JPH1033987A - Catalyst for producing aromatic hydrocarbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst which suppresses a zinc scattering amount and can maintain aromatic substance selectivity at a higher rate by causing zinc oxide and zinc aluminate to be coexistent at a specific ratio in zeolite catalyst with a middle pore diameter for converting hydrocarbons to an aromatic hydrocarbon. SOLUTION: This zeolite catalyst for manufacturing an aromatic hydrocarbon has a middle pore diameter and is used when hydrocarbons containing paraffin, olefin and/or naphthene are converted to an aromatic hydrocarbon. Before te use of this catalyst for chemical reaction, 1.2-20wt.% of zinc oxide and 82-50wt.% of zinc aluminate are caused to be coexistent in the catalyst. In addition, the zeolite with a middle a pore diameter has a zeolite skeleton with an atomic ratio between Si and Al of 12 or more. This coexistence of zinc aluminate serves as a zinc oxide supply source to inhibit a decrease in the amount of zinc aluminate. Consequently, it is possible to maintain the effects to increase the rate of aromatic substance selection.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for producing aromatic hydrocarbons carrying zinc, which can suppress a decrease in the aromatic yield due to long-term use of the catalyst, and the production of the catalyst. About the method.

[0002]

2. Description of the Related Art Conventionally, zinc is often carried as zinc oxide in a catalyst for producing aromatic hydrocarbons carrying zinc, and is reduced by hydrogen generated during the reaction to become zinc metal and scattered from the catalyst. There was a problem. Further, as described in JP-B-7-29948, there is a method of converting zinc into zinc aluminate having a spinel structure in order to more stably fix zinc on a catalyst. Although the scattering of zinc from the catalyst is suppressed, there is a problem that the effect of improving the aromatic selectivity, which is the original purpose of supporting zinc, is lost. Tokuho 7
According to JP-A-29948, it is expected that zinc oxide and zinc aluminate coexist, but a certain amount or more of zinc oxide is required to exhibit the effect of improving aromatic selectivity. It is important that a specific amount of zinc oxide and zinc aluminate coexist as described above, but the publication does not specify the amount of zinc oxide.

[0003]

As described above, in the prior art, when zinc is supported on a catalyst as zinc oxide, it is reduced by hydrogen generated during the reaction to become zinc metal and scattered from the catalyst. There was a problem. In addition, when zinc is supported on the catalyst in the form of zinc aluminate, the scattering of zinc from the catalyst is suppressed, but the problem of improving the aromatic selectivity, which is the original purpose of supporting zinc, is lost. there were. The present invention provides, as a catalyst for producing aromatic hydrocarbons, a reaction for converting a hydrocarbon containing paraffins, olefins and / or naphthenes into aromatic hydrocarbons, which suppresses the amount of zinc scattered and has a higher aromatic selectivity. It is an object of the present invention to provide a catalyst capable of maintaining the above.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a zeolite catalyst having an intermediate pore diameter in which a specific amount of zinc oxide and zinc aluminate coexist has been obtained. Have been found to be effective in solving the above problem, and have completed the present invention.

That is, the present invention relates to (1) a zeolite catalyst having an intermediate pore diameter which is used in a reaction for converting a hydrocarbon containing paraffin, olefin and / or naphthene into an aromatic hydrocarbon; At this point, the catalyst contains 1.2 to 20% by weight of zinc oxide and 8.2% of zinc aluminate.
A mesoporous zeolite-based catalyst characterized by being present in an amount of about 50% by weight. (2) The catalyst according to (1), wherein the intermediate pore diameter zeolite constituting the intermediate pore diameter zeolite-based catalyst has a zeolite skeleton having an Si / Al atomic ratio of 12 or more.

(3) The catalyst according to (1) or (2), wherein the intermediate pore zeolite constituting the intermediate pore zeolite catalyst is a ZSM-5 type zeolite. (4) The catalyst activity of the mesoporous zeolite catalyst is 50
Initial 1 of n-hexane decomposition measured at 0 ° C. under atmospheric pressure
The catalyst according to any one of (1) to (3), wherein the value of the subsequent reaction rate constant is 0.2 sec ^-1 or more. (5) An alumina sol, a compound having zinc as a cation, and a zeolite having an intermediate pore size are mixed, dried, and then heated to 300 ° C. or more.
Firing at a temperature of 800 ° C. or less (1)
The method for producing a catalyst according to any one of (1) to (4).

(6) An alumina sol and a compound having zinc as a cation are mixed, dried, calcined at a temperature of 300 ° C. or more and 800 ° C. or less, steam-treated and mixed with a medium pore diameter zeolite, and dried. After 300 ° C or more, 80
Characterized by firing at a temperature of 0 ° C. or less (1) to
The method for producing a catalyst according to any of (4). (7) The method for producing a catalyst according to (5) or (6), wherein the mixture is mixed with zeolite having an intermediate pore size, dried, calcined, and further subjected to steam treatment.

Hereinafter, the present invention will be described in detail. The "medium pore size zeolite" constituting the mesopore size zeolite catalyst of the present invention is a so-called crystalline aluminosilicate having an intermediate pore size, that is, one having an effective pore size of about 5 to 6.5 angstroms. No. Further, "medium pore diameter zeolite catalyst", the intermediate pore diameter zeolite and other required other components, for example,
A catalyst prepared using zinc oxide, zinc aluminate, etc.

Specific examples of the mesopore zeolite include:
For example, β-zeolite, Ω-zeolite, Y-zeolite, L-zeolite, erionite, offretite, mordenite, ferrierite, ZSM-5, ZSM-
8, ZSM-11, ZSM-12, ZSM-35, ZS
M-38 and the like, ZSM-5, ZSM-
8, ZSM-5 type crystalline aluminosilicate or metallosilicate such as ZSM-11 is preferred. These zeolites have an ion exchange ability, and as the ionic species present in the zeolites, for example, hydrogen (H ⁺ ) and silver (Ag ⁺ ) are preferable, but sodium (Na ⁺ ) and the like may be present. Absent.

The amount of zinc oxide and zinc aluminate relative to the weight of the intermediate pore diameter zeolite catalyst of the present invention is 1.2 to 20 weight% before the intermediate pore diameter zeolite catalyst is used in the reaction. %, 8.2 to 50% by weight, preferably 1.8 to 5.0% by weight of zinc oxide and 14 to 40% by weight of zinc aluminate. If there is no zinc oxide and zinc aluminate alone, there is no effect of improving the aromatic selectivity by supporting zinc in the reaction of converting a hydrocarbon containing paraffin, olefin and / or naphthene into an aromatic hydrocarbon. In addition, when zinc oxide is large, the effect of improving aromatic selectivity is maintained for a long time, but the amount of zinc scattered increases, zinc adheres to the downstream of the process, embrittles equipment materials due to deposition, heat exchangers, etc. Adverse effects such as a decrease in efficiency of the system.

