JPH0549936A - Catalyst for producing aromatic hydrocarbon and its production by using said catalyst - Google Patents

Abstract

PURPOSE:To efficiently produce aromatic hydrocarbon from non-aromatic hydrocarbon using a catalyst capable of being simply produced and having high catalytic activity and long life. CONSTITUTION:The objective catalyst for producing aromatic hydrocarbon is produced by simultaneously supporting a platinum component and halogen on L-type zeolite and aromatic hydrocarbon is produced from various hydrocarbons using said catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic production catalyst and a method for producing an aromatic hydrocarbon using the same, and more specifically, an aromatization reaction in which platinum and a halogen component are simultaneously supported on L-type zeolite. And a method for efficiently producing an aromatic hydrocarbon from a non-aromatic hydrocarbon such as a paraffinic hydrocarbon using the catalyst.

[0002]

2. Description of the Related Art Conventionally, platinum-alumina catalysts have been used as catalysts for aromatizing non-aromatic hydrocarbons such as aliphatic hydrocarbons to produce aromatic hydrocarbons. However, in recent years, a method of using a platinum-supported L-type zeolite catalyst having an improved conversion rate has been proposed (Japanese Patent Publication No. 58-57408, Japanese Patent Laid-Open No. 58-2).
23,614, JP-A-59-80333).

However, none of the platinum-supported L-type zeolite catalysts used in these methods has a low aromatic selectivity and a short catalyst life, which is unsatisfactory. As an improved version of this, alkaline earth metals (B
Although a platinum-supported L-type zeolite catalyst into which (a, Sr, Ca) has been introduced has been proposed (Japanese Patent Laid-Open No. 58-133835), according to the additional examination by the present inventors, this catalyst also has an aromatic selectivity. Moreover, the catalyst life is not sufficiently improved, and the catalyst stability is low, which is not practical.

Further, by subjecting the L-type zeolite carrying a Group VIII metal to oxychlorination treatment, a catalyst having improved catalytic activity and catalyst life (Japanese Patent Laid-Open No. 60-168539).
(JP-A-61-138539), a catalyst which is treated with a solution consisting of a platinum solution and a non-platinum metal salt for uniformly dispersing and supporting platinum (JP-A-61-138539), and an L-type zeolite treated with a halogen-containing compound. A catalyst supporting platinum (JP-A-62-57653), a catalyst in which platinum-supporting L-type zeolite is treated with a halogen-containing compound (JP-A-63-91334), and the like have been proposed.

However, since the oxychlorination treatment is carried out at a high temperature in the step of preparing the catalyst, the processing equipment is expensive and the economical efficiency is extremely low, and the catalyst activity of the catalyst is insufficient. Further, in the cases of and, although the catalyst activity is improved, the catalyst life is not sufficient, and special equipment for halogen treatment is required. In addition, as the halogen-containing compound, chlorofluorocarbon, which has recently become a problem in terms of environmental impact, has been used, and its use is environmentally undesirable. As described above, the conventional catalysts have problems in preparation process, catalyst activity, catalyst life, and the like, and the present situation is that no catalyst that is practically satisfactory has been proposed yet.

[0006]

Therefore, the present inventors have
As a catalyst for aromatics production, the above-mentioned problems of conventional catalysts are solved, and it is earnest to develop a catalyst that can be obtained in a simple process without requiring special equipment for preparation, has high activity, and has a long life. Repeated research. As a result, a catalyst obtained by simultaneously supporting a platinum component and a halogen component on L-type zeolite is
It has been found that it is suitable for the above purpose. The present invention has been completed based on such findings.

That is, the present invention provides a catalyst for aromatic production, which is obtained by simultaneously carrying out a treatment of a platinum-containing compound and a halogen-containing compound (excluding alkali metal salt and alkaline earth metal salt) on L-type zeolite. It is a thing. Further, the present invention provides one or more hydrocarbons selected from the group consisting of paraffinic hydrocarbons, olefinic hydrocarbons, acetylene hydrocarbons, cyclic paraffinic hydrocarbons and cyclic olefinic hydrocarbons as described above. The present invention also provides a method for producing an aromatic hydrocarbon, which is characterized by contacting with a catalyst.

