JP6780369B2 - Aromatic compound production catalyst and method for producing aromatic compounds - Google Patents

Description

The present invention relates to a catalyst for producing an aromatic compound containing a specific MFI-type zeolite and a method for producing an aromatic compound using the catalyst, and particularly for production containing an MFI-type zeolite having a relatively uniform mesopore group. The present invention relates to an aromatic compound production catalyst having excellent properties, stability, swing operability, and long life, and a method for producing an aromatic compound using the catalyst.

MFI-type zeolite is used as a highly selective catalyst utilizing uniform pores derived from the zeolite structure. Examples of using MFI-type zeolite as a catalyst include disproportionation of toluene (see, for example, Patent Document 1), isomerization of xylene (see, for example, Patent Document 2) and the like.

These reactions mainly utilize the characteristics of the micropores of MFI-type zeolite. The micropores of the MFI-type zeolite have an inlet diameter of about 0.5 nm, and are considered to be an effective reaction field for molecules having a molecular diameter close to the pore diameter.

Further, research is being conducted on MFI-type zeolite having pores larger than micropores (less than 2 nm), that is, mesopores (pore diameter 2 to 50 nm) (see, for example, Non-Patent Document 1).

Then, as a promising material for industrial use, a novel MFI-type zeolite having uniform mesopores of 10 nm or more and a method for producing the same (see, for example, Patent Document 3) have been proposed, and a zeolite having mesopores has been proposed. As an example of using as a catalyst, fluid catalytic cracking (FCC) of vacuum light oil using ultrastable Y-zeolite (USY) (see, for example, Patent Documents 4 and 5) has been proposed. Since the process involves advancing a catalytic cracking reaction using heavy oil as a raw material, a catalyst having pores in which molecules having a large size equivalent to heavy oil can diffuse is desired. Cases in which zeolite having mesopores is used as a catalyst have long been limited to those using a relatively large space inside the mesopores as a reaction field and using relatively large molecules such as heavy oil as a raw material. .. Therefore, there are few reports that specific results were obtained by using zeolite having mesopores as a catalyst, especially in a reaction using a relatively small molecule having 10 or less carbon atoms as a raw material.

Benzene, toluene, and xylene (hereinafter collectively referred to as aromatic compounds) are often obtained by decomposing raw material oil (for example, naphtha) obtained by petroleum refining with a pyrolysis reactor. It is obtained by separating and purifying an aromatic compound from the resulting pyrolysis product by distillation or extraction. In the production of aromatic compounds by these production methods, aliphatic and alicyclic hydrocarbons are included as thermal decomposition products other than aromatic compounds. Therefore, since the aliphatic and alicyclic hydrocarbons are produced at the same time as the aromatic compound is produced, the production amount of the aromatic compound is adjusted in proportion to the production amount of the aliphatic and alicyclic hydrocarbons. Naturally, there was a limit to the amount of production. Further, an aromatic compound can be produced by contacting an aliphatic or alicyclic hydrocarbon raw material with a catalyst mainly containing medium pore size zeolite at a temperature of about 400 ° C. to about 800 ° C. ( For example, Non-Patent Documents 2-5). Compared with the method for producing an aromatic compound by thermal decomposition, the production method has advantages that the added value is low and the aromatic compound can be produced from a surplus hydrocarbon raw material. In addition, catalysts used in the production of these aromatic compounds are also being developed. For example, Patent Document 6 provides a zinc-supported intermediate pore size zeolite-based catalyst in which the amount of zinc scattering is suppressed as a catalyst for producing an aromatic compound using a hydrocarbon containing paraffin, olefin, and naphthene as a raw material. Alternatively, in Patent Document 7, as a catalyst used for producing an aromatic compound using paraffin, olefin, acetylene hydrocarbon, cyclic paraffin and cyclic olefin as raw materials, L-type zeolite is simultaneously supported with platinum and halogen components. Provides a catalyst. Alternatively, in Patent Document 8, the size of the structure is 0.1 to 100 mm, crystalline porous aluminosilicate is present on the surface layer portion of the structure, and an inorganic support is provided on the inner layer excluding the surface layer portion of the structure. Provided is a catalyst for an aromatization reaction, characterized in that zinc and / or gallium is supported on the structure in which zinc and / or gallium are present. In addition, Patent Documents 9 to 10 provide catalysts for producing aromatic compounds using hydrocarbons as raw materials.

In the method for producing an aromatic compound using these catalytic reactions, the catalyst life (the time from the active state of the catalyst to the deactivation of the catalyst after the start of the reaction) becomes a problem from the viewpoint of production cost. Therefore, a method for selectively and stably producing an aromatic compound from a hydrocarbon raw material having a relatively small molecule (particularly 10 or less carbon atoms) over a long period of time is very meaningful.

Japanese Patent No. 401479 Japanese Patent No. 2598127 Japanese Unexamined Patent Publication No. 2013-227203 Japanese Patent No. 5339845 Japanese Patent No. 4773420 JP-A-1998-33987 Japanese Patent No. 3264447 Japanese Patent No. 5447468 Japanese Patent No. 3966429 Japanese Patent No. 5564769

Microporous and Mesoporous Materials, Vol. 137, p. 92 (2011) Industrial & Engineering Chemistry Research Vol. 31, p. 995 (1992) Industrial & Engineering Chemistry Research Vol. 26, p. 647 (1987) Applied Catalysis Vol. 78, p. 15 (1991) Microporous and Mesoporous Materials, Vol. 47, pp. 253 (2001)

An object of the present invention is a novel aromatic compound capable of selectively and stably producing an aromatic compound from a hydrocarbon raw material having a relatively small molecule (particularly 10 or less carbon atoms) over a long period of time. A catalyst for producing a group compound and a method for producing an aromatic compound using the same are provided.

