KR970010333B1 - Catalyst for the production of aromatic hydrocarbons and process for producing aromatic hydrocarbons by the use thereof - Google Patents

Abstract

None.

Description

Catalyst for producing aromatic hydrocarbons and preparation of aromatic hydrocarbons using the same

1 is a graph showing the time-dependent change in the aromatic hydrocarbon yield in Example 1, Comparative Example 1 and Comparative Example 2.

The present invention relates to a catalyst for producing an aromatic hydrocarbon and a method for producing an aromatic hydrocarbon using the same. Specifically, a catalyst suitable for an aromatization reaction for simultaneously supporting platinum and a halogen component in an L-type zeolite and a paraffin-based catalyst using the catalyst A method for efficiently producing aromatic hydrocarbons from non-aromatic hydrocarbons such as hydrocarbons.

Conventionally, platinum alumina-based catalysts have been used as catalysts for producing aromatic hydrocarbons by aromatizing non-aromatic hydrocarbons such as aliphatic hydrocarbons. Recently, a method using a platinum-supported L-type zeolite catalyst with improved conversion has been proposed (Japan JP-A-58-57408, JP-A-58-223614, 59-80333).

However, the platinum-supported L-type zeolite catalysts used in these methods are all unsatisfactory because of their low aromatic selectivity and low catalyst life.

In addition, a platinum-supported L-type zeolite catalyst incorporating alkaline earth metals (Ba, Sr, and Ca) has been proposed as an improvement (Japanese Patent Laid-Open No. 58-133835). Aromatic selectivity and catalyst life are not sufficient, and catalyst stability is low, so it is not practical.

In addition, (1) A catalyst which improves catalytic activity and catalyst life by oxychlorination treatment of L-type zeolite supporting metal (Japanese Patent Application Laid-Open No. 60-168539), and in order to uniformly disperse platinum, Catalyst treated with a solution of platinum metal salt (Japanese Patent Laid-Open No. 61-138539), ③ Catalyst supported by platinum to L-type zeolite treated with a halogen-containing compound (Japanese Patent Laid-Open No. 62-57653) And (4) A catalyst in which an L-type zeolite supporting platinum is treated with a halogen-containing compound (JP-A-63-91334) is proposed.

However, in the catalyst production process of ①, since the oxychlorination treatment is performed at high temperature, the treatment apparatus is expensive and the economic efficiency is very low.

The catalyst of ② has insufficient catalytic activity.

In addition, ③ and ④ have improved catalytic activity, but the catalyst life is not sufficient and a special facility for halogen treatment is required.

In addition, as the halogen-containing compound, proton gas (fluoro alkanes, chloro fluoro alkanes), which have recently been affected by environmental problems, is used, but it is not preferable for the environment.

As described above, the conventional catalysts have problems in manufacturing process, catalytic activity, catalyst life, and the like. However, a catalyst which is practically satisfactory has not been proposed.

Thus, the present inventors have solved the problem of the conventional catalyst and can be obtained in a simple process without the need for a special device in the production as a catalyst for producing an aromatic hydrocarbon, and concentrated research to develop a catalyst with high activity and long life.

As a result, it was found that the catalyst obtained by simultaneously supporting the platinum component and the halogen component in the L-type zeolite was bonded to the above object.

The present invention has been completed based on these findings.

In other words, the present invention provides a catalyst for producing an aromatic hydrocarbon obtained by simultaneously supporting L-type zeolite with a platinum-containing compound and a halogen-containing compound (except alkali metal salts and alkaline earth metal salts).

The present invention also provides an aromatic hydrocarbon comprising contacting one or two or more hydrocarbons selected from paraffinic hydrocarbons, olefinic hydrocarbons, acetylene hydrocarbons, cyclic paraffinic hydrocarbons and cyclic olefinic hydrocarbons with the above catalysts. It also provides a method.

As the catalyst of the present invention, L-type zeolite is used as a carrier.

Here, L-type zeolite is a composition formula

As represented by _{0.9~1.3M 2 / n O · Al 2} O 3 · 5.0~7.0SiO 2 · 0~9H 2 O (M represents an alkali metal or alkaline earth metal, n represents the valence of M.), Specifically, it is disclosed in Japanese Patent Laid-Open No. 58-133835, page 9-10 and 59-80333, page 5.

The catalyst of the present invention is characterized by producing a platinum-containing compound and a halogen-containing compound simultaneously with L-zeolite.