The catalyst of the present invention uses L-type zeolite as a carrier. Here, the L-type zeolite is a composition formula 0.
9-1.3M _{2 / n} O ・ Al ₂ O ₃・ 5.0-7.0SiO ₂・
0-9H ₂ O (in the formula, M represents an alkali metal or an alkaline earth metal, and n represents a valence of M), and specifically, it is described in JP-A-58-133835.
Nos. 9 to 10 and Japanese Patent Laid-Open No. 59-80333, page 5.

The catalyst of the present invention is characterized in that the above L-type zeolite is prepared by simultaneously supporting and treating a platinum-containing compound and a halogen-containing compound. in this way,
By supporting the platinum component and the halogen component at the same time, it is possible to impart unprecedented excellent catalytic activity and catalyst life.

The platinum-containing compound is not particularly limited as long as it serves as a platinum source, but a platinum salt is usually used. Specific examples thereof include tetraammineplatinum chloride, chloroplatinic acid, chloroplatinate, tetraammineplatinum hydroxide, and dinitrodiaminoplatinum.

Various kinds of halogen-containing compounds can be mentioned, but alkali metal salts and alkaline earth metal salts are excluded. Specifically, chlorine-containing compounds such as hydrogen chloride and ammonium chloride, fluorine-containing compounds such as hydrogen fluoride and ammonium fluoride, iodine-containing compounds such as hydrogen iodide and ammonium iodide, hydrogen bromide and ammonium bromide, etc. Examples thereof include bromine-containing compounds. As the halogen-containing compound, one kind or a mixture of two or more kinds of the above compounds may be used.

The catalyst of the present invention is prepared by simultaneously supporting the platinum-containing compound and the halogen-containing compound on the above-mentioned L-type zeolite. The method of supporting treatment is not particularly limited as long as the platinum component and the halogen component are simultaneously supported, and can be carried out by a normal pressure impregnation method, a vacuum impregnation method, an infiltration method, an ion exchange method or the like. .. The loading amount in the loading treatment is not particularly limited, but the loading amount of the platinum-containing compound is usually 0.1 to 5 as platinum based on the total weight of the catalyst.
0% by weight is preferable, and the range of 0.3 to 1.5% by weight is most suitable. Further, the supported amount of the halogen-containing compound is preferably 0.1 to 5% by weight in terms of halogen based on the total weight of the catalyst. The conditions of the supporting treatment are not particularly limited and may be appropriately selected depending on various circumstances, but the L-type zeolite is contacted with the platinum-containing compound and the halogen-containing compound at the same time at room temperature to 90 ° C. for 1 minute to 10 hours. You can do it.

If desired, natural or synthetic inorganic oxides such as alumina, silica, aluminosilicate and the like can be added to the catalyst of the present invention as a binder. The amount of these binders used is preferably 5 to 25% by weight based on the total weight of the catalyst.

As described above, the catalyst of the present invention has a special device,
It can be prepared without any steps. The obtained catalyst is used as a so-called aromatization catalyst, which produces aromatic hydrocarbons from various hydrocarbons under suitable reaction conditions in high yield, but according to the method of the present invention, it is extremely efficient. Aromatic hydrocarbons can be produced well.

In the method for producing an aromatic hydrocarbon of the present invention, the group consisting of paraffinic hydrocarbons, olefinic hydrocarbons, acetylene hydrocarbons, cyclic paraffinic hydrocarbons and cyclic olefinic hydrocarbons as the raw material hydrocarbons. One or two or more kinds of hydrocarbons selected from the above are used and brought into contact with the catalyst of the present invention to produce an aromatic hydrocarbon.