As a result of diligent studies to solve the above problems, the present inventor selectively and stably produces an aromatic compound for a long period of time with a catalyst for producing an aromatic compound containing a specific MFI-type zeolite. We have found that it can be a catalyst that can be used, and have completed the present invention.

That is, the present invention is a group consisting of an aromatic compound production catalyst characterized by containing an MFI-type zeolite satisfying the properties shown in (i) to (iii) below, and an olefin having 2 to 6 carbon atoms. The present invention relates to a method for producing an aromatic compound, which comprises contacting a lower olefin containing at least one of them to form an aromatic compound.
(I) The mesopore distribution curve has a peak, the full width at half maximum (hw) of the peak is hw ≦ 20 nm, and the center value (μ) of the peak is 10 nm ≦ μ ≦ 20 nm, which corresponds to the peak. It has a mesopore group in which the mesopore volume (pv) of the mesopores is 0.05 ml / g ≦ pv.
(Ii) There is no peak in the range of 0.1 to 3 degrees in the powder X-ray diffraction measurement with the diffraction angle set to 2θ.
(Iii) The average particle size (PD) is PD ≦ 100 nm.

The present invention will be described in detail below.

The aromatic compound production catalyst of the present invention comprises a specific MFI-type zeolite, and by containing the specific MFI-type zeolite, the aromatic compound is selectively and stable for a long period of time. It is a catalyst that can be produced in Japan.

The MFI-type zeolite constituting the aromatic compound production catalyst of the present invention satisfies the properties shown in (i) to (iii) above, and the MFI-type zeolite has a structure code MFI defined by the International Zeolite Society. Indicates an aluminosilicate compound belonging to. Further, the mesopores referred to in the present invention are mesopores defined by IUPAC, and indicate pores having a pore diameter in the range of 2 to 50 nm. Then, the mesopores can be measured by a general nitrogen adsorption method at a liquid nitrogen temperature. Moreover, the value of the pore volume of the mesopores can be obtained by analyzing the measurement result obtained by the nitrogen adsorption method. For the analysis, for example, the following method can be used.

Specifically, a method of analyzing the desorption process by the Barret-Joiner-Halenda method (Journal of the American Chemical Society, 1951, pp. 373 to 380) can be mentioned. For example, the pore diameter is 2 nm or more and 50 nm or less. By integrating the amount of nitrogen gas desorbed in the range corresponding to, the value of the total pore volume of the pores belonging to the mesopores can be obtained.

First, a cumulative curve is obtained in which the vertical axis represents the amount of nitrogen desorption V / m (mL / g) per unit mass and the horizontal axis represents the mesopore diameter D (nm), and then the vertical axis represents the mesopores. By setting the differential value (d (V / m) / d (D)) of the amount of nitrogen gas desorbed from the mesopore diameter value, the amount of increase in the amount of nitrogen desorption per unit mass in the mesopore diameter You can get a peak.

The aromatic compound production catalyst of the present invention comprises an MFI-type zeolite having a mesopore group having a substantially uniform pore diameter, and in the present invention, the mesopores having a substantially uniform pore diameter. The group may also be referred to as a uniform mesopore. Specifically, the uniform mesopore means that the largest peak among the peaks related to the mesopore in the pore distribution curve is approximated by a Gaussian function, and the standard deviation from the center value (μ) of the Gaussian function. Mesopores having a pore diameter within the range (μ ± 2σ) of twice (2σ). Further, the pore volume of the uniform mesopores can be obtained by integrating the amount of nitrogen gas desorption in the range of μ ± 2σ.

The aromatic compound production catalyst of the present invention has a peak in (i) mesopore distribution curve among MFI-type zeolites having a substantially uniform mesopore group, and the half width (hw) of the peak. ) Is hw ≦ 20 nm, the center value (μ) of the peak is 10 nm ≦ μ ≦ 20 nm, and the mesopore volume (pv) of the mesopores corresponding to the peak is pv ≧ 0.05 ml / g. It contains an MFI-type zeolite having a more uniform mesopore group.

In the aromatic compound production catalyst of the present invention, the pore distribution curve of the mesopores has a peak, and the peak is an MFI-type zeolite having a peak of hw ≦ 20 nm or less, which is a substantially uniform meso with a small variation in the size of the pore diameter. By containing the MFI-type zeolite having a pore group, the reaction selectivity becomes excellent, and the effect becomes more remarkable and preferable when hw ≦ 15 nm. The lower limit of hw is not particularly set, but it is preferably 1 nm or more because the reaction selectivity is more excellent. When hp> 20 nm, the reaction selectivity is inferior. Further, by containing an MFI-type zeolite whose center value (μ) when the peak is approximated by a Gaussian function is 10 nm ≦ μ ≦ 20 nm, it becomes possible to selectively react with a molecule having a larger size, which is excellent. It serves as a catalyst for producing aromatic compounds. Further, when pv ≧ 0.05 ml / g, it becomes a catalyst having a long life, preferably 0.05 ml / g ≦ pv ≦ 0.70 ml / g, and particularly 0.10 ml / g ≦. It is preferable that pv ≦ 0.7 ml / g, and further preferably 0.20 ml / g ≦ pv ≦ 0.5 ml / g. Here, when pv <0.05 ml / g, the pores are easily clogged due to the accumulation of coke and the like produced as a by-product during the reaction, and the catalyst life is deteriorated.