Thus, by simultaneously supporting the platinum component and the halogen component, it is possible to provide excellent catalytic activity and catalyst life that have not existed in the past.

Here, the platinum-containing compound is not particularly limited as long as it is a platinum source, and platinum salts are usually used.

Specific examples include tetraamine platinum, chloroplatinic acid, chlorinated platinum salts, tetraamine hydride platinum, dinitrodiamine platinum, and the like.

In addition, various examples of the halogen-containing compound include alkali metal salts and alkaline earth metal salts.

Specific examples include 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, and bromine-containing compounds such as hydrogen bromide and ammonium bromide. have. The halogen-containing compound may be used alone or in combination of two or more kinds thereof.

The catalyst of the present invention is prepared by simultaneously supporting a platinum-containing compound and a halogen-containing compound on L-type zeolite. The method of the support treatment is not particularly limited as long as the platinum component and the halogen component are simultaneously supported, and can be a normal pressure impregnation method, a vacuum impregnation method, a penetration method, an ion exchange method, or the like.

The amount of the support in the support treatment is not particularly limited, but the amount of the platinum-containing compound is usually 0.1-5.0% by weight based on the total weight of the catalyst, particularly 0.3-1.5% by weight.

In addition, the support amount of the halogen-containing compound is preferably 0.1-5% by weight of halogen based on the total weight of the catalyst.

In addition, the support treatment conditions are not particularly limited and may be appropriately selected according to various situations, but the L-type zeolite may be brought into contact with the platinum-containing compound and the halogen-containing compound at room temperature at -90 ° C for 1 minute to 10 hours.

To the catalyst of the present invention, natural or synthetic inorganic oxides such as alumina, silica, aluminum silicate and the like may be added as binders as necessary.

It is preferable that the usage-amount of these binders shall be 5-90 weight% on the basis of the weight before a catalyst.

As such, the catalyst of the present invention can be produced without requiring any special apparatus or process.

The catalyst obtained is used as a so-called aromatization catalyst, which produces aromatic hydrocarbons in high yields under appropriate reaction conditions from various hydrocarbons, but aromatic hydrocarbons can be produced with very high efficiency according to the process of the present invention.

In the method for producing an aromatic hydrocarbon of the present invention, the catalyst of the present invention is used as one or two or more hydrocarbons selected from paraffinic hydrocarbons, olefinic hydrocarbons, acetylene hydrocarbons, cyclic paraffinic hydrocarbons and cyclic olefinic hydrocarbons as hydrocarbons as raw materials. To make an aromatic hydrocarbon.

The paraffinic hydrocarbon preferably has 6 to 10 carbon atoms, and specific examples thereof include n-hexane, methyl pentane, n-heptane, methyl hexane, dimethyl pentane and n-octane.

Examples of the olefinic hydrocarbons include olefins having 6-10 carbon atoms, specifically hexene, methylpentene, heptene, methyl hexene, dimethyl pentene and octene.

Examples of the acetylene hydrocarbons include those having 6 to 10 carbon atoms, specifically hexine, heptin, octin, and the like.

Examples of the cyclic paraffinic hydrocarbon include those having 6 to 10 carbon atoms, specifically methylcyclopentane, cyclohexane, methylcyclohexane, dimethyl cyclohexane, and the like.

Examples of the cyclic olefin hydrocarbons include those having 6 to 10 carbon atoms, specifically methyl cyclopentene, cyclohexene, methyl cyclohexene, dimethyl cyclohexene, and the like.

The method of the present invention proceeds as the raw hydrocarbon is brought into contact with an electric catalyst, and there is no particular limitation on the conditions and the like.

However, in order to obtain good results, a temperature of 350-600 ° C., preferably 400-500 ° C., pressure 0-40 kg / cm 2 G, preferably 0-10 kg / cm 2 G, liquid space velocity (LHSV) 0.1-20 hr ⁻¹ , Preferably it should be 1-10hr ^-1 .

In addition, if the feed ratio of hydrogen gas / raw hydrocarbon is selected in the range of 0-50 mol / mol can be expected better results.

As described above, the catalyst of the present invention can be prepared by a conventional simple process without requiring a special apparatus, and can produce aromatic hydrocarbons from various hydrocarbons in high activity and high yield, and also stably produce them for a long time. As it can, it can be effectively used as a catalyst for producing aromatic hydrocarbons.