Also, zinc aluminate is a reaction for converting a hydrocarbon containing paraffins, olefins and / or naphthenes into aromatic hydrocarbons, and further converts carbon or hydrocarbons adhering to the catalyst with air diluted with nitrogen. Zinc oxide is also generated by repetition of the regeneration process for burning and removing the catalyst. Therefore, although zinc aluminate itself does not have an effect of improving aromatic selectivity, it serves as a supply source of zinc oxide and suppresses a decrease in zinc oxide. As a result, the effect of improving aromatic selectivity can be maintained for a long time. Therefore, the coexistence of zinc aluminate with zinc oxide in the catalyst is effective for maintaining the aromatic selectivity improving effect.

Further, the presence of zinc aluminate allows
It also has the effect of suppressing the scattering speed of zinc oxide due to hydrogen reduction and the like. However, if the amount of zinc aluminate is too large, it becomes difficult to secure the activity and strength of the catalyst. Therefore, the zinc aluminate content is preferably not more than 50%, more preferably not more than 40%. The term "coexistence of zinc oxide and zinc aluminate" refers to a state in which zinc oxide and zinc aluminate are simultaneously present in the catalyst, regardless of a method such as physical mixing or impregnation followed by firing.

For the determination of zinc oxide and zinc aluminate, the presence of zinc aluminate and zinc oxide was confirmed by X-ray diffraction analysis, and the total amount of zinc was determined using a fluorescent X-ray analyzer (Rigaku RIX 1000). It can be determined from a calibration curve, from which the amount of zinc oxide is subtracted from the result of atomic absorption analysis of zinc oxide described below. As a method for analyzing zinc oxide, 1 g of the catalyst is ground to a few hundred microns in a mortar, dried at 120 ° C. for 1 hour, accurately weighed out about 0.5 g, and placed in a 200 cc beaker. Then, 150 cc of a 3% hydrochloric acid aqueous solution was added thereto, and the mixture was heated at 80 ° C. for 2 hours on an electric heater.
Heat for hours. Thereafter, the solution was filtered through a 0.2 μm membrane filter, and the filtrate was subjected to atomic absorption spectrometry (Shimadzu Seismic Atomic Absorption / Frame Spectrophotometer AA-640-12).
Type), flame analysis, and quantitative analysis of zinc oxide by the standard addition method.

In the present invention, zinc oxide refers to a substance measured by the above-mentioned analysis method. Therefore, zinc oxide in the present invention is a zinc component eluted from the catalyst with a 3% hydrochloric acid aqueous solution. In addition to zinc oxide generally represented by ZnO, unstable zinc aluminate and the like other than zinc oxide are generally used. Ingredients may also be included. Zinc aluminate is defined as JC when observed with an X-ray diffractometer such as XD-610 of Shimadzu Corporation.
PDS 5-0669 NBS Circ. , 539,
Vol. II, 38 (1953) having the same X-ray diffraction pattern as the pattern shown in FIG.

The intermediate pore zeolite used for producing the intermediate pore zeolite catalyst of the present invention preferably has a zeolite skeleton having an Si / Al atomic ratio of 12 or more. Here, the Si / Al atomic ratio of the zeolite skeleton refers to the Si / Al atomic ratio obtained from ²⁹ Si-NMR. The method for determining the Si / Al atomic ratio in zeolite using ²⁹ Si-NMR is described in "Experimental Chemistry Lecture 5, NMR", 4th edition (Nippon Kuni Maruzen Co., Ltd., 199
2) It is described in 232 to 233. The Na concentration in the catalyst was determined by placing the catalyst in a 1N-HCl aqueous solution, heating it for 5 minutes, filtering, and analyzing the filtrate with an atomic absorption analyzer (AA-640-12 manufactured by Shimadzu Corporation).

Further, a zeolite catalyst having an intermediate pore diameter of 0.2 sec ^-1 or more as a value of an initial primary reaction rate constant of n-hexane decomposition measured at 500 ° C. under atmospheric pressure is preferable. In order to suppress the deterioration of the activity of the catalyst, steam treatment may be applied to the mesoporous zeolite catalyst. However, the value of the initial first-order rate constant of n-hexane decomposition measured at 500 ° C. and atmospheric pressure is 0. If it is less than 0.2 sec ^-1 , the generation rate of aromatics will be low, and the productivity will be poor.
It is preferable to perform steam treatment within a range of 2 sec ⁻¹ or more.

In the present invention, the initial first-order reaction rate constant (hereinafter referred to as “initial first-order reaction rate constant for n-hexane decomposition”) of the decomposition of n-hexane by the mesoporous zeolite catalyst is shown in FIG. N-hexane decomposition reaction using the apparatus shown in FIG. 1 and the intermediate pore diameter zeolite catalyst, the volume of the intermediate pore diameter zeolite catalyst used, the flow rate of the raw material n-hexane, and the n-hexane in the reaction product obtained. From the concentration, it is determined as follows.

That is, in FIG. 1, quartz wool 8, catalyst 7, and Raschig ring 4 were filled in order from below into a 10 mmφ quartz reaction tube 1, and the temperature of catalyst 7 measured by thermometer 2 was 5.
The quartz reaction tube 1 is heated in an electric furnace 5 whose temperature can be adjusted by a thermocouple 6 for temperature adjustment so as to be an isothermal temperature of 00 ° C., under the conditions of atmospheric pressure, weight hourly space velocity (WHSV) 4 hr ⁻¹ ,
From the raw material inlet 3 to the catalyst 7 through the Raschig ring 4
After supplying hexane and cooling the reaction product for 0.75 hours to 1 hour after the supply of n-hexane, that is, 0.25 hours, with the condenser 9, the reaction product is further dried with ethanol in the oil trap 10. After cooling with a refrigerant, the oil component separated in the oil trap 10 and the gas component separated in the generated gas collecting bag 11 are all collected. And F, manufactured by Hewlett-Packard Company, USA
ID-TCD gas chromatography (HP-5890)
In series II), the gas composition was determined by Shimadzu FID.
By substituting the n-hexane concentration in the reaction product obtained by analyzing the oil composition by gas chromatography (GC-17A) together with the volume of the catalyst to be used and the flow rate of the starting n-hexane, 0.25 The average of the time, the initial n-hexane decomposition first-order rate constant is determined.

[0019]

[Equation 1] {First-order reaction rate constant (hr ^-1 ) of initial n-hexane decomposition at gas and oil sampling time of 0.25 hours} =
(1 / θ) × ln {100 / [100− (n-hexane conversion)]} where θ (hr) = volume of catalyst (m ³ ) / flow rate of raw material n-hexane (m ³ / hr), n-hexane conversion (%) =
100—concentration of n-hexane (wt%) in the reaction product.