Further, since the MFI-type zeolite contained in the aromatic compound production catalyst of the present invention is a catalyst that enables a particularly selective reaction, the ratio of pv to the total pore volume shown in (i) above (i). pvr) is preferably 30% ≦ pvr ≦ 100%, and more preferably 40% ≦ pvr ≦ 100%.

The MFI-type zeolite contained in the aromatic compound production catalyst of the present invention does not have a peak in the range of 0.1 to 3 degrees in (ii) powder X-ray diffraction measurement with a diffraction angle of 2θ. This indicates that there is no regularity in the arrangement between the mesopores and that there is no wall separating the mesopores, and when used as a catalyst, mass transfer between the mesopores is easy. Therefore, it becomes a catalyst for producing an aromatic compound having excellent reaction efficiency.

The MFI-type zeolite contained in the aromatic compound production catalyst of the present invention has (iii) PD ≦ 100 nm, and is particularly excellent in heat resistance. Therefore, the MFI type zeolite may have 3 nm ≦ PD. It is preferable that 5 nm ≦ PD. Here, when the zeolite has a PD> 100 nm, a substantially uniform mesopore group is not formed, and the selectivity is high. The PD can be obtained by calculating from the outer surface area, for example, using the following formula (1).
PD = 6 / S (1 / 2.29 × 10 ⁶ + 0.18 × ^10-6 ) (1)
(Here, S indicates the outer surface area (m ² / g).)
The outer surface area (S (m ² / g)) in the formula (1) can be obtained from the t-prot method using a general nitrogen adsorption method at a liquid nitrogen temperature. For example, when t is the thickness of the adsorption amount, the measurement points in the range of 0.6 to 1 nm are linearly approximated with respect to t, and the outer surface area is obtained from the slope of the obtained regression line.

As another method for measuring the particle size of the MFI type zeolite, for example, 10 or more arbitrary particles are selected from photographs of a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and the average surface diameter thereof. Can be mentioned as a method of finding.

The SiO ₂ / Al ₂ O ₃ (molar ratio) of the MFI-type zeolite contained in the aromatic compound production catalyst of the present invention is not limited, and among them, a catalyst having excellent heat resistance, reaction selectivity, and productivity. Therefore, the SiO ₂ / Al ₂ O ₃ (molar ratio) is preferably 20 or more and 200 or less.

The MFI-type zeolite contained in the aromatic compound production catalyst of the present invention is a catalyst having excellent reaction selectivity and productivity, and therefore does not contain a structure-directing agent such as a tetrapropylammonium salt in the pores. It is preferable to have.

The form when the MFI-type zeolite is used as the catalyst for producing an aromatic compound of the present invention is not limited, and for example, the synthesized MFI-type zeolite powder can be used as it is as a catalyst, or compression molding is performed to obtain a specific shape. It can be used in any form, such as being used as an object, being mixed with a binder or the like and being molded and used as a specific shaped object.

The aromatic compound production catalyst of the present invention contains the MFI type zeolite and thus becomes an aromatic compound production catalyst excellent in efficiency such as reaction selectivity and productivity. For example, the aromatic compound production catalyst has 2 to 6 carbon atoms. By contacting with a hydrocarbon, it is possible to efficiently produce an aromatic compound. At that time, any hydrocarbon having 2 to 6 carbon atoms can be mentioned as long as it belongs to the category. For example, saturated hydrocarbons, unsaturated hydrocarbons, alicyclic hydrocarbons, mixtures thereof and the like can be mentioned. More specifically, ethane, ethylene, propane, propylene, cyclopropane, n-butane, isobutane, 1-butene, 2-butene, isobutene, butadiene, cyclobutene, cyclobutane, n-pentane, 1- Pentan, 2-pentane, 1-pentene, 2-pentene, 3-pentene, n-hexane, 1-hexane, 2-hexane, 1-hexene, 2-hexane, 3-hexene, hexadiene, cyclohexane and mixtures thereof, etc. Can be mentioned.

The aromatic compound production catalyst of the present invention contains the MFI type zeolite and thus becomes an aromatic compound production catalyst excellent in efficiency such as reaction selectivity and productivity. For example, it has 2 to 2 carbon atoms. By contacting with at least one lower olefin in the group consisting of 6 olefins, it is possible to efficiently produce an aromatic compound. Examples of the olefin at that time include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 1-hexene, 2-hexene, 3-hexene and mixtures thereof. Can be mentioned.

Further, by contacting a hydrocarbon mixture having 4 carbon atoms with a catalyst containing the MFI type zeolite, it becomes a method for producing an aromatic compound having excellent efficiency such as reaction selectivity and productivity, and carbon. Examples of the hydrocarbon mixture of No. 4 include those called C4 fractions among the decomposition fractions of petroleum such as naphtha, and more specifically, n-butane, isobutane, 1 Examples thereof include a mixture composed of −butene, 2-butene, isobutene, butadiene, cyclobutene, cyclobutane and the like.