In addition, according to the aromatic hydrocarbon production method of the present invention, the aromatic hydrocarbon can be produced in high yield, and the catalyst can maintain high activity for a long time, so the yield of the aromatic hydrocarbon is very high even after continuous operation for a long time.

In addition, the catalyst of the present invention has an industrial advantage that the catalyst life is remarkably improved, and thus, the regeneration frequency of the catalyst can be reduced, and the productivity is improved, thereby reducing the production cost.

Therefore, the present invention is widely and effectively used in the fields of the petrochemical industry for producing aromatic hydrocarbons or the petroleum industry for producing high octane fuel.

Next, an Example and a comparative example demonstrate this invention in detail.

Example 1

(1) Preparation of catalyst

20 parts by weight of silica binder (Nissan Chemical Co., Ltd. product: Snowtex) was added to 100 parts by weight of L-type zeolite (Toso) Co., Ltd. product: TSZ-500KOA), and the mixture was molded.

Thereafter, air firing at 500 ° C. for 2 hours yields a silica binder-molded L-zeolite.

Next, an impregnating solution was prepared by mixing 1.39 g of 3.6 wt% hydrogen chloride solution, 0.097 g of ammonium fluoride, tetraamine platinum chloride, 0.171 g, and 3.6 g of ion-exchanged water.

The impregnation solution thus prepared was slowly added dropwise to 10 g of silica binder-molded L-type zeolite with stirring to simultaneously support the treatment of platinum and halogen.

Thereafter, the mixture was dried at room temperature overnight and then treated at 300 ° C. for 30 minutes in air to prepare a catalyst.

(2) Preparation of Aromatic Hydrocarbons

0.5 g of the catalyst prepared in Example 1 was charged to a quartz reaction tube, and then treated at 540 ° C. for 24 hours in a hydrogen stream.

Subsequently, hard naphtha and hydrogen having a weight composition ratio of n-hexane / isohexane / methylcyclopentane = 49/43/8 were respectively supplied at a weight space velocity of 2 ^{hr −1} and hydrogen / hard naphtha = 5 mol / 1 mol, The conversion reaction of the aromatic hydrocarbon was carried out by adjusting the pressure to 5 kg / cm 2 G and the temperature of 500 ° C.

The time-dependent change of the aromatic hydrocarbon yield at this time is shown in FIG.

Comparative Example 1

(1) Preparation of catalyst

20 g of the silica binder-formed L-type zeolite obtained in Example 1 (1) was charged into a quartz reaction tube and held at 200 ° C. for 30 minutes while flowing nitrogen gas, and then the gas was replaced with monochlorotrifluoromethane and 500 ° C. Raised the temperature.

After raising to 500 ° C., the mixture was treated for 2 hours, the gas was replaced with nitrogen gas, and the temperature was lowered to obtain a halogenated L zeolite.

Next, 10 g of halogenated L-type zeolite was slowly added dropwise while supporting an impregnation solution of 0.171 g of tetraamine platinum chloride and 4.0 g of ion-exchanged water with stirring.

After the support, the resultant was dried at 80 DEG C for 3 hours to prepare a catalyst.

(2) Preparation of Aromatic Hydrocarbons

In Example 1 (2), the conversion reaction was conducted in the same manner as in Example 1 (2) except that the catalyst obtained in Comparative Example 1 (1) was used as the catalyst.

The hourly change of the aromatic hydrocarbon yield is shown in FIG.

Comparative Example 2

(1) Preparation of catalyst

10 g of silica binder-formed L-type zeolite obtained in Example 1 (1) was slowly added dropwise with stirring to a solution of 0.171 g of tetraamine platinum chloride and 4.8 g of ion-exchanged water, dried at room temperature for 2 hours, and then at 80 ° C in air. The catalyst was treated for 3 hours.

The obtained catalyst was charged in a quartz reaction tube, maintained at 200 ° C for 1 hour while flowing nitrogen gas, and then heated up to 480 ° C.

It was replaced with a gas of Pron 112 (1,1,2,2-tetrachloro-1,2-difluoroethane) /nitrogen=0.1/99.9 (vol%) at 480 ° C. and treated for 10 hours.

Thereafter, the gas was again replaced with nitrogen gas and the temperature was lowered to prepare a catalyst.

