collected components by gas chromatography, the conversion rate of TMPB per hour was 43.4%, the selectivity of 2,3-DM2B was 59.0%, the selectivity of 2,3-DM1B was 22.0%, The total selectivity for grade olefins was 81.0%.

Example 9 A 500 ml flask was charged with 10 g of tungstophosphoric acid (Nacalai Tesque, Inc., reagent grade) and 35 g of TMPB, and the temperature was raised to 216 ° C. while stirring. Supplying TMPB at 2.9 g / h while blowing nitrogen at 50 ml / min into the liquid, and after reacting for 36 hours,
The components distilled off were cooled and collected for 4.5 hours. As a result of analyzing the collected components by gas chromatography, the conversion of TMPB per hour was 19.6%, the selectivity of 2,3-DM2B was 62.2%,
The selectivity of 2,3-DM1B was 23.9%, and the selectivity of the target tertiary olefin was 86.1% in total.

Example 10 A 500 ml flask was charged with 10 g of tungstosilicic acid (Nacalai Tesque, Inc., reagent grade) and 35 g of TMPB, and the temperature was raised to 216 ° C. while stirring. While blowing nitrogen into the solution at 50 ml / min, TMPB was supplied at 3.44 g / h, and after 34 hours of reaction, the distilled components were cooled and collected for 4.5 hours.

As a result of analyzing the collected components by gas chromatography, the conversion of TMPB per hour was 15.9%, the selectivity of 2,3-DM2B was 63.0%, the selectivity of 2,3-DM1B was 22.4%, The total selectivity for grade olefins was 85.4%.

Example 11 89 modified silica prepared in Reference Example 13 in a 500 ml flask
g and 35 g of TMPB were added, and the temperature was raised to 217 ° C. while stirring. While blowing nitrogen at 50 ml / min into the liquid,
After feeding at 1.22 g / h and reacting for 107 hours, the distilled components were cooled and collected for 4.5 hours.

As a result of analyzing the collected components by gas chromatography, the conversion of TMPB per hour was 21.2%, the selectivity of 2,3-DM2B was 60.5%, the selectivity of 2,3-DM1B was 30.0%, The total selectivity for grade olefins was 90.5%.

Example 12 H ⁺ type X zeolite prepared in Reference Example 3 in a quartz reaction tube
0.88 g, TMPB supplied at 3 g / h at normal pressure, nitrogen
It was distributed at 0 ml / min. During this time, the catalyst was heated to 298 ° C. in an electric furnace to react for 1 hour. The reaction gas was cooled, collected, and analyzed by gas chromatography. TMPB conversion rate 2
0.2%, selectivity of 2,3-DM2B 46.5%, selectivity of 2,3-DM1B 2
3.5%, total selectivity of target tertiary olefin 70.0
%Met.

Comparative Example 2 0.7 g of MgO / Li ⁺ ZSM-5 zeolite prepared in Reference Example 12
And the feed rate of TMPB is 2.25 g / h and the reaction temperature is 400
The reaction was carried out according to Example 12, except that the temperature was changed to ° C.

As a result of the reaction, the conversion of TMPB was 0.6% and the selectivity of 2,3-DM2B was 0.
%, Selectivity of 2,3-DM1B was 0%, and total selectivity of the target tertiary olefin was 0%.

Comparative Example 3 The reaction was carried out in the same manner as in Example 12, except that 0.63 g of the H ⁺ type ZSM-5 zeolite prepared in Reference Example 11 was charged and the reaction temperature was changed to 298 ° C.

As a result of the reaction, the conversion of TMPB was 24.3% and the selectivity of 2,3-DM2B
The selectivity of 2.1%, the selectivity of 2,3-DM1B was 4.5%, and the selectivity of the target tertiary olefin was 6.6% in total.

Comparative Example 4 1.0 g of the H ⁺ type A zeolite prepared in Reference Example 10 was filled,
The reaction was carried out according to Example 12, except that the reaction temperature was 300 ° C.

 As a result, no reaction proceeded.

Comparative Example 5 The reaction was carried out in the same manner as in Example 12 except that 0.86 g of the H ⁺ -type Y zeolite prepared in Reference Example 7 was charged, and the reaction temperature was changed to 298 ° C.

As a result of the reaction, the conversion of TMPB was 28.1% and the selectivity of 2,3-DM2B was 3
The selectivity of 4.5%, the selectivity of 2,3-DM1B was 17.4%, and the selectivity of the target tertiary olefin was 51.9% in total.