By contacting a hydrocarbon mixture having 6 carbon atoms with a catalyst containing the MFI-type zeolite, it becomes a method for producing an aromatic compound having excellent efficiency such as reaction selectivity and productivity, and has 6 carbon atoms. Examples of the hydrocarbon mixture of the above include those referred to as C6 fractions and the like among the decomposition fractions of petroleum such as naphtha, and more specifically. Examples thereof include a mixture composed of n-hexane, 1-hexene, 2-hexene, hexadiene, cyclohexane and the like.

Further, the aromatic compound production catalyst of the present invention is a conversion catalyst having excellent efficiency such as reaction selectivity and productivity by containing the MFI type zeolite, and is, for example, saturated with 2 to 6 carbon atoms. By contacting with an aliphatic hydrocarbon or an alicyclic hydrocarbon, it is possible to efficiently produce an aromatic compound. Examples of the saturated aliphatic hydrocarbon or alicyclic hydrocarbon at that time include ethane, propane, butane, isobutane, pentane, hexane, cyclopropane, cyclobutane, cyclohexane and a mixture thereof.

In the reaction according to the embodiment at that time, the reaction temperature is not particularly limited as long as it is possible to produce an aromatic compound. Among them, the formation of olefins or alkanes is suppressed and the heat resistance is higher than necessary. The temperature range of 400 to 800 ° C. is desirable because it enables an efficient reaction of aromatic compounds that do not require a reactor. Further, the reaction pressure is not limited, and the operation can be performed in a pressure range of, for example, about 0.05 MPa to 5 MPa. The supply of the olefin as a reaction raw material to the aromatic compound production catalyst of the present invention is not particularly limited as the ratio of the volume of the raw material gas to the catalyst volume, and is, for example, a space of about 1h ^{-1 to} 50,000h ^-1. You can increase the speed. When the olefin is supplied as a raw material gas, the olefin is diluted with a single gas, a mixed gas, and a single or mixed gas selected from an inert gas such as nitrogen, hydrogen, carbon monoxide, and carbon dioxide. It can also be used as a thing.

The reaction form is not limited, and for example, a fixed bed, a transport bed, a fluidized bed, a moving bed, a multi-tube reactor, a continuous flow reactor, an intermittent flow reactor, a swing reactor, and the like can be used. A reaction type using a swing reactor is preferable because it is a particularly efficient method for producing an aromatic compound. The aromatic compound production catalyst of the present invention is preferably a catalyst for swing operation because it is excellent in production efficiency of aromatic compounds, long catalyst life, and excellent regeneration resistance.

The aromatic compound to be produced is not particularly limited as long as it belongs to the category called aromatic compound, for example, benzene, toluene, xylene, trimethylbenzene, ethylbenzene, propylbenzene, butylbenzene, naphthalene, etc. Methylnaphthalene and the like can be mentioned, and benzene, toluene and xylene are particularly preferable.

The present invention relates to a catalyst for producing an aromatic compound containing a specific MFI type zeolite, and is particularly long when producing an aromatic compound from an olefin, a saturated aliphatic hydrocarbon, or an alicyclic hydrocarbon. It provides a catalyst for producing an aromatic compound which can have a long life and is suitable for swing operation, and a method for producing an aromatic compound using the catalyst, which is very useful industrially.

Hereinafter, the present invention will be specifically described with reference to Examples.
The MFI-type zeolite and aromatic compound production catalyst used in the examples were measured and defined by the following methods.

~ Measurement of pore distribution, pore diameter, and outer surface area ~
The pore distribution and pore diameter of zeolite were measured by nitrogen adsorption measurement.

As the nitrogen adsorption measurement at that time, a nitrogen adsorption device ((trade name) OMNISORP360CX, manufactured by Beckman Coulter) was used, and both adsorption and desorption were measured under the condition of 30 torr / step. The outer surface area was determined by linearly approximating the range of the thickness (t = 0.6 to 1.0 nm) of the adsorption layer by the t-prot method.

Then, the desorption process of nitrogen adsorption measurement was analyzed by the Barret-Joiner-Halenda method (Journal of the American Chemical Society, 1951, pp. 373-380). The pore distribution curve of the mesopores, which is the differential value of the amount of desorption of The total pore volume of the mesopores was determined by integrating the amount of nitrogen gas desorption in the range of 2 nm or more and 50 nm or less.

Then, among the peaks of the differential value (d (V / m) / d (D)) of the amount of nitrogen gas desorbed from the mesopores at the mesopore diameter value, the largest peak is analyzed by the intensity approximation of the Gaussian function. Then, the mesopores having a diameter within the range (= μ ± 2σ) of twice the standard deviation (2σ) from the center value (μ) of the Gaussian function were defined as uniform mesopores. The pore volume of the uniform mesopores was determined by integrating the amount of nitrogen gas desorption in the range of ± 2σ with reference to the median value (μ).

~ Measurement of average particle size ~
The average particle size was calculated from the outer surface area using the above formula (1). In formula (1), S is the outer surface area (m ² / g) and PD is the average particle size (m). The outer surface area (S (m ² / g)) in the formula (1) was determined by the t-prot method by the nitrogen adsorption method at the temperature of liquid nitrogen.