(2) Preparation of Aromatic Hydrocarbons

In Example 1 (2), the conversion reaction was conducted in the same manner as in Example 1 (2) except that the catalyst obtained in Comparative Example 2 (1) was used as the catalyst.

The hourly change of the aromatic hydrocarbon yield is shown in FIG.

Example 2

(1) Preparation of catalyst

It is the same as Example 1 (1).

(2) Preparation of Aromatic Hydrocarbons

0.05 g of the catalyst obtained in Example 2 (1) was charged to a pulsed reactor.

Thereafter, the temperature was raised to 500 ° C. over 1 hour in a hydrogen gas stream and maintained at 500 ° C. for 1 hour.

The reaction temperature was adjusted to 470 ° C. and n-hexane was converted into 3 μl pulses in a hydrogen gas stream (2.2 L / hr).

The benzene yield at this time was 55.7%.

Comparative Example 3

(1) Preparation of catalyst

An impregnation liquid was prepared by mixing 0.0735 g of potassium chloride, 0.107 g of potassium fluoride, 0.120 g of tetraamine chloride, and 3.50 g of ion-exchanged water.

The impregnation liquid thus prepared was gradually added dropwise to 7 g of the silica binder-molded L-zeolite obtained in Example 1 (1) with stirring.

Thereafter, the mixture was dried at room temperature overnight, and then stirred at 300 ° C in air for 30 minutes to prepare a catalyst.

(2) Preparation of Aromatic Hydrocarbons

In Example 2 (2), the conversion reaction was conducted in the same manner as in Example 2 (2) except that the catalyst obtained in Comparative Example 3 (1) was used as the catalyst.

The benzene yield at this time was 10.8%.

[Comparative Example 4]

(1) Preparation of catalyst

An impregnation solution was prepared by mixing 1.39 g of 3.6 wt% hydrochloric acid solution, 0.097 g of ammonium fluoride and 3.6 g of ion-exchanged water.

The impregnated liquid thus prepared was gradually added dropwise to 10 g of silica binder-molded L-type zeolite obtained in Example 1 (1) with stirring to provide halogen support.

Thereafter, the mixture was dried overnight at room temperature and then treated to 300 ° C. in air for 30 minutes to obtain a halogen supported catalyst.

To 8 g of the obtained halogen-supported catalyst, an impregnation solution of 0.137 g of tetraamine chloride and 3.68 g of ion-exchanged water was slowly added dropwise with stirring, followed by drying overnight at room temperature to prepare a catalyst.

(2) Preparation of Aromatic Hydrocarbons

In Example 2 (2), the conversion reaction was conducted in the same manner as in Example 2 (2) except that the catalyst obtained in Comparative Example 4 (1) was used as the catalyst. The benzene yield at this time was 47.1%.

[Comparative Example 5]

(1) Preparation of catalyst

10 g of silica binder-formed L-type zeolite obtained in Example 1 (1) was slowly added dropwise with stirring to impregnated with 0.171 g of tetraamine platinum and 4.8 g of ion-exchanged water, dried at room temperature for 2 hours, and then again in air at 120 ° C. 3 hours of treatment gave a platinum support catalyst.

The impregnation liquid which mixed 0.514g of 6.8 weight% hydrogen chloride solutions, 0.0682g of ammonium fluoride, and 3.34g of ion-exchange water was dripped gradually to 7 g of obtained platinum support catalysts, stirring.

After drying overnight at room temperature, the catalyst was prepared by treating at 300 ° C. for 30 minutes in air.

(2) Preparation of Aromatic Hydrocarbons

In Example 2 (2), the conversion reaction was conducted in the same manner as in Example 2 (2) except that the catalyst obtained in Comparative Example 5 (1) was used as the catalyst.

The benzene yield at this time was 39.2%.

Comparative Example 6

(1) Preparation of catalyst

10 g of silica binder-formed L-type zeolite obtained in Example 1 (1) was slowly added dropwise with stirring to a solution of 0.171 g of tetraamine platinum and 4.8 g of ion-exchanged water, dried overnight at room temperature, and then dried at 300 ° C in air. Treatment was performed for minutes to prepare a catalyst.

(2) Preparation of Aromatic Hydrocarbons

In Example 2 (2), the conversion reaction was conducted in the same manner as in Example 2 (2) except that the catalyst obtained in Comparative Example 6 (1) was used as the catalyst.

The yield of benzene at this time was 32.1%.