The paraffinic hydrocarbon preferably has 6 to 10 carbon atoms, specifically n-hexane, methylpentane, n-heptane, methylhexane,
Examples thereof include dimethyl pentane and n-octane.

Examples of the olefinic hydrocarbons include olefins having 6 to 10 carbon atoms, specifically hexene, methylpentene, heptene, methylhexene, dimethylpentene, octene and the like. As the acetylene-based hydrocarbon, those having a carbon number of 6 to 10, specifically, hexyne, heptin, octyne and the like can be mentioned.

The cyclic paraffin hydrocarbon has a carbon number of 6 to 10, specifically, methylcyclopentane,
Examples thereof include cyclohexane, methylcyclohexane and dimethylcyclohexane. Further, the cyclic olefin hydrocarbon has a carbon number of 6 to 10,
Specific examples include methylcyclopentene, cyclohexene, methylcyclohexene, dimethylcyclohexene and the like.

The method of the present invention proceeds by bringing the above-mentioned raw material hydrocarbon into contact with the above-mentioned catalyst, and there are no particular restrictions on the conditions at that time. However, in order to obtain good results, a temperature of 350-600 ° C, preferably 400
˜550 ° C., pressure 0-40 kg / cm ² G, preferably 0-10 kg / cm ² G, liquid hourly space velocity (LHSV) 0.
It should be ¹ to 20 hr ^-1 , preferably ¹ to 10 hr ^-1 . Furthermore, the supply ratio of hydrogen gas / raw hydrocarbons is 0.1
If it is selected in the range of ˜50 mol / mol, even better results can be expected.

[0020]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Example 1 (1) Preparation of catalyst L-type zeolite (manufactured by Tosoh Corporation; TSZ-500KO)
A) 100 parts by weight of silica binder (Nissan Chemical Co., Ltd.)
(Manufactured by Snowtex) 20 parts by weight was added and kneaded and molded. Then, the mixture was air-baked at 500 ° C. for 2 hours to obtain a silica binder-molded L-type zeolite. Then 1.39 g of 3.6% by weight hydrogen chloride solution, ammonium fluoride 0.0
97 g, tetraammineplatinum chloride 0.171 g and ion-exchanged water 3.6 g were mixed to prepare an impregnation liquid. The impregnating solution prepared in this manner was used as the above silica binder molding L.
The mixture was gradually added dropwise to 10 g of type zeolite while stirring, and the platinum and halogen loading treatments were simultaneously performed. Then, after drying at room temperature overnight, the catalyst was prepared by treating in air at 300 ° C. for 30 minutes.

(2) Production of Aromatic Hydrocarbon 0.5 g of the catalyst prepared in Example (1) was charged into a quartz reaction tube and then treated in a hydrogen stream at 540 ° C. for 24 hours. Then, light naphtha having a weight composition ratio of n-hexane / isohexane / methylcyclopentane = 49/43/8 and hydrogen are respectively supplied at a weight hourly space velocity of 2 hr ⁻¹ and hydrogen / light naphtha = 5 mol / mol, Pressure 5kg /
It was adjusted to cm ² G and the temperature was 500 ° C., and the conversion reaction to aromatic was carried out. The change with time in the aromatic yield at this time is shown in FIG.

Comparative Example 1 (1) Preparation of catalyst Silica binder molding L obtained in Example 1 (1) above
20 g of type zeolite was filled in a quartz reaction tube and kept at 200 ° C. for 30 minutes while flowing nitrogen, after which the gas was switched to monochlorotrifluoromethane and the temperature was raised to 500 ° C. After heating to 500 ° C. and treating for 2 hours, the gas was switched to nitrogen again and the temperature was lowered to obtain a halogen-treated L-type zeolite. Next, this halogen-treated L-type zeolite
An impregnating solution consisting of 0.171 g of tetraammineplatinum chloride and 4.0 g of ion-exchanged water was gradually added dropwise to 0 g of the solution while stirring to carry it. After the supporting, the catalyst was prepared by drying in a dryer at 80 ° C. for 3 hours.