~ Measurement of SiO ₂ / Al ₂ O ₃ molar ratio ~
For the SiO ₂ / Al ₂ O ₃ molar ratio of zeolite, MFI type zeolite is dissolved in a mixed aqueous solution of hydrofluoric acid and nitric acid, and this is inductively coupled plasma by a general ICP device ((trade name) OPTIMA3300DV, manufactured by PerkinElmer). It was measured and determined by emission spectroscopic analysis (ICP-AES).

~ Measurement of aggregate diameter ~
As the agglomeration diameter, the volume mean diameter (D ₅₀ ) of the agglomeration particle diameter was measured by the dynamic scattering method. A (trade name) Microtrack HRA (Model9320-x100) (manufactured by Nikkiso Co., Ltd.) was used for the measurement. In the measurement, the refractive index of the particles was 1.66, the setting of the particles was transparent non-spherical particles, and the liquid refractive index of the solvent was 1.33.

~ Measurement of powder X-ray diffraction ~
It was measured in the atmosphere using an X-ray diffraction measuring device (manufactured by Spectris, (trade name) X'pert PRO MPD), using CuKα1 as a tube voltage of 45 kV and a tube current of 40 mA. The range of 0.04 to 5 degrees was analyzed at 0.08 degrees / step and 200 seconds / step. In addition, the background corrected by the absorption rate of the direct beam is removed.

The presence or absence of a peak can be visually confirmed, or a peak search program may be used. As the peak search program, a general program can be used. For example, when the measurement results of 2θ (degrees) on the horizontal axis and intensity (a.u.) on the vertical axis are smoothed by the SAVITSKY & GOLAY equation and the Sliding Polynomial filter, and then the second derivative is performed, three or more points are continuous. If there is a negative value, it is determined that there is a peak.

~ Aromatic compound manufacturing equipment and its manufacturing method ~
For the aromatic compound production catalyst obtained in Examples, an aromatic compound was produced by the following method and evaluated.

A swing reactor in which two fixed-bed gas-phase flow reactors using stainless steel reactor tubes (inner diameter 16 mm, length 600 mm) were connected in parallel was used. The middle stage of each of the two stainless steel reaction tubes is filled with an aromatic compound production catalyst, pretreated by heating under dry air flow, and then switched to the two reaction devices at predetermined time intervals. The operation was performed and the raw material gas was alternately fed. While the raw material gas was supplied and reacted by one reaction device (reaction side), air gas was circulated in the other reaction device (regeneration side) to regenerate the aromatic compound production catalyst by coke combustion. The apparatus conditions and operating conditions of the swing reactor are not limited to the conditions described in this embodiment, and can be appropriately selected. Then, a ceramic tube furnace was used for heating, and the temperature of the catalyst layer was controlled. The reaction outlet gas and the reaction solution were collected, and the gas component and the liquid component were analyzed individually using a gas chromatograph. The gas component was analyzed using a gas chromatograph equipped with a TCD detector (manufactured by Shimadzu Corporation, (trade name) GC-1700). As the filler, PorapakQ (trade name) manufactured by Waters or MS-5A (trade name) manufactured by GL Science was used. The liquid components were analyzed using a gas chromatograph equipped with a FID detector (manufactured by Shimadzu Corporation, (trade name) GC-2015). As the separation column, a capillary column (manufactured by GL Science Co., Ltd. (trade name) TC-1) was used.

The reaction conditions were set as follows.

(Aromatic compound production conditions)
Catalyst temperature: 600 ° C.
Distribution gas: Mixed gas of raw material gas 50 mol% + nitrogen 50 mol%, 100 ml / min.
Ratio of raw material gas volume to catalyst volume: 1000 / hour.
Catalyst weight: 1.5 g.
Catalyst shape: MFI-type zeolite powder was molded at 400 kgf / cm ² for 1 minute and then pulverized to obtain a pellet shape of about 1 mm.
Reaction pressure: 0.1 MPa.

(Catalyst regeneration conditions and air purge conditions during swing operation)
Catalyst temperature: 600 ° C.
Flowing gas: Air 50 ml / min.
Ratio of air gas volume to catalyst volume: 1000 / hour.
Pressure: 0.1 MPa.

(Nitrogen purge conditions)
Catalyst temperature: 600 ° C.
Flowing gas: Nitrogen 50 ml / min.
Ratio of nitrogen gas volume to catalyst volume: 1000 / hour.
Pressure: 0.1 MPa.

The MFI-type zeolite was produced with reference to JP2013-227203A.

Example 1
Amorphous aluminosilicate gel was added to an aqueous solution of tetrapropylammonium (hereinafter sometimes abbreviated as TPA) hydroxide and sodium hydroxide and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. The amount of the seed crystal added at that time was 0.7% by weight with respect to the weight of Al ₂ O ₃ and SiO _{2 in} the raw material composition. In addition, the by-produced ethanol was removed by evaporation.

The composition of the raw material composition is as follows.
SiO ₂ / Al ₂ O ₃ molar ratio = 44, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.16, OH / Si molar ratio = 0.21, H ₂ O / Si molar ratio = 10
The obtained raw material composition was sealed in a stainless steel autoclave and crystallized for 4 days with stirring at 115 ° C. to obtain a slurry-like mixed solution. The slurry-like mixed solution after crystallization was solid-liquid separated by a centrifugal sedimentation machine, and then the solid particles were washed with a sufficient amount of pure water and dried at 110 ° C. to obtain a dry powder.