Example 3

(1) Preparation of catalyst

20 parts by weight of a silica binder (Nissan Chemical Co., Ltd.: Snowtex) was added to 100 parts by weight of L-type zeolite (product of TSOS-500 KOA) and mixed molding.

Thereafter, air firing was performed at 500 ° C. for 2 hours to obtain a silica binder-molded L-zeolite.

Thereafter, 0.097 g of ammonium fluoride, 0.171 g of tetraamine chloride, and 4.8 g of ion-exchanged water were mixed to prepare an impregnation solution.

The impregnated liquid thus prepared was slowly added dropwise to 10 g of silica binder-molded L-type zeolite with stirring, and the support treatment of platinum and halogen was simultaneously performed.

Next, the mixture was dried overnight at room temperature and then treated at 300 ° C. for 3 hours in air to prepare a catalyst.

(2) Preparation of Aromatic Hydrocarbons

0.5 g of the catalyst prepared in Example 3 (1) was charged to a quartz reaction tube, and then treated at 540 ° C. in a hydrogen stream for 24 hours.

Thereafter, hard naphtha having a weight composition ratio of n-hexane / isohexane / methyl cyclopentane = 49/43/8 was supplied at a weight space velocity of 16hr ⁻¹ and hydrogen / hard naphtha = 5 mol / 1 mol, and the pressure was 5 kg / cm 2. After controlling to G and the temperature of 517 degreeC, it hold | maintained for 20 hours, and converted into aromatic hydrocarbon.

The yield of the aromatic hydrocarbon at this time was 52.9%.

Comparative Example 7

(1) Preparation of catalyst

10 g of silica binder-formed L-type zeolite obtained in Example 3 (1) was slowly added dropwise while stirring with an aqueous solution of 0.097 g of ammonium fluoride and 4.8 g of ion-exchanged water, followed by drying overnight at room temperature, followed by 3 hours at 300 ° C in air. Treatment gave a halogen supported catalyst.

An impregnation solution containing 0.171 g of tetraamine chloride and 4.8 g of ion-exchanged water was slowly added dropwise to 10 g of the obtained halogen-supported catalyst while stirring, followed by drying overnight at room temperature to prepare a catalyst.

(2) Preparation of Aromatic Hydrocarbons

In Example 3 (2), the conversion reaction was conducted in the same manner as in Example 3 (2) except that the catalyst obtained in Comparative Example 7 (1) was used as the catalyst.

The yield of the aromatic hydrocarbon at this time was 48.1%.

Comparative Example 8

(1) Preparation of catalyst

10 g of silica binder-formed L-type zeolite obtained in Example 3 (1) was slowly added dropwise while stirring the impregnation solution of tetraamine platinum chloride and 4.8 g of ion-exchanged water, followed by drying at room temperature for 2 hours, followed by 120 ° C in air. 3 hours of treatment gave a platinum supported catalyst.

The impregnation liquid which mixed 0.097 g of ammonium fluoride and 4.8 g of ion-exchange water was dripped gradually, stirring 10 g of the obtained platinum support catalyst.

After drying overnight at room temperature, the catalyst was prepared by treating at 300 ° C. for 3 hours in air.

(2) Preparation of Aromatic Hydrocarbons

In Example 3 (2), the conversion reaction was conducted in the same manner as in Example 3 (2) except that the catalyst obtained in Comparative Example 8 (1) was used as the catalyst.

The benzene yield at this time was 40.0%.

Example 4

(1) Preparation of catalyst

To 10 g of silica binder-formed L-type zeolite obtained in Example 3 (1), an impregnation solution of 0.097 g of ammonium fluoride, 0.075 g of ammonium chloride, 0.171 g of tetraamine chloride, and 4.8 of ion-exchanged water was slowly added dropwise while stirring and overnight at room temperature. After drying, the mixture was treated at 300 ° C. for 3 hours in air to prepare a catalyst.

(2) Preparation of Aromatic Hydrocarbons

In Example 3 (2), the conversion reaction was conducted in the same manner as in Example 3 (2) except that the catalyst obtained in Comparative Example 4 (1) was used as the catalyst. The yield of benzene at this time was 63.8%.