(2) Production of Aromatic Hydrocarbon In Comparative Example 1 as a catalyst in the above Example 1 (2)
Example 1 except that the catalyst obtained in (1) was used
The conversion reaction was carried out in the same manner as (2). The time-dependent change in aromatic yield is shown in FIG.

Comparative Example 2 (1) Preparation of Catalyst L Silica binder molding L obtained in Example 1 (1) above
Tetraammineplatinum chloride 0.
An impregnation solution consisting of 171 g and ion-exchanged water 4.8 g was gradually added dropwise with stirring, dried at room temperature for 2 hours, and further treated in air at 80 ° C. for 3 hours to obtain a catalyst. The obtained catalyst was filled in a quartz reaction tube, kept at 200 ° C. for 1 hour while flowing nitrogen, and then heated to 480 ° C. At 480 ° C., the gas was changed to Freon 112 / nitrogen = 0.1 / 99.9 (volume%) and treated for 10 hours. Then, the gas was switched to nitrogen again and the temperature was lowered to prepare a catalyst.

(2) Production of Aromatic Hydrocarbon In Comparative Example 2 as the catalyst in Example 1 (2) above.
Example 1 except that the catalyst obtained in (1) was used
The conversion reaction was carried out in the same manner as (2). The time-dependent change in aromatic yield is shown in FIG.

Example 2 (1) Preparation of catalyst The same as in Example 1 (1) above.

(2) Production of aromatic hydrocarbons 0.05 g of the catalyst obtained in Example 2 (1) was sampled and charged in a pulse reactor. Then, the temperature was raised to 500 ° C. over 1 hour in a hydrogen stream, and the temperature was kept at 500 ° C. for 1 hour. The reaction temperature was adjusted to 470 ° C., and 3 microliters of n-hexane was pulsed in a hydrogen stream (2.2 liter / hour),
The conversion reaction was carried out. The yield of benzene in this case is 55.7%
Met.

Comparative Example 3 (1) Preparation of catalyst 0.0735 g of potassium chloride, 0.107 of potassium fluoride
g, tetraammineplatinum chloride 0.120 g and ion-exchanged water 3.50 g were mixed to prepare an impregnation liquid. The impregnating liquid thus prepared was gradually added dropwise to 7 g of the silica binder-molded L-type zeolite obtained in Example 1 (1) above while stirring. Then, it was dried at room temperature overnight and then treated in air at 300 ° C. for 30 minutes to prepare a catalyst.

(2) Production of Aromatic Hydrocarbon In Comparative Example 3 as the catalyst in Example 2 (2) above.
Example 2 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). The yield of benzene at this time was 10.8%.

Comparative Example 4 (1) Preparation of catalyst 1.39 g of 3.6% by weight hydrochloric acid solution, ammonium fluoride 0.1.
An impregnating liquid was prepared by mixing 097 g and ion-exchanged water 3.6 g. The impregnating solution thus prepared was gradually added dropwise to 10 g of the silica binder-molded L-type zeolite obtained in Example 1 (1) while stirring to carry halogen. Then, after drying overnight at room temperature,
A halogen-supported catalyst was obtained by treating at 0 ° C. for 30 minutes. 8 g of the obtained halogen-supported catalyst was added to tetraammine platinum chloride.
An impregnation liquid consisting of 0.137 g and ion-exchanged water 3.68 g was gradually added dropwise with stirring, and dried at room temperature overnight to prepare a catalyst.

(2) Production of Aromatic Hydrocarbon In Comparative Example 4 as the catalyst in Example 2 (2) above.
Example 2 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the yield of benzene was 47.1%.