The term "volume of catalyst" as used herein means the volume of only the catalyst which does not include the volume of inert substances (Raschig rings, and, in some cases, glass beads, etc.) contained in the catalyst bed in the above-mentioned measurement test. In the present invention, the initial n-hexane decomposition first-order reaction rate constant (hr ^-1 ) obtained by the above equation is used after being converted into a unit of (sec ^-1 ).

The hydrocarbon as a raw material for the reaction using the catalyst of the present invention is a hydrocarbon containing paraffin, olefin and / or naphthene, and is a hydrocarbon having 2 or more carbon atoms.
It is a hydrocarbon having a% distillation temperature of 190 ° C or lower. For example, paraffins include ethane, propane, butane,
Pentane, hexane, heptane, octane, nonane, etc .; olefins include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, etc., and naphthenes include cyclopentane, cyclopentene, methylcyclopentane, cyclohexane. ,
Methylcyclopentene, cyclohexene, cyclohexadiene and the like can be mentioned.

The mixture may be a mixture of the above, or a C4 fraction of a pyrolysis product such as naphtha, a fraction obtained by removing butadiene or butadiene and i-butene from the C4 fraction, and a pyrolysis product such as naphtha. C5 fraction of the product, fraction obtained by removing dienes from the C5 fraction, pyrolysis gasoline, raffinate obtained by BTX extraction from pyrolysis gasoline, FCC cracked gas, FCC cracked gasoline, raffinate extracted BTX from reformate, etc. No.

The reaction conditions for converting a hydrocarbon containing paraffins, olefins and / or naphthenes into aromatic hydrocarbons are as follows: temperature: 350 to 600 ° C., pressure: atmospheric pressure to 30 kg / cm ² G, weight hourly space velocity (WHSV) ) 0.
It is preferably from ¹ to 50 hr ^-1 , and more preferably a temperature of 4 hr- ^1.
00 ~ 560 ° C, pressure atmospheric pressure ~ 10kg / cm ² G, W
HSV is 0.2 to 20 hr ^-1 .

The method for producing the mesoporous zeolite catalyst of the present invention includes, for example, the following method. The first catalyst production method comprises, as a binder, an alumina source of alumina serving as a binder, a compound having zinc as a cation of zinc as a cation, and a zeolite having an intermediate pore diameter, and optionally water,
And adding molding aids such as crystalline cellulose, mixing, molding,
After drying, it is calcined in air at a temperature of 300 ° C. or more and 800 ° C. or less.
In this method, zinc aluminate is produced by performing steam treatment so that the content of zinc aluminate is 8.2% by weight or more and 50% by weight or less, and zinc oxide and zinc aluminate coexist on the catalyst.

In the second method for producing a catalyst, a compound having zinc as a cation and an alumina source of alumina serving as a binder and water as needed are added, mixed, and dried. Above, calcination at a temperature of 800 ° C. or less, further subjected to steam treatment, and then added an intermediate pore size zeolite, and other water and, if necessary, a molding aid such as crystalline cellulose, mixed, molded, and dried. And calcined in air at a temperature of 300 ° C. or more and 800 ° C. or less, and further, zinc oxide becomes 1.2% by weight or more and 20% by weight or less and zinc aluminate becomes 8.2% by weight or more and 50% by weight or less This is a method in which zinc aluminate is generated by performing steam treatment, and zinc oxide and zinc aluminate coexist on the catalyst.

The third method for producing a catalyst comprises a zinc oxide powder, a zinc aluminate powder, an alumina source of alumina or a silica source of silica serving as a binder and an intermediate pore diameter zeolite, and optionally water and a crystalline zeolite. After adding a molding aid such as cellulose, mixing, molding and drying, the mixture is fired in air at a temperature of 300 ° C. or more and 800 ° C. or less. This is a method in which steam treatment is performed so that the zinc acid content becomes 8.2% by weight or more and 50% by weight or less to generate zinc aluminate, and zinc oxide and zinc aluminate coexist on the catalyst.

The fourth method for producing a catalyst comprises a method in which a compound having zinc as a cation, zinc aluminate powder, an alumina source of alumina or a silica source of silica serving as a binder and an intermediate pore diameter zeolite, and, if necessary, water. , And a molding aid such as crystalline cellulose are added, mixed, molded and dried, and then calcined in air at a temperature of 300 ° C. or more and 800 ° C. or less. %, Zinc aluminate is 8.2% by weight or more and 50% by weight
This is a method in which zinc aluminate is produced by performing steam treatment as described below, and zinc oxide and zinc aluminate coexist on the catalyst.

The zinc source used is a compound having zinc as a cation, that is, a compound generating zinc ion.
For example, zinc nitrate, zinc sulfate, zinc carbonate, zinc hydroxide,
Zinc chloride, zinc acetate, zinc oxalate and the like can be mentioned. Alumina sources used include gibbsite,
Bayerite, boehmite, diaspore, γ-alumina, δ-alumina, anhydrous alumina composed of alumina such as θ-alumina or hydrate of alumina, preferably boehmite, anhydrous alumina composed of alumina such as γ-alumina or water of alumina Japanese foods, but in addition,
For example, a raw material that produces anhydrous alumina or alumina hydrate by hydrolysis, thermal decomposition, oxidation, or the like, such as an aluminum salt, can be used.

Furthermore, in the present invention, it is preferable to use alumina sol among alumina hydrates as the alumina source. If an alumina source, such as alumina sol, which is reactive with the zinc source and easily produces zinc aluminate, the steam treatment step of the catalyst can be omitted,
Higher activity catalysts can be obtained. The alumina sol referred to here is an alumina hydrate having a colloidal size of 5 μm to 200 μm, having an alumina concentration of 5 to 25% by weight, and having polymerized particles of CH ₃ COO in water.
H ^-, NO ₃ ^- is a liquid anion dispersed as stabilizers or the like.

In the present invention, zinc aluminate is not used as a raw material of the catalyst, but the alumina source and the zinc source are allowed to react with each other by calcination, steam treatment, or the like in the production process of the catalyst to produce zinc aluminate. When the generation of zinc is insufficient, a more reactive alumina source or zinc source may be used from the above-mentioned alumina source and zinc source. The firing temperature of the catalyst is 300 ° C. or higher and 800 ° C. or lower, preferably 450 ° C. or higher and 650 ° C. or lower. If the firing temperature is lower than 300 ° C., it is difficult to obtain the strength of the catalyst, and if the firing temperature is higher than 800 ° C., the activity of the catalyst is reduced.

In the present invention, after adjusting the ratio of zinc oxide to zinc aluminate, a steam treatment, that is, a heat treatment in a steam stream can be performed for the purpose of pretreatment of the intermediate pore zeolite contained in the catalyst. By this treatment, coking to the catalyst is prevented, and deterioration of the activity of the catalyst can be suppressed. The steam treatment is usually performed at a partial steam pressure of 0.1 to 10 kg /
cm ² , processing temperature 500-800 ° C., preferably 550
The treatment is carried out at ７００700 ° C. for a treatment time of 0.1 to 50 hours in the presence of steam alone or a diluent such as nitrogen or air.