Comparative Example 9

(1) Preparation of catalyst

10 g of silica binder-formed L-type zeolite obtained in Example 3 (1) was slowly added dropwise with stirring with 0.097 g of ammonium fluoride, 0.075 g of ammonium chloride and 4.8 g of ion-exchanged water, dried overnight at room temperature, and then again in air. The mixture was treated at 300 ° C. for 3 hours to obtain a halogen supported catalyst.

The impregnation liquid which mixed 0.171 g of tetra-amine chlorine platinum and 4.8 g of ion-exchange water was dripped gradually to 10 g of the obtained halogen support catalysts, and it dried at room temperature overnight, and prepared the catalyst.

(2) Preparation of Aromatic Hydrocarbons

In Example 3 (2), the conversion reaction was conducted in the same manner as in Example 3 (2) except that the catalyst obtained in Comparative Example 9 (2) was used as the catalyst.

The benzene yield at this time was 55.0.

Comparative Example 10

(1) Preparation of catalyst

10 g of silica binder-formed L-type zeolite obtained in Example 3 (1) was slowly added dropwise while stirring with an aqueous solution of 0.171 g of tetraamine chloride and 4.8 g of ion-exchanged water, dried for 2 hours, and further dried at 120 ° C in air. Time treatment gave a platinum supported catalyst.

The impregnation liquid which mixed 0.097 g of ammonium fluoride, 0.075 g of ammonium chlorides, and 4.8 g of ion-exchange water was dripped gradually, stirring 10 g of obtained platinum support catalysts.

After drying overnight at room temperature, the catalyst was prepared by treating at 300 ° C. for 3 hours in air.

(2) Preparation of aromatic hydrocarbons

In Example 3 (2), the conversion reaction was conducted in the same manner as in Example 3 (2) except that the catalyst obtained in Comparative Example 10 (1) was used as the catalyst.

The yield of the aromatic hydrocarbon at this time was 50.5%.

Example 5

(1) Preparation of catalyst

10 g of silica binder-formed L-type zeolite obtained in Example 3 (1) was slowly added dropwise while stirring with an impregnation solution of 0.097 g of ammonium fluoride, 0.061 g of ammonium bromide, 0.171 g of tetraamine chloride, and 4.8 g of ion-exchanged water. After drying overnight, the catalyst was prepared by treating at 300 ° C. for 3 hours in air.

(2) Preparation of Aromatic Hydrocarbons

In Example 3 (2), the conversion reaction was conducted in the same manner as in Example 3 (2) except that the catalyst obtained in Comparative Example 5 (1) was used as the catalyst.

The yield of the aromatic hydrocarbon at this time was 60.9%.

Comparative Example 11

(1) Preparation of catalyst

10 g of the silica binder-formed L-type zeolite obtained in Example 3 (1) was slowly added dropwise with stirring with an impregnation solution of 0.097 g of ammonium fluoride, 0.061 g of ammonium bromide and 4.8 g of ion-exchanged water, followed by drying overnight at room temperature. The mixture was treated at 300 ° C. for 3 hours to obtain a halogen support catalyst.

An impregnation solution containing 0.171 g of tetraamine chloride and 4.8 g of ion-exchanged water was slowly added dropwise to 10 g of the obtained halogen-supported catalyst while stirring, followed by drying overnight at room temperature to prepare a catalyst.

(2) Preparation of Aromatic Hydrocarbons

In Example 3 (2), the conversion reaction was conducted in the same manner as in Example 3 (2) except that the catalyst obtained in Comparative Example 11 (1) was used as the catalyst.

The yield of the aromatic hydrocarbon at this time was 56.3%.

Comparative Example 12

(1) Preparation of catalyst

10 g of silica binder-formed L-type zeolite obtained in Example 3 (1) was slowly added dropwise while stirring the impregnation solution of tetraamine platinum chloride and 4.8 g of ion-exchanged water, followed by drying at room temperature for 2 hours, followed by 120 ° C in air. 3 hours of treatment gave a platinum supported catalyst.

The impregnation liquid which mixed 0.097 g of ammonium fluoride, 0.061 g of ammonium bromide, and 4.8 g of ion-exchange water was dripped gradually, stirring 10 g of the obtained platinum support catalyst.

The catalyst was prepared by drying overnight at room temperature and treating at 300 ° C. for 3 hours in air.

(2) Preparation of Aromatic Hydrocarbons

In Example 3 (2), the conversion reaction was conducted in the same manner as in Example 3 (2) except that the catalyst obtained in Comparative Example 12 (1) was used as the catalyst.