Comparative Example 5 (1) Preparation of catalyst Silica binder molding L obtained in Example 1 (1) above
Tetraammineplatinum chloride 0.171 on 10g type zeolite
g and ion-exchanged water (4.8 g) are slowly added dropwise with stirring, dried at room temperature for 2 hours, and further in air 1
It was treated at 20 ° C. for 3 hours to obtain a platinum-supported catalyst. 0.5 g of a 6.8 wt% hydrogen chloride solution was added to 7 g of the obtained platinum-supported catalyst.
An impregnating solution obtained by mixing 4 g, 0.0682 g of ammonium fluoride and 3.34 g of ion-exchanged water was gradually added dropwise with stirring. After drying overnight at room temperature, 3 at 300 ° C in air
The catalyst was prepared by treating for 0 minutes.

(2) Production of Aromatic Hydrocarbon In Comparative Example 5 as the catalyst in Example 2 (2) above.
Example 2 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the yield of benzene was 39.2%.

Comparative Example 6 (1) Preparation of catalyst Silica binder molding L obtained in the above Example 1 (1)
Tetraammineplatinum chloride 0.171 on 10g type zeolite
g and ion-exchanged water (4.8 g) were gradually added dropwise with stirring, and the mixture was dried overnight at room temperature and then dried in air.
The catalyst was prepared by treating at 0 ° C. for 30 minutes.

(2) Production of Aromatic Hydrocarbon In the above Example 2 (2), the above Comparative Example 6 was used as a catalyst.
Example 2 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the yield of benzene was 32.1%.

Example 3 (1) Preparation of catalyst L-type zeolite (manufactured by Tosoh Corp .; TSZ-500KO)
A) 100 parts by weight of silica binder (Nissan Chemical Co., Ltd.)
(Manufactured by Snowtex) 20 parts by weight was added and kneaded and molded. Then, the mixture was air-baked at 500 ° C. for 2 hours to obtain a silica binder-molded L-type zeolite. Next, 0.097 g of ammonium fluoride and tetraammineplatinum chloride.
171 g and 4.8 g of deionized water were mixed to prepare an impregnating liquid. The impregnating solution thus prepared was gradually added dropwise to 10 g of the above-mentioned silica binder-molded L-type zeolite while stirring to carry out the platinum and halogen loading treatment simultaneously. Then, after drying overnight at room temperature, 300 in air
The catalyst was prepared by treating at 3 ° C. for 3 hours.

(2) Production of Aromatic Hydrocarbon 0.5 g of the catalyst prepared in Example 3 (1) was charged in a quartz reaction tube and then treated in a hydrogen stream at 540 ° C. for 24 hours. Then, light naphtha having a weight composition ratio of n-hexane / isohexane / methylcyclopentane = 49/43/8 was supplied at a weight hourly space velocity of 16 hr ⁻¹ and hydrogen / light naphtha = 5 mol / mol, and a pressure of 5 kg. / Cm ²
After adjusting G and temperature to 517 ° C., the temperature was maintained for 20 hours to carry out a conversion reaction to aromatics. The yield of aromatics in this case is 52.
It was 9%.

Comparative Example 7 (1) Preparation of Catalyst L Silica binder molding L obtained in Example 3 (1) above
An impregnating solution consisting of 0.097 g of ammonium fluoride and 4.8 g of ion-exchanged water was gradually added dropwise to 10 g of type zeolite while stirring, dried overnight at room temperature, and further dried in air at 300 ° C.
For 3 hours to obtain a halogen-supported catalyst. To 10 g of the obtained halogen-supported catalyst, tetraammine platinum chloride 0.1
An impregnating solution prepared by mixing 71 g and 4.8 g of ion-exchanged water was gradually added dropwise with stirring, and dried at room temperature overnight to prepare a catalyst.

(2) Production of Aromatic Hydrocarbon In Comparative Example 7 as the catalyst in Example 3 (2) above.
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the yield of aromatics was 48.1%.