[0032]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below with reference to examples.

[0033]

【Example】

Example 1 50 g of zinc nitrate hexahydrate was dissolved in 200 g of water, and 100 g of alumina sol (alumina sol 52 manufactured by Nissan Chemical Industries, Ltd.) was used.
0) and H-ZSM-5 having an Si / Al atomic ratio of 25
Add 0 g and heat at 50 ° C and mix for 2 hours. Then, the above-mentioned mixture reduced in water content and formed into a clay shape was formed into a columnar shape having a diameter of 1.6 mm and a length of 5 mm, dried at 120 ° C. for 2 hours, and then fired at 500 ° C. for 3 hours in an air atmosphere in an electric furnace. .
15 g of this catalyst was charged into a reaction tube and placed in a nitrogen stream (6 [L /
Hr]) 20 [g / Hr] of pure water was supplied, and a steaming treatment was performed at 650 ° C. for 5 hours. As a result of performing atomic absorption analysis after treating the catalyst with fluorescent X-rays and hydrochloric acid,
The weight of the catalyst was 4.8% by weight of zinc oxide and 26.5% by weight of zinc aluminate.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of the hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 1. As a result, compared with Comparative Example 2, the residual amount of zinc oxide was larger and the aromatic selectivity after 8016 hours was higher.

Example 2 50 g of zinc nitrate hexahydrate was dissolved in 100 g of water, and 200 g of alumina sol (Cataloid-catalyst manufactured by Catalyst Chemical Industry Co., Ltd.) was used.
AS-2) and H-ZSM- having an Si / Al atomic ratio of 25.
50g is added and heated at 50 ° C and mixed for 2 hours. Then, the above mixture whose water content has been reduced and becomes clay-like is 1.6 m in diameter.
After molding into a column having a length of 5 mm and a length of 5 mm, the resultant was dried at 120 ° C. for 2 hours, and then fired in an air atmosphere at 500 ° C. for 3 hours in an electric furnace. 15 g of this catalyst was filled in a reaction tube and placed in a nitrogen stream (6
[L / Hr]) Supplying 20 g / Hr of pure water, 650 ° C
For 5 hours. Atomic absorption analysis was performed after treating the catalyst with fluorescent X-rays and hydrochloric acid. As a result, it was 4.6% by weight of zinc oxide and 26.8% by weight of zinc aluminate based on the weight of the catalyst.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of the hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 1. As a result, compared with Comparative Example 2, the residual amount of zinc oxide was larger and the aromatic selectivity after 8016 hours was higher.

Example 3 50 g of zinc nitrate hexahydrate was dissolved in 80 g of water, 2 g of acetic acid was added, 50 g of alumina sol (alumina sol 520 manufactured by Nissan Chemical Industries, Ltd.), 10 g of boehmite, and H-ZSM having an Si / Al atomic ratio of 25 were used. Add 50 g of -5 and mix with a ball mill for 2 hours. The clay-like mixture was molded into a column having a diameter of 1.6 mm and a length of 5 mm.
And then calcined in an air atmosphere at 500 ° C. for 3 hours in an electric furnace. 15 g of this catalyst was filled in a reaction tube, and 20 [g / Hr] of pure water was supplied in a nitrogen stream (6 [L / Hr]), and a steaming treatment was performed at 650 ° C. for 5 hours. After the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was carried out. As a result, it was 4.9% by weight of zinc oxide and 26.2% by weight of zinc aluminate based on the weight of the catalyst.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of the hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 1. As a result, compared with Comparative Example 2, the residual amount of zinc oxide was larger and the aromatic selectivity after 8016 hours was higher.

Example 4 15 g of zinc nitrate hexahydrate was dissolved in 40 g of water, 50 g of silica sol (Snowtex N manufactured by Nissan Chemical Industries, Ltd.), 22 g of zinc aluminate powder, and an Si / Al atomic ratio of 25
50 g of H-ZSM-5, and heated at 50 ° C. and mixed for 2 hours. Then, the above mixture, which has become watery and has become clay-like, is molded into a columnar shape having a diameter of 1.6 mm and a length of 5 mm.
After drying at 0 ° C. for 2 hours, the mixture was placed in an electric furnace in an air atmosphere at 500 ° C.
Calcination was performed at 3 ° C. for 3 hours. 15 g of this catalyst was filled in a reaction tube, and 20 [g / Hr] of pure water was supplied in a nitrogen stream (6 [L / Hr]), and a steaming treatment was performed at 650 ° C. for 5 hours. After the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was carried out. As a result, it was 4.8% by weight of zinc oxide and 25.5% by weight of zinc aluminate based on the weight of the catalyst.

10 g of this catalyst was filled in a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of the hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 1. As a result, compared with Comparative Example 2, the residual amount of zinc oxide was larger and the aromatic selectivity after 8016 hours was higher.

Example 5 4 g of zinc oxide, 50 g of silica sol (Snowtex N manufactured by Nissan Chemical Industry Co., Ltd.), 22 g of zinc aluminate powder, 20 g of water
g, 50 g of H-ZSM-5 having an Si / Al atomic ratio of 25 and 2 g of crystalline cellulose (Avicel TG-101 manufactured by Asahi Kasei Kogyo Co., Ltd.) are added and mixed for 2 hours. The clay-like mixture was formed into a column having a diameter of 1.6 mm and a length of 5 mm, dried at 120 ° C. for 2 hours, and fired in an air atmosphere at 500 ° C. for 3 hours in an air atmosphere. This catalyst 15
g was filled in a reaction tube, and 20 [g / Hr] of pure water was supplied in a nitrogen stream (6 [L / Hr]) to perform a steaming treatment at 650 ° C for 5 hours. Then, after the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was carried out. As a result, it was 4.6% by weight of zinc oxide and 25.8% by weight of zinc aluminate based on the weight of the catalyst.

10 g of this catalyst was filled in a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of the hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 1. As a result, compared with Comparative Example 2, the residual amount of zinc oxide was larger and the aromatic selectivity after 8016 hours was higher.

Example 6 20 g of zinc nitrate hexahydrate was dissolved in 50 g of water, and 200 g of alumina sol (alumina sol 10 manufactured by Kawaken Fine Chemical Co., Ltd.) and 50 g of H-ZSM-5 having an Si / Al atomic ratio of 25 were added. Heat and mix for 2 hours. Then, the above mixture in which the water content is reduced and becomes clay is 1.6 mm in diameter,
After being molded into a column having a length of 5 mm, it was dried at 120 ° C. for 2 hours, and then fired in an air atmosphere at 500 ° C. for 3 hours. 15 g of this catalyst was filled in a reaction tube and placed in a nitrogen stream (6
[L / Hr]) Supplying 20 g / Hr of pure water, 650 ° C
For 5 hours. After the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was carried out. As a result, it was found that zinc oxide was 2.1% by weight and zinc aluminate was 9.6% by weight based on the weight of the catalyst.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of the hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 1. As a result, compared with Comparative Example 2, the residual amount of zinc oxide was larger and the aromatic selectivity after 8016 hours was higher.