The yield of the aromatic hydrocarbon at this time was 48.2%.

Comparative Example 13

(1) Preparation of catalyst

10 g of silica binder-formed L-type zeolite obtained in Example 3 (1) was slowly added dropwise with stirring to an aqueous solution of 0.171 g of tetraamine platinum and 4.8 g of ion-exchanged water, dried at room temperature for 2 hours, and then at 120 ° C in air. 3 hours of treatment gave a platinum supported catalyst.

(2) Preparation of Aromatic Hydrocarbons

In Example 3 (2), the conversion reaction was conducted in the same manner as in Example 3 (2) except that the catalyst obtained in Comparative Example 13 (1) was used as the catalyst.

The yield of the aromatic hydrocarbon at this time was 35.2%.

Claims (16)

A catalyst for producing an aromatic hydrocarbon in which an L-type zeolite is simultaneously supported by a platinum-containing compound and a halogen-containing compound (except for alkali metal salts and alkaline earth metal salts). The catalyst for producing an aromatic hydrocarbon according to claim 1, wherein the platinum-containing compound is one or two or more selected from tetraamine chlorine platinum, chloroplatinic acid, chloroplatinate, chlorinated tetraamine platinum and dinitrodiamine platinum. The catalyst for producing an aromatic hydrocarbon according to claim 1, wherein the halogen-containing compound is one or more selected from hydrogen chloride, ammonium chloride, hydrogen fluoride, ammonium fluoride, hydrogen iodide, ammonium iodide, hydrogen bromide, and ammonium bromide. The catalyst for producing an aromatic hydrocarbon according to claim 1, wherein the support amount of the platinum-containing compound is 0.1-5.0 wt% platinum based on the total weight of the catalyst. The catalyst for producing an aromatic hydrocarbon according to claim 1, wherein the amount of the halogen-containing compound is 0.1-5.0% by weight of halogen based on the total weight of the catalyst. The catalyst for producing an aromatic hydrocarbon according to claim 1, wherein the amount used in the binder is 5-90% by weight based on the weight before the catalyst by adding a platinum-containing compound and a halogen-containing compound to the zeolite. The catalyst for producing an aromatic hydrocarbon according to claim 6, wherein the binder is selected from alumina, silica and aluminum silicate. One or two or more types of raw hydrocarbons selected from paraffinic hydrocarbons, olefinic hydrocarbons, acetylene hydrocarbons, cyclic paraffinic hydrocarbons and cyclic olefinic hydrocarbons are added to the L-type zeolite with platinum-containing compounds and halogen-containing compounds (alkali metal salts and alkalis). A method for producing an aromatic hydrocarbon, characterized by contacting the catalyst (except for the earth metal salt) with a catalyst which is simultaneously supported. The method for producing an aromatic hydrocarbon according to claim 8, wherein the platinum-containing compound is one or two or more selected from tetraamine platinum, chloroplatinic acid, chloroplatinate, tetraamine platinum and dinitrodiamine platinum. The method for producing an aromatic hydrocarbon according to claim 8, wherein the halogen-containing compound is one or more selected from hydrogen chloride, ammonium chloride, hydrogen fluoride, ammonium fluoride, hydrogen iodide, ammonium iodide, hydrogen bromide and ammonium bromide. The method for producing an aromatic hydrocarbon according to claim 8, wherein the support amount of the platinum-containing compound is 0.1-5.0 wt% platinum based on the total weight of the catalyst. The process for producing an aromatic hydrocarbon according to claim 8, wherein the support amount of the halogen-containing compound is 0.1-5.0 wt% of halogen based on the total weight of the catalyst. The method for producing an aromatic hydrocarbon according to claim 8, wherein the amount of the binder is 5-90% by weight based on the total weight of the catalyst by adding a platinum-containing compound and a halogen-containing compound to the zeolite. The method of claim 13, wherein the binder is selected from alumina, silica and aluminum silicate. The method for producing an aromatic hydrocarbon according to claim 8, wherein the raw hydrocarbon is 6-10 carbon atoms. The raw hydrocarbon is contacted with the catalyst at a temperature of 350-600 ° C., pressure of 0-40 kg / cm 2 G, liquid space velocity (LHSV) of 0.1-2hr ⁻¹ , and a feed ratio of hydrogen / hydrocarbon 0-50 mol / mol. A method for producing an aromatic hydrocarbon.