Comparative Example 8 (1) Preparation of catalyst Silica binder molding L obtained in the above Example 3 (1)
Tetraammineplatinum chloride 0.171 on 10g type zeolite
g and ion-exchanged water (4.8 g) are slowly added dropwise with stirring, dried at room temperature for 2 hours, and further in air 1
It was treated at 20 ° C. for 3 hours to obtain a platinum-supported catalyst. Ammonium fluoride 0.097 g was added to the obtained platinum-supported catalyst 10 g.
And an impregnating solution in which 4.8 g of ion-exchanged water were mixed were gradually added dropwise with stirring. After drying overnight at room temperature, 3 in air
The catalyst was prepared by treating at 00 ° C. for 3 hours.

(2) Production of Aromatic Hydrocarbon In Comparative Example 8 as the catalyst in Example 3 (2) above.
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the yield of aromatics was 40.0%.

Example 4 (1) Preparation of catalyst Silica binder molding L obtained in the above Example 3 (1)
Type zeolite 10g to ammonium fluoride 0.097g,
Ammonium chloride 0.075g, tetraammine platinum chloride
An impregnating liquid consisting of 0.171 g and 4.8 g of ion-exchanged water was gradually added dropwise with stirring, dried overnight at room temperature, and further treated in air at 300 ° C. for 3 hours to prepare a catalyst.

(2) Production of aromatic hydrocarbon In Example 3 (2), the above-mentioned Example 4 was used as a catalyst.
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the aromatic yield was 63.8%.

Comparative Example 9 (1) Preparation of catalyst Silica binder molding L obtained in the above Example 3 (1)
Type zeolite 10g to ammonium fluoride 0.097g,
An impregnation liquid consisting of 0.075 g of ammonium chloride and 4.8 g of ion-exchanged water was gradually added dropwise with stirring, dried overnight at room temperature, and further treated in air at 300 ° C. for 3 hours to obtain a halogen-supported catalyst. 10 g of the resulting halogen-supported catalyst
A 0.11 g of tetraammineplatinum chloride and 4.8 g of ion-exchanged water were slowly added dropwise to the impregnating solution while stirring, and dried overnight at room temperature to prepare a catalyst.

(2) Production of Aromatic Hydrocarbon In Comparative Example 9 as the catalyst in Example 3 (2) above.
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the yield of aromatics was 55.0%.

Comparative Example 10 (1) Preparation of Catalyst L Silica binder molding L obtained in Example 3 (1) above
Tetraammineplatinum chloride 0.171 on 10g type zeolite
g and ion-exchanged water (4.8 g) are slowly added dropwise with stirring, dried at room temperature for 2 hours, and further in air 1
It was treated at 20 ° C. for 3 hours to obtain a platinum-supported catalyst. Ammonium fluoride 0.097 was added to 10 g of the obtained platinum-supported catalyst.
g, ammonium chloride 0.075 g and deionized water 4.8
The impregnating liquid containing g was gradually added dropwise with stirring. After drying overnight at room temperature, the catalyst was prepared by treating in air at 300 ° C. for 3 hours.

(2) Production of Aromatic Hydrocarbon In Comparative Example 10 as the catalyst in Example 3 (2).
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the aromatic yield was 50.5%.

Example 5 (1) Preparation of catalyst Silica binder molding L obtained in the above Example 3 (1)
Type zeolite 10g to ammonium fluoride 0.097g,
Ammonium bromide 0.061 g, tetraammine platinum chloride
An impregnating liquid consisting of 0.171 g and 4.8 g of ion-exchanged water was gradually added dropwise with stirring, dried overnight at room temperature, and further treated in air at 300 ° C. for 3 hours to prepare a catalyst.

(2) Production of Aromatic Hydrocarbon In Example 3 (2), the above-mentioned Example 5 was used as a catalyst.
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the yield of aromatics was 60.9%.