Example 7 50 g of zinc nitrate hexahydrate was dissolved in 100 g of water, and 200 g of alumina sol (catalyst-catalyst manufactured by Catalyst Chemical Industry Co., Ltd.) was used.
Add AS-2), heat at 50 ° C and mix for 2 hours. Then, the above mixture whose water content has been reduced and becomes clay-like has a diameter of 1.6.
After being molded into a column having a length of 5 mm and a length of 5 mm, it was dried at 120 ° C. for 2 hours, and then fired at 500 ° C. for 3 hours in an air atmosphere in an electric furnace. 15 g of this catalyst was charged into a reaction tube, and 20 g / Hr of pure water in a nitrogen stream (6 [L / Hr]) was supplied to the reaction tube.
After performing a steaming treatment at 0 ° C. for 5 hours, the mixture was ground in a mortar, and H-ZSM-5 having an Si / Al atomic ratio of 25 was added to 22 pieces.
g and 50 g of water, and the mixture is heated at 50 ° C. and mixed for 2 hours. Then, the above mixture whose water content has been reduced and becomes clay-like has a diameter of 1.
After molding into a column having a length of 6 mm and a length of 5 mm, the resultant was dried at 120 ° C. for 2 hours, and then fired in an electric furnace at 500 ° C. for 3 hours in an air atmosphere. Atomic absorption analysis was performed after treating the catalyst with fluorescent X-rays and hydrochloric acid. As a result, it was 4.8% by weight of zinc oxide and 25.3% by weight of zinc aluminate based on the weight of the catalyst.

10 g of this catalyst was filled in a reaction tube, and 200 [g / Hr] of hexane was supplied under normal pressure and undiluted at 550 ° C.
For 24 hours, and then the temperature is lowered to 450 ° C. at 1 Hr while replacing with 20 [L / Hr] of nitrogen. When the oxygen concentration was changed to 20 [L / Hr], the gas diluted with nitrogen to 2%, and the temperature was reduced to 500 ° C.
After 15 hours, the temperature is raised to 550 ° C., and after 20 hours, nitrogen 20 [L]
/ Hr] and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Experiment 8016
The aromatic selectivity in the hexane reaction after Hr was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate were shown in Table 1.
It was shown to. As a result, compared with Comparative Example 4, the residual amount of zinc oxide was large, and the aromatic selectivity after 8016 hours was also high.

Comparative Example 1 20 g of zinc nitrate hexahydrate was dissolved in 50 g of water, and 50 g of silica sol (Snowtex N manufactured by Nissan Chemical Industries, Ltd.) and S
50 g of H-ZSM-5 having an i / Al atomic ratio of 25 was added and 5
Heat at 0 ° C. and mix for 2 hours. Then, the above-mentioned mixture reduced in water content and formed into a clay shape was formed into a columnar shape having a diameter of 1.6 mm and a length of 5 mm, dried at 120 ° C. for 2 hours, and then fired at 500 ° C. for 3 hours in an air atmosphere in an electric furnace. . This catalyst 1
5 g was filled in a reaction tube, and 20 [g / Hr] of pure water was supplied in a nitrogen stream (6 [L / Hr]), and a steaming treatment was performed at 650 ° C for 5 hours. Then, after the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was carried out. As a result, it was found to be 16.2% by weight of zinc oxide based on the weight of the catalyst.

10 g of this catalyst was filled in a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of the hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 1. As a result, in the case of only zinc oxide, 8016Hr
In order to obtain the same aromatic selectivity as in Examples 1 to 5 later, zinc scattering is fast, so zinc oxide is required to be nearly twice, and the amount of zinc scattering is also almost twice as large.

Comparative Example 2 9 g of zinc nitrate hexahydrate was dissolved in 30 g of water, and 50 g of silica sol (Snowtex N manufactured by Nissan Chemical Industries, Ltd.) and Si
50 g of H-ZSM-5 having an / Al atomic ratio of 25
Heat at 0 ° C. and mix for 2 hours. Then, the above-mentioned mixture reduced in water content and formed into a clay shape was formed into a columnar shape having a diameter of 1.6 mm and a length of 5 mm, dried at 120 ° C. for 2 hours, and then fired at 500 ° C. for 3 hours in an air atmosphere in an electric furnace. . This catalyst 15
g was filled in a reaction tube, and 20 [g / Hr] of pure water was supplied in a nitrogen stream (6 [L / Hr]) to perform a steaming treatment at 650 ° C for 5 hours. Then, after the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was performed. As a result, it was 4.8% by weight of zinc oxide based on the weight of the catalyst.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of the hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 1.

Comparative Example 3 50 g of silica sol (Snowtex N manufactured by Nissan Chemical Industries, Ltd.), 31 g of zinc aluminate powder, 20 g of water and S
50 g of H-ZSM-5 having an i / Al atomic ratio of 25 and 2 g of crystalline cellulose (Avicel TG-10 manufactured by Asahi Kasei Corporation)
Add 1) and mix for 2 hours. The clay-like mixture was formed into a column having a diameter of 1.6 mm and a length of 5 mm, dried at 120 ° C. for 2 hours, and fired in an air atmosphere at 500 ° C. for 3 hours in an air atmosphere. 15 g of this catalyst was filled in a reaction tube, and 20 g of pure water in a nitrogen stream (6 [L / Hr]).
[Hr] was supplied, and a steaming treatment was performed at 650 ° C. for 5 hours. Atomic absorption analysis was performed after treating the catalyst with fluorescent X-rays and hydrochloric acid. As a result, it was found that zinc oxide was 0% and zinc aluminate was 34.1% by weight based on the weight of the catalyst.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the aromatic selectivity in the hexane reaction after one hour at 550 ° C. was measured.
Table 1 also shows the measurement results of the amounts of zinc oxide and zinc aluminate. As a result, compared to Examples 1 to 6, only zinc aluminate and no zinc oxide have a low aromatic selectivity from the beginning.

Comparative Example 4 20 g of zinc nitrate hexahydrate was dissolved in 50 g of water, and 50 g of silica sol (Snowtex N manufactured by Nissan Chemical Industries, Ltd.) and S
50 g of H-ZSM-5 having an i / Al atomic ratio of 25 was added and 5
Heat at 0 ° C. and mix for 2 hours. Then, the above-mentioned mixture reduced in water content and formed into a clay shape was formed into a columnar shape having a diameter of 1.6 mm and a length of 5 mm, dried at 120 ° C. for 2 hours, and then fired at 500 ° C. for 3 hours in an air atmosphere in an electric furnace. . Then, after the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was carried out. As a result, it was found to be 16.2% by weight of zinc oxide based on the weight of the catalyst.