10 g of the obtained dry powder was calcined at 550 ° C. for 1 hour, then exchanged, filtered and washed in 100 ml of a 20 wt% ammonium chloride aqueous solution at 60 ° C. for 20 hours to obtain an ammonium type MFI type zeolite. Then, the ammonium type MFI type zeolite was calcined at 550 ° C. for 1 hour to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 27 nm, a SiO ₂ / Al ₂ O ₃ molar ratio of 40, and an aggregation diameter of 46 μm. The total pore volume of the mesopores present in the obtained MFI-type zeolite was 0.39 ml / g. The mesopore distribution curve in the pore distribution curve had a peak, and the half width of the peak of the uniform mesopore was 9 nm and μ = 16 nm. The pore volume of the uniform mesopores was 0.31 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 78%. Table 1 shows the physical properties of the obtained MFI-type zeolite. Further, in the powder X-ray diffraction of the obtained MFI-type zeolite, there was no peak in the range of 0.1 to 3 degrees, and it was shown that the mesopores were irregularly connected.

The obtained MFI-type zeolite was used as a catalyst for producing an aromatic compound, and ethylene was used as a raw material to produce an aromatic compound under the above conditions. The conditions on the reaction side and the regeneration side of the swing reactor at that time are as follows.

(Reaction side)
The raw material gas was circulated through the reaction tube heated at 600 ° C. for 140 minutes, and then the raw material gas feed was immediately switched toward the reaction tube on the regeneration side.

(Playback side)
At the same time as the raw material gas feed of the reaction tube on the reaction side starts, nitrogen purge (1) is started on the reaction tube on the regeneration side heated at 600 ° C., and nitrogen purge is performed for 30 minutes to make the inside of the reaction tube sufficiently nitrogen atmosphere. Replaced. Then, the supply gas was immediately switched from nitrogen to air, and air was purged for 10 minutes to sufficiently replace the inside of the reaction tube with an air atmosphere. Next, air was circulated for 60 minutes to regenerate the aromatic compound production catalyst. Then, the supply gas was immediately switched from air to nitrogen, and nitrogen purge (2) was performed for 10 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, nitrogen purging (3) was carried out for 30 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Then, the nitrogen gas feed line was immediately switched to the reaction tube on the reaction side, and at the same time, the raw material gas feed was started on the reaction tube on the regeneration side. After that, the same series of processing as above was repeated to continuously obtain a product feed. In the reactions described in the following Examples and Comparative Examples, the operation was carried out in the same procedure, and only the raw material gas flow time, the regeneration treatment time and the nitrogen purge (3) time were changed. Table 2 shows the gas circulation time in each process.

Table 3 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 1395 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 2
Using the MFI-type zeolite obtained in Example 1 as a catalyst for producing an aromatic compound and using propylene as a raw material, a conversion reaction to an aromatic compound was carried out under the above conditions.

Table 2 shows the gas circulation time in each process. Table 4 shows the raw material gas flow time, conversion rate, and yield of each product. Up to the raw material gas flow time of 2295 minutes, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 3
Aluminum hydroxide was dissolved in an aqueous solution of TPA bromide and sodium hydroxide. After adding tetraethoxysilane to the obtained aqueous solution, MFI-type zeolite was added to the aqueous solution as a seed crystal to prepare a raw material composition, and ethanol produced as a by-product was removed by evaporation.

In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 28, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.17, OH / Si molar ratio = 0.17, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 1 to obtain MFI-type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 26 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 26. The total pore volume of the mesopores present in the obtained MFI-type zeolite is 0.42 ml / g, the mesopore distribution curve in the pore distribution curve has a peak, and the peak of the uniform mesopores. The half width was 15 nm and μ = 17 nm. The pore volume of the uniform mesopores was 0.39 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 92%. Table 1 shows the physical properties of the obtained MFI-type zeolite. Further, in the powder X-ray diffraction of the obtained MFI-type zeolite, there was no peak in the range of 0.1 to 3 degrees, and it was shown that the mesopores were irregularly connected.

The obtained MFI-type zeolite was used as a catalyst for producing an aromatic compound, ethylene was used as a raw material, and a conversion reaction to an aromatic compound was carried out under the above conditions.

Table 2 shows the gas circulation time in each process.

Table 5 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 1395 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 4
Using the MFI-type zeolite obtained in Example 3 as a catalyst for producing an aromatic compound, a conversion reaction to an aromatic compound using propylene as a raw material was carried out. The reaction was carried out under the above conditions.

Table 2 shows the gas circulation time in each process. Table 6 shows the raw material gas flow time, conversion rate, and yield of each product. Up to a raw material gas flow time of 2295 minutes, it was possible to continuously obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Comparative Example 1
Aluminum hydroxide was dissolved in an aqueous solution of sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. By-product ethanol was removed by evaporation.

The composition of the raw material composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 48, Na / Si molar ratio = 0.18, OH / Si molar ratio = 0.18, H ₂ O / Si molar ratio = 18
The raw material composition was reacted and treated in the same manner as in Example 1 except that the crystallization temperature was set to 180 ° C. to obtain an MFI-type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 115 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 42. The total pore volume of the mesopores present in the obtained MFI-type zeolite is 0.05 ml / g, and the half width of the peak of the uniform mesopores in the pore distribution curve is 0.3 nm, μ = 4 nm. there were. The pore volume of the uniform mesopores was 0.01 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 26%. Table 1 shows the physical properties of the obtained MFI-type zeolite.