Example 13 A quartz reaction tube was filled with 0.87 g of Mg ²⁺ type zeolite prepared in Reference Example 5 and (1,1-dimethylpropyl) was added under normal pressure.
Benzene (hereinafter abbreviated as TAB) was supplied at 3.33 g / h, and nitrogen was passed at 50 ml / min. During this time, the catalyst was placed in an electric furnace for 296
The mixture was heated to ℃ and reacted for 1 hour. Cooling the reaction gas,
As a result of collecting and analyzing by gas chromatography, TAB
Conversion rate 83.6%, selectivity of 2-methyl-2-butene (hereinafter abbreviated as 2M2B) 60.0%, selectivity of 2-methyl-1-butene (hereinafter abbreviated as 2M1B) 22.2%, target third The total selectivity for grade olefins was 82.8%.

Example 14 The reaction was carried out in the same manner as in Example 13 except that 11.0 g of the H ⁺ type X zeolite prepared in Reference Example 3 was charged, and the reaction temperature was changed to 297 ° C.

As a result of the reaction, the TAB conversion rate was 48.0% and the selectivity for 2M2B was 66.2.
%, The selectivity of 2M1B was 20.4%, and the selectivity of the target tertiary olefin was 86.6% in total.

Example 15 The reaction was carried out according to Example 13 except that 0.872 g of the Li ⁺ type X zeolite prepared in Reference Example 4 was charged and the reaction temperature was changed to 295 ° C.

As a result of the reaction, the TAB conversion rate was 34.8% and the selectivity for 2M2B was 67.1.
%, The selectivity of 2M1B was 20.8%, and the selectivity of the target tertiary olefin was 87.9% in total.

Example 16 A reaction was carried out in the same manner as in Example 13 except that 0.612 g of 10% by weight tungstophosphoric acid / silica prepared in Reference Example 14 was filled and the reaction temperature was changed to 346 ° C.

As a result of the reaction, the TAB conversion rate was 28.5% and the selectivity of 2M2B was 66.4.
%, The selectivity of 2M1B was 24.2%, and the selectivity of the target tertiary olefin was 90.6% in total.

Comparative Example 6 The reaction was carried out in the same manner as in Example 13 except that 0.825 g of Na ⁺ type X zeolite (Molecular Sieve 13X manufactured by Union Showa Co., Ltd.) was filled and the reaction temperature was changed to 300 ° C.

As a result of the reaction, TAB conversion rate was 0.2%, selectivity of 2M2B was 0%, 2M
The selectivity of 1B was 0%, and the total selectivity of the target tertiary olefin was 0%.

Comparative Example 7 The reaction was carried out in the same manner as in Example 13 except that 0.892 g of the Mg ²⁺ type Y zeolite prepared in Reference Example 9 was charged and the reaction temperature was changed to 245 ° C.

As a result of the reaction, the TAB conversion rate was 49.5% and the selectivity for 2M2B was 37.9.
%, The selectivity of 2M1B was 10.1%, and the selectivity of the target tertiary olefin was 48.0% in total.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B01J 29/18 B01J 29/18 C07C 4/18 C07C 4/18 // C07B 61/00 300 C07B 61/00 300 (72) Invention Person Takeo Suzugamo 2-10-1 Tsukahara, Takatsuki City, Osaka Prefecture Within Sumitomo Chemical Co., Ltd. (56) References JP-A-61-47424 (JP, A) JP-A-61-47425 (JP, A) 59-216835 (JP, A) JP-A-3-220136 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 11 / 02,4 / 18 B01J 21 / 12,21 / 16,27 / 188 B01J 29 / 08,29 / 18 C07B 61/00 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] (1) An aromatic hydrocarbon represented by the general formula (I) having an alkyl group in a side chain is dealkylated to obtain a compound represented by the general formula (I)
In the method for producing a tertiary olefin represented by I) and / or (III), as a catalyst, a modified silica obtained by supporting and calcining an aluminum compound on silica, ion-exchanged X zeolite, ion-exchanged mordenite,
A method for producing a tertiary olefin, comprising using at least one catalyst among heteropoly acids. ((I), (II) , (III) formula R _1, R _2, R ₄ each represents a hydrogen atom or a lower alkyl group, R _2, R ₄ is not simultaneously hydrogen atoms .R ₃ Represents a lower alkyl group, and R ₅ represents a hydrogen atom or a lower alkyl group.)