10 g of this catalyst was charged into a reaction tube, and hexane was supplied at 200 g / Hr under normal pressure and undiluted.
For 24 hours, and then the temperature is lowered to 450 ° C. at 1 Hr while replacing with 20 [L / Hr] of nitrogen. When the oxygen concentration was changed to 20 [L / Hr], the gas diluted with nitrogen to 2%, and the temperature was reduced to 500 ° C.
After 15 hours, the temperature is raised to 550 ° C., and after 20 hours, nitrogen 20 [L]
/ Hr] and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Experiment 8016
The aromatic selectivity in the hexane reaction after Hr was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate were shown in Table 1.
It was shown to. As a result, in the case of only zinc oxide, 8016H
In order to obtain the same aromatic selectivity as Example 7 after r, zinc scattering is fast, so that zinc oxide is required to be almost twice,
The amount of zinc scattered is almost doubled.

[0055]

[Table 1]

Comparative Example 5 H-ZSM-5 having an Si / Al atomic ratio of 25 was converted to [15 ton /
cm ² ] and compressed into a plate of 1-2 mm, crushed with a spoon and sieved to form 8 to 20 mesh. 60 g of this was filled in a reaction tube and placed in a nitrogen stream (6 [L /
Hr]) 20 [g / Hr] of pure water was supplied, and a steaming treatment was performed at 650 ° C. for 1 hour. Then, the steamed H-ZSM-5 is ground in a mortar to obtain
g of zinc nitrate hexahydrate dissolved in 20 g of water, and 50 g of silica sol (Snowtex N manufactured by Nissan Chemical Industries, Ltd.) is heated at 50 ° C. and mixed for 2 hours. Then, the above mixture in which the water content was reduced and became a clay was formed into a columnar shape having a diameter of 1.6 mm and a length of 5 mm.
And then calcined in an air atmosphere at 500 ° C. for 3 hours in an electric furnace. Then, after the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was carried out. As a result, it was 6.5% by weight of zinc oxide based on the weight of the catalyst.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 2.

Example 8 H-ZSM-5 having an Si / Al atomic ratio of 25 was converted to [15 ton /
cm ² ] and compressed into a plate of 1-2 mm, crushed with a spoon and sieved to form 8 to 20 mesh. The reaction tube was filled with 50 g and charged in a nitrogen stream (6 [L /
Hr]) 20 [g / Hr] of pure water was supplied, and a steaming treatment was performed at 650 ° C. for 1 hour. Then, the steamed H-ZSM-5 was ground into a powder in a mortar and added to a solution prepared by dissolving 6 g of zinc nitrate hexahydrate in 20 g of water.
Further, 50 g of silica sol (Snowtex N manufactured by Nissan Chemical Industries, Ltd.) and 7 g of zinc aluminate powder are heated at 50 ° C. and mixed for 2 hours. Then, the above-mentioned mixture reduced in water content and formed into a clay shape was formed into a columnar shape having a diameter of 1.6 mm and a length of 5 mm, dried at 120 ° C. for 2 hours, and then fired at 500 ° C. for 3 hours in an air atmosphere in an electric furnace. . As a result of performing atomic absorption analysis after treating the catalyst with fluorescent X-rays and hydrochloric acid,
The weight of the catalyst was 2.3% by weight of zinc oxide and 9.9% by weight of zinc aluminate.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. Then, while replacing with 20 [L / Hr] of nitrogen, The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 2. As a result, compared with Comparative Example 5, the residual amount of zinc oxide was larger and the aromatic selectivity after 8016 hours was higher.

Comparative Example 6 2 g of zinc oxide, 50 g of silica sol (Snowtex N manufactured by Nissan Chemical Industries, Ltd.) and 50 g of H-ZSM-5 having an Si / Al atomic ratio of 25 were added and mixed for 2 hours. Then, the above mixture in the form of clay is 1.6 mm in diameter and 5 mm in length.
After being molded into a columnar shape and dried at 120 ° C. for 2 hours, it was fired in an air atmosphere at 500 ° C. for 3 hours in an electric furnace. Then, after the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was carried out. As a result, it was 2.7% by weight of zinc oxide based on the weight of the catalyst.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 2.

Example 9 2 g of zinc oxide, 50 g of silica sol (Snowtex N manufactured by Nissan Chemical Industries, Ltd.), 7 g of zinc aluminate powder, 20 g of water
Then, H-ZSM-5 having an Si / Al atomic ratio of 25
Add 0 g and mix for 2 hours. Then, after the clay-like mixture is molded into a column having a diameter of 1.6 mm and a length of 5 mm,
After drying at 120 ° C. for 2 hours, the mixture is placed in an electric furnace in an air atmosphere for 5 hours.
It was baked at 00 ° C. for 3 hours. After treating the catalyst with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was carried out. As a result, 2.6% by weight of zinc oxide and 9.9% of zinc aluminate were calculated based on the weight of the catalyst.
It was 6% by weight.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 2. As a result, compared with Comparative Example 6, the residual amount of zinc oxide was larger and the aromatic selectivity after 8016 hours was higher.

[0064]

[Table 2]

Example 10 51% by weight of H-type ZSM-5 crystalline aluminosilicate having an Si / Al atomic ratio of 25, 14% by weight of γ-alumina and 35% by weight of zinc nitrate were dissolved in water, kneaded, and extruded. Was carried out to form a diameter of 1.6 mm and a length of 4 to 6 mm. Then, after drying at 120 ° C for 3 hours, 500 ° C for 3 hours.
After calcining for an hour, a ZSM-5 zeolite forming catalyst containing 10% by weight of zinc was obtained.

Next, this catalyst was filled in a fixed-bed one-stage adiabatic reactor, and in a steam-nitrogen mixed gas containing 40% by volume of steam at a pressure of 1 kg / cm ² · G and a temperature of 650 ° C. for 5 hours. Heat treated. After the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was carried out. As a result, 2.7% by weight of zinc oxide and 21.0% of zinc aluminate were calculated based on the weight of the catalyst.
% By weight. Next, using the device described in the text,
An isothermal n-hexane conversion reaction test of this zeolite molded catalyst was performed. Under the conditions of pressure and atmospheric pressure, temperature of 500 ° C., and weight hourly space velocity (WHSV) of 4 hr ⁻¹ , the decomposition reaction of n-hexane was carried out for 0.25 hours, and the average n−
Hexane decomposition fresh activity was determined by the following equation to be 0.28
Met.