The conversion reaction was carried out under the above conditions using the obtained MFI-type zeolite as a catalyst and ethylene as a raw material.

Table 2 shows the gas circulation time in each process.

Table 7 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 1395 minutes, and it was difficult to say that the production was stable.

Comparative Example 2
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 1 as a catalyst and ethylene as a raw material.

Table 2 shows the gas circulation time in each process.

Table 8 shows the raw material gas flow time, conversion rate, and yield of each product. When the ethylene flow time was 535 minutes, the conversion rate was 51%, the benzene yield was 8 wt%, the toluene yield was 9 wt%, and the xylene yield was 2 wt%, which were inferior in productivity.

Comparative Example 3
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 1 as a catalyst and propylene as a raw material.

Table 2 shows the gas circulation time in each process.

Table 9 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 2295 minutes, and it was difficult to say that the production was stable.

Comparative Example 4
Aluminum hydroxide was dissolved in an aqueous solution of TPA hydroxide and sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. By-product ethanol was removed by evaporation.

In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 59, TPA / Si molar ratio = 0.20, Na / Si molar ratio = 0.06, OH / Si molar ratio = 0.26, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 1 to obtain an MFI-type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 42 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 49. The total pore volume of the mesopores present in the obtained MFI-type zeolite was 0.20 ml / g, and the half width of the peak of the uniform mesopores in the pore distribution curve was 3 nm and μ = 6 nm. .. The pore volume of the uniform mesopores was 0.04 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 23%. Table 1 shows the physical properties of the obtained MFI-type zeolite.

The conversion reaction was carried out under the above conditions using the obtained MFI-type zeolite as a catalyst and ethylene as a raw material.

Table 2 shows the gas circulation time in each process.

Table 10 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 1395 minutes, and it was difficult to say that the production was stable.

Comparative Example 5
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 4 as a catalyst and ethylene as a raw material.

Table 2 shows the gas circulation time in each process.

Table 11 shows the raw material gas flow time, conversion rate, and yield of each product. When the ethylene flow time was 895 minutes, the conversion rate was 52%, the benzene yield was 10 wt%, the toluene yield was 8 wt%, and the xylene yield was 2 wt%, which were inferior in productivity.

Comparative Example 6
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 4 as a catalyst and propylene as a raw material.

Table 2 shows the gas circulation time in each process.

Table 12 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 2295 minutes, and it was difficult to say that the production was stable.

Example 5
Amorphous aluminosilicate gel was added to an aqueous solution of tetrapropylammonium (hereinafter sometimes abbreviated as TPA) hydroxide and sodium hydroxide and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. The amount of the seed crystal added at that time was 0.7% by weight with respect to the weight of Al ₂ O ₃ and SiO _{2 in} the raw material composition. In addition, the by-produced ethanol was removed by evaporation.

The composition of the raw material composition is as follows.
SiO ₂ / Al ₂ O ₃ molar ratio = 44, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.16, OH / Si molar ratio = 0.21, H ₂ O / Si molar ratio = 10
The obtained raw material composition was sealed in a stainless steel autoclave and crystallized for 4 days with stirring at 115 ° C. to obtain a slurry-like mixed solution. The slurry-like mixed solution after crystallization was solid-liquid separated by a centrifugal sedimentation machine, and then the solid particles were washed with a sufficient amount of pure water and dried at 110 ° C. to obtain a dry powder.

10 g of the obtained dry powder was calcined at 550 ° C. for 1 hour, then exchanged, filtered and washed in 100 ml of a 20 wt% ammonium chloride aqueous solution at 60 ° C. for 20 hours to obtain an ammonium type MFI type zeolite. Then, the ammonium type MFI type zeolite was calcined at 550 ° C. for 1 hour to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 26 nm, a SiO ₂ / Al ₂ O ₃ molar ratio of 40, and an aggregation diameter of 46 μm. The total pore volume of the mesopores present in the obtained MFI-type zeolite was 0.40 ml / g. The mesopore distribution curve in the pore distribution curve had a peak, and the half width of the peak of the uniform mesopore was 9 nm and μ = 16 nm. The pore volume of the uniform mesopores was 0.32 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 80%. The physical properties of the obtained MFI-type zeolite are shown in Table 13. Further, in the powder X-ray diffraction of the obtained MFI-type zeolite, there was no peak in the range of 0.1 to 3 degrees, and it was shown that the mesopores were irregularly connected.

The obtained MFI-type zeolite was used as a catalyst for producing an aromatic compound, and n-butane was used as a raw material, and an aromatic compound was produced under the above conditions. The conditions on the reaction side and the regeneration side of the swing reactor at that time are as follows.

(Reaction side)
The raw material gas was circulated for 1000 minutes through the reaction tube heated at 600 ° C., and then the raw material gas feed was immediately switched toward the reaction tube on the regeneration side.