Comparative Example 11 (1) Preparation of Catalyst L Silica binder molding L obtained in Example 3 (1) above
Type zeolite 10g to ammonium fluoride 0.097g,
An impregnating solution consisting of 0.061 g of ammonium bromide and 4.8 g of ion-exchanged water was gradually added dropwise with stirring, dried overnight at room temperature, and further treated in air at 300 ° C. for 3 hours to obtain a halogen-supported catalyst. .. 10 g of the resulting halogen-supported catalyst
A 0.11 g of tetraammineplatinum chloride and 4.8 g of ion-exchanged water were slowly added dropwise to the impregnating solution while stirring, and dried overnight at room temperature to prepare a catalyst.

(2) Production of Aromatic Hydrocarbon In Comparative Example 11 as a catalyst in the above Example 3 (2).
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the yield of aromatics was 56.3%.

Comparative Example 12 (1) Preparation of Catalyst L Silica binder molding L obtained in Example 3 (1) above
Tetraammineplatinum chloride 0.171 on 10g type zeolite
g and ion-exchanged water (4.8 g) are slowly added dropwise with stirring, dried at room temperature for 2 hours, and further in air 1
It was treated at 20 ° C. for 3 hours to obtain a platinum-supported catalyst. Ammonium fluoride 0.097 was added to 10 g of the obtained platinum-supported catalyst.
g, ammonium bromide 0.061 g and deionized water 4.8
The impregnating liquid containing g was gradually added dropwise with stirring. After drying overnight at room temperature, the catalyst was prepared by treating in air at 300 ° C. for 3 hours.

(2) Production of Aromatic Hydrocarbon In Comparative Example 12 as the catalyst in Example 3 (2).
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the yield of aromatics was 48.2%.

Comparative Example 13 (1) Preparation of catalyst Silica binder molding L obtained in the above Example 3 (1)
Tetraammineplatinum chloride 0.171 on 10g type zeolite
g and ion-exchanged water (4.8 g) are slowly added dropwise with stirring, dried at room temperature for 2 hours, and further in air 1
It was treated at 20 ° C. for 3 hours to obtain a platinum-supported catalyst.

(2) Production of Aromatic Hydrocarbon In Example 3 (2), the above Comparative Example 13 was used as a catalyst.
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as (2). At this time, the yield of aromatics was 35.2%.

[0056]

INDUSTRIAL APPLICABILITY As described above, the catalyst of the present invention can be prepared by a simple process which has been conventionally performed without requiring a special device and the like, and can enhance aromatic hydrocarbon from various hydrocarbons. It can be produced with high activity and high yield and stably over a long period of time, and can be effectively used as a catalyst for producing aromatic hydrocarbons. Further, according to the method for producing an aromatic hydrocarbon of the present invention, an aromatic hydrocarbon can be produced in a high yield, and since the catalyst can maintain high activity for a long time, continuous operation over a long period of time is performed. Also, the yield of aromatic hydrocarbons is very high. Furthermore, the catalyst of the present invention has a significantly improved catalyst life,
It has an industrial advantage that the frequency of catalyst regeneration is reduced, the productivity is improved, and the manufacturing cost is reduced, and its utility value is very high. Therefore, the present invention can be widely and effectively used in the fields such as the petrochemical industry for producing aromatic hydrocarbons and the petroleum industry for producing high-octane fuel.

[Brief description of drawings]

FIG. 1 is a graph showing changes in aromatic yield over time in Example 1, Comparative Example 1 and Comparative Example 2.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C07C 15/04 8619-4H C10G 35/095 6958-4H 45/70 2115-4H // C07B 61 / 00 300

Claims (2)

[Claims] 1. A catalyst for aromatic production, which is obtained by carrying out a treatment to simultaneously support a platinum-containing compound and a halogen-containing compound (excluding an alkali metal salt and an alkaline earth metal salt) on L-type zeolite. 2. One or more hydrocarbons selected from the group consisting of paraffinic hydrocarbons, olefinic hydrocarbons, acetylene hydrocarbons, cyclic paraffinic hydrocarbons and cyclic olefinic hydrocarbons, 1. A method for producing an aromatic hydrocarbon, which comprises contacting with the catalyst of 1.