Next, the C4 fraction shown in Table 3 and the C4 fraction shown in Table 4
A raw material (unsaturated hydrocarbon / saturated hydrocarbon ratio: 1.54) obtained by mixing the 5 fractions at a ratio of 6: 4 (weight ratio) was heated to 530 ° C.
Feed to reactor. The reaction is carried out for 48 hours. Then, at 450 ° C. with 2 hours while replacing with nitrogen as a regeneration process
Cool down to Then, the oxygen concentration was switched to a gas diluted with nitrogen to 1%, and the temperature was set to 500 when the regeneration was performed for 20 hours.
C. to 10 hours, and further to 530 ° C., and after 10 hours of regeneration, switch to nitrogen. This 48 hour cycle reaction,
The regeneration process was repeated and operation continued for one year. Table 5 shows the reaction results of the catalyst, the aromatic yield at the start of the repetition of regeneration and one year later, and the measurement results of the amounts of zinc oxide and zinc aluminate together with the reaction conditions.

Comparative Example 7 H-type ZSM-5 crystalline aluminosilicate having an Si / Al atomic ratio of 25 (SiO ₂ / Al ₂ O ₃ molar ratio 70) 35
%, Silica sol 45% (Nissan Chemical Industry Co., Ltd. Snowtex N) and zinc nitrate 20% are dissolved in water, kneaded, extruded, 1.6 mm in diameter and 4-6 mm in length.
Molded. Then, after drying at 120 ° C. for 3 hours, 500
C. for 3 hours to obtain a ZSM-5 zeolite shaped catalyst containing 10% by weight of zinc.

Next, this catalyst was filled in a fixed-bed one-stage adiabatic reactor, and in a steam-nitrogen mixed gas containing 40% by volume of steam at a pressure of 1 kg / cm ² · G and a temperature of 650 ° C. for 5 hours. Heat treated. After the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was carried out. As a result, the weight was 9.8% by weight of zinc oxide and 0.0% by weight of zinc aluminate based on the weight of the catalyst. Next, an isothermal n-hexane conversion reaction test of this zeolite molded catalyst was performed using the apparatus described above in the text. Under the conditions of pressure atmospheric pressure, temperature 500 ° C., and weight hourly space velocity (WHSV) 4 hr ⁻¹ , the decomposition reaction of n-hexane was performed for 0.25 hours, and the average n-hexane decomposition fresh activity during the reaction was calculated by the following formula. Was found to be 0.28.

Next, the C4 fraction shown in Table 3 and the C4 fraction shown in Table 4
A raw material (unsaturated hydrocarbon / saturated hydrocarbon ratio: 1.54) obtained by mixing the 5 fractions at a ratio of 6: 4 (weight ratio) was heated to 530 ° C.
Feed to reactor. The reaction is carried out for 48 hours. Then, at 450 ° C. with 2 hours while replacing with nitrogen as a regeneration process
Cool down to Then, the oxygen concentration was switched to a gas diluted with nitrogen to 1%, and the temperature was set to 500 when the regeneration was performed for 20 hours.
C. to 10 hours, and further to 530 ° C., and after 10 hours of regeneration, switch to nitrogen. This 48 hour cycle reaction,
The regeneration process was repeated and operation continued for one year. Table 5 shows the reaction results of the catalyst, the aromatic yield at the start of the repetition of regeneration and one year later, and the measurement results of the amounts of zinc oxide and zinc aluminate together with the reaction conditions.

Comparative Example 8 35% by weight of H-type ZSM-5 crystalline aluminosilicate having an Si / Al atomic ratio of 25, 60% by weight of silica sol (Snowtex N manufactured by Nissan Chemical Industries, Ltd.) and 5% of zinc nitrate were dissolved in water. Then, after kneading, extrusion molding was performed, and the diameter was 1.
It was formed into a size of 6 mm and a length of 4 to 6 mm. Then, 120
After drying for 3 hours at 500 ° C, baking for 3 hours at 500 ° C
A ZSM-5 zeolite shaped catalyst containing 5% by weight was obtained.

Next, this catalyst was filled in a fixed-bed one-stage adiabatic reactor, and in a steam-nitrogen mixed gas containing 40% by volume of steam at a pressure of 1 kg / cm ² · G and a temperature of 650 ° C. for 5 hours. Heat treated. Then, after the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was performed. As a result, it was 2.7% by weight of zinc oxide and 0.0% by weight of zinc aluminate based on the weight of the catalyst. Next, using the device described in the text,
An isothermal n-hexane conversion reaction test of this zeolite molded catalyst was performed. Under the conditions of pressure and atmospheric pressure, temperature of 500 ° C., and weight hourly space velocity (WHSV) of 4 hr ⁻¹ , the decomposition reaction of n-hexane was carried out for 0.25 hours, and the average n−
Hexane decomposition fresh activity was determined by the following equation to be 0.28
Met.

Next, the C4 fraction shown in Table 3 and the C4 fraction shown in Table 4
A raw material (unsaturated hydrocarbon / saturated hydrocarbon ratio: 1.54) obtained by mixing the 5 fractions at a ratio of 6: 4 (weight ratio) was heated to 530 ° C.
Feed to reactor. The reaction is carried out for 48 hours. Then, at 450 ° C. with 2 hours while replacing with nitrogen as a regeneration process
Cool down to Then, the oxygen concentration was switched to a gas diluted with nitrogen to 1%, and the temperature was set to 500 when the regeneration was performed for 20 hours.
C. to 10 hours, and further to 530 ° C., and after 10 hours of regeneration, switch to nitrogen. This 48 hour cycle reaction,
The regeneration process was repeated and operation continued for one year. Table 5 shows the reaction results of the catalyst, the aromatic yield at the start of the repetition of regeneration and one year later, and the measurement results of the amounts of zinc oxide and zinc aluminate together with the reaction conditions.

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

Example 11 36 g of zinc nitrate hexahydrate was dissolved in 100 g of water, and 100 g of alumina sol (alumina sol 52 manufactured by Nissan Chemical Industries, Ltd.) was used.
0) and H-ZSM-5 having an Si / Al atomic ratio of 25
g and heat at 50 ° C and mix for 2 hours. Then, the above-mentioned mixture reduced in water content and formed into a clay shape was formed into a columnar shape having a diameter of 1.6 mm and a length of 5 mm, dried at 120 ° C. for 2 hours, and then fired at 500 ° C. for 3 hours in an air atmosphere in an electric furnace. .
15 g of this catalyst was charged into a reaction tube and placed in a nitrogen stream (6 [L /
Hr]) 20 [g / Hr] of pure water was supplied, and a steaming treatment was performed at 650 ° C. for 5 hours. As a result of performing atomic absorption analysis after treating the catalyst with fluorescent X-rays and hydrochloric acid,
The weight of the catalyst was 2.9% by weight of zinc oxide and 22.4% by weight of zinc aluminate. 10 g of this catalyst was charged into a reaction tube, and hydrogen was passed at 20 [L / Hr] at 550 ° C. for 20 hours.
To reduce. Table 6 shows the measurement results of the amounts of zinc oxide and zinc aluminate after the hydrogen reduction.

Comparative Example 9 7 g of zinc nitrate hexahydrate was dissolved in 30 g of water, and 100 g of silica sol (Snowtex N manufactured by Nissan Chemical Industries, Ltd.) and H-
Add 50 g of ZSM-5, heat at 50 ° C. and mix for 2 hours. Then, the above mixture in which the water content was reduced and became a clay was formed into a columnar shape having a diameter of 1.6 mm and a length of 5 mm.
And then calcined in an air atmosphere at 500 ° C. for 3 hours in an electric furnace. 15 g of this catalyst was filled in a reaction tube, and 20 [g / Hr] of pure water was supplied in a nitrogen stream (6 [L / Hr]), and a steaming treatment was performed at 650 ° C. for 5 hours. Then, after the catalyst was treated with fluorescent X-rays and hydrochloric acid, atomic absorption analysis was performed. As a result, it was 2.4% by weight of zinc oxide and 0.0% by weight of zinc aluminate based on the weight of the catalyst. This catalyst 1
0 g was charged into a reaction tube, and hydrogen was supplied at 20 [L / Hr].
Reduce for 20 hr at 50 ° C. Table 6 shows the measurement results of the amounts of zinc oxide and zinc aluminate after the hydrogen reduction.

[0079]

[Table 6]

Example 12 Ammonium ion type ZSM having an Si / Al atomic ratio of 25
Zinc nitrate (14 g as zinc metal) and alumina sol (Al ₂
50 g of O ₃ ) was added, kneaded, and extruded to form a column having a diameter of 1.6 mm and a length of 4 to 6 mm, dried at 120 ° C. for 4 hours, and then placed in an electric furnace in an air atmosphere at 500 ° C. For 3 hours. 20 g of this catalyst is
A 2 mm quartz glass reaction tube was filled and subjected to a heat treatment at 650 ° C. for 1 hour under atmospheric pressure in a mixed gas of steam and nitrogen containing 80% of steam. Atomic absorption analysis was performed after treating the catalyst with fluorescent X-rays and hydrochloric acid. As a result, it was found that zinc oxide was 2.5% by weight and zinc aluminate was 8.6% by weight based on the weight of the catalyst.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 20 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 530 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of the hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 7 together. As a result, the aromatic selectivity was 1 compared to Comparative Example 10.
It is higher both after 80 hours and after 80 hours.

Comparative Example 10 Ammonium ion type ZSM having an Si / Al atomic ratio of 25
-5 crystal aluminosilicate 200 g, zinc nitrate (4.6 g as zinc metal) and alumina sol (Al
50 g of ₂ O ₃ ) was added, kneaded, extruded, formed into a column having a diameter of 1.6 mm and a length of 4 to 6 mm, dried at 120 ° C. for 4 hours, and then placed in an electric furnace in an air atmosphere. Calcination was performed at 3 ° C. for 3 hours. 20 g of this catalyst is
A 2 mm quartz glass reaction tube was filled and subjected to a heat treatment at 650 ° C. for 1 hour under atmospheric pressure in a mixed gas of steam and nitrogen containing 80% of steam. Atomic absorption analysis was performed after treating the catalyst with fluorescent X-rays and hydrochloric acid. As a result, it was found that zinc oxide was 1.1% by weight and zinc aluminate was 8.1% by weight based on the weight of the catalyst.

10 g of this catalyst was charged into a reaction tube, hexane was supplied at 50 [g / Hr] under normal pressure and undiluted, and the reaction was carried out at 550 ° C. for 24 hours. The temperature is lowered to 450 ° C. at 1 hour. Then, the oxygen concentration was switched to 20 [L / Hr], which was diluted with nitrogen to 2%, and the temperature was raised to 500 ° C. at the time of regeneration for 10 hours.
After 5 hours, the temperature was raised to 550 ° C., and after 20 hours, nitrogen 20 [L /
Hr], and the reproduction process is completed in 24 hours. The process of this reaction and regeneration was repeated, and the experiment of 8016Hr was continued. Before repeating the reaction and regeneration of this catalyst and experiment 8016H
The aromatic selectivity at the time of the hexane reaction after r was measured, and the measurement results of the amounts of zinc oxide and zinc aluminate are shown in Table 7 together.

[0084]

[Table 7]

[0085]

Industrial Applicability The catalyst for producing aromatic hydrocarbons of the present invention comprises:
By the coexistence of zinc oxide and zinc aluminate, the reduction of zinc oxide in the catalyst is suppressed, and in the reaction of converting hydrocarbons containing paraffins, olefins and / or naphthenes to aromatic hydrocarbons, zinc is more dispersed than before. It has an excellent effect that the amount can be suppressed and higher aromatic selectivity can be maintained.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a reaction apparatus used for obtaining a first-order rate constant for n-hexane decomposition.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Quartz reaction tube 2 Thermometer 3 Raw material inlet 4 Raschig ring 5 Electric furnace 6 Thermocouple 7 Catalyst 8 Quartz wool 9 Condenser 10 Oil trap 11 Bag for collecting generated gas

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Yukito Nagamori 3-13-1 Shiodori, Kurashiki-shi, Okayama Prefecture Sanyo Oil Chemical Co., Ltd.

Claims (7)

[Claims] 1. A zeolite catalyst having an intermediate pore diameter which is used in a reaction for converting a hydrocarbon containing paraffin, olefin and / or naphthene into an aromatic hydrocarbon. Zinc oxide 1.2-
A zeolite catalyst having an intermediate pore diameter, wherein 20% by weight and 8.2 to 50% by weight of zinc aluminate coexist. 2. The catalyst according to claim 1, wherein the intermediate pore diameter zeolite constituting the intermediate pore diameter zeolite-based catalyst has a zeolite skeleton having an Si / Al atomic ratio of 12 or more. 3. The catalyst according to claim 1, wherein the intermediate pore diameter zeolite constituting the intermediate pore diameter zeolite-based catalyst is a ZSM-5 type zeolite. 4. The catalyst according to claim 1, wherein the catalytic activity of the mesoporous zeolite-based catalyst is 0.2 sec ⁻¹ or more as a value of an initial primary reaction rate constant of n-hexane decomposition measured at 500 ° C. and atmospheric pressure. The catalyst according to any one of claims 1 to 3, characterized in that: 5. A method comprising mixing an alumina sol, a compound having zinc as a cation and a zeolite having an intermediate pore size, drying the mixture,
The method for producing a catalyst according to any one of claims 1 to 4, wherein the calcination is carried out at a temperature of not lower than 800C and not higher than 800C. 6. An alumina sol and a compound having zinc as a cation are mixed, dried, calcined at a temperature of 300 ° C. or more and 800 ° C. or less, steam-treated and mixed with a medium pore diameter zeolite, and dried. 300 ° C or higher, 800 ° C
The method for producing a catalyst according to any one of claims 1 to 4, wherein the catalyst is calcined at the following temperature. 7. The method for producing a catalyst according to claim 5, wherein the mixture is mixed with zeolite having an intermediate pore size, dried and calcined, and further subjected to steam treatment.