(Playback side)
At the same time as the raw material gas feed of the reaction tube on the reaction side starts, nitrogen purge (1) is started on the reaction tube on the regeneration side heated at 600 ° C., and nitrogen purge is performed for 30 minutes to make the inside of the reaction tube sufficiently nitrogen atmosphere. Replaced. Then, the supply gas was immediately switched from nitrogen to air, and air was purged for 10 minutes to sufficiently replace the inside of the reaction tube with an air atmosphere. Next, air was circulated for 60 minutes to regenerate the aromatic compound production catalyst. Then, the supply gas was immediately switched from air to nitrogen, and nitrogen purge (2) was performed for 10 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, nitrogen purging (3) was carried out for 890 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Then, the nitrogen gas feed line was immediately switched to the reaction tube on the reaction side, and at the same time, the raw material gas feed was started on the reaction tube on the regeneration side. After that, the same series of processing as above was repeated to continuously obtain a product feed. In the reactions described in the following Examples and Comparative Examples, the operation was carried out in the same procedure, and only the raw material gas flow time, the regeneration treatment time and the nitrogen purge (3) time were changed. Table 14 shows the gas circulation time in each process.

Table 15 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 9995 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 6
Using the MFI-type zeolite obtained in Example 5 as a catalyst for producing an aromatic compound and isobutane as a raw material, a conversion reaction to an aromatic compound was carried out under the above conditions.

Table 14 shows the gas circulation time in each process. Table 16 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 9795 minutes of raw material gas flow time, it was possible to obtain a stable product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 7
Using the MFI-type zeolite obtained in Example 5 as a catalyst for producing an aromatic compound and using n-hexane as a raw material, a conversion reaction to an aromatic compound was carried out under the above conditions.

Table 14 shows the gas circulation time in each process. Table 17 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 10495 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 8
Using the MFI-type zeolite obtained in Example 5 as a catalyst for producing an aromatic compound and methylcyclopentane as a raw material, a conversion reaction to an aromatic compound was carried out under the above conditions.

Table 14 shows the gas circulation time in each process. Table 18 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 9995 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 9
Aluminum hydroxide was dissolved in an aqueous solution of TPA bromide and sodium hydroxide. After adding tetraethoxysilane to the obtained aqueous solution, MFI-type zeolite was added to the aqueous solution as a seed crystal to prepare a raw material composition, and ethanol produced as a by-product was removed by evaporation.

In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 28, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.17, OH / Si molar ratio = 0.17, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 1 to obtain MFI-type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 25 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 26. The total pore volume of the mesopores present in the obtained MFI-type zeolite is 0.43 ml / g, the mesopore distribution curve in the pore distribution curve has a peak, and the peak of the uniform mesopores. The half width was 15 nm and μ = 17 nm. The pore volume of the uniform mesopores was 0.40 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 93%. The physical properties of the obtained MFI-type zeolite are shown in Table 13. Further, in the powder X-ray diffraction of the obtained MFI-type zeolite, there was no peak in the range of 0.1 to 3 degrees, and it was shown that the mesopores were irregularly connected.

Using the obtained MFI-type zeolite as a catalyst for producing an aromatic compound and n-butane as a raw material, a conversion reaction to an aromatic compound was carried out under the above conditions.

Table 14 shows the gas circulation time in each process.

Table 19 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 9995 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 10
Using the MFI-type zeolite obtained in Example 9 as a catalyst for producing an aromatic compound, a conversion reaction to an aromatic compound using isobutylene as a raw material was carried out. The reaction was carried out under the above conditions.

Table 14 shows the gas circulation time in each process. Table 20 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 9795 minutes of raw material gas flow time, it was possible to continuously obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 11
Using the MFI-type zeolite obtained in Example 9 as a catalyst for producing an aromatic compound, a conversion reaction to an aromatic compound using n-hexane as a raw material was carried out. The reaction was carried out under the above conditions.

Table 14 shows the gas circulation time in each process. Table 21 shows the raw material gas flow time, conversion rate, and yield of each product. Up to a raw material gas flow time of 10495 minutes, it was possible to continuously obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 12
Using the MFI-type zeolite obtained in Example 9 as a catalyst for producing an aromatic compound, a conversion reaction to an aromatic compound using methylcyclopentane as a raw material was carried out. The reaction was carried out under the above conditions.

Table 14 shows the gas circulation time in each process. Table 22 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 9995 minutes of raw material gas flow time, it was possible to continuously obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Comparative Example 7
Aluminum hydroxide was dissolved in an aqueous solution of sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. By-product ethanol was removed by evaporation.

The composition of the raw material composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 48, Na / Si molar ratio = 0.18, OH / Si molar ratio = 0.18, H ₂ O / Si molar ratio = 18
The raw material composition was reacted and treated in the same manner as in Example 1 except that the crystallization temperature was set to 180 ° C. to obtain an MFI-type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 115 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 42. The total pore volume of the mesopores present in the obtained MFI-type zeolite is 0.05 ml / g, and the half width of the peak of the uniform mesopores in the pore distribution curve is 0.3 nm, μ = 4 nm. there were. The pore volume of the uniform mesopores was 0.01 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 26%. The physical properties of the obtained MFI-type zeolite are shown in Table 13.

The conversion reaction was carried out under the above conditions using the obtained MFI-type zeolite as a catalyst and n-butane as a raw material.

Table 14 shows the gas circulation time in each process.

Table 23 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 9995 minutes, and it was difficult to say that the production was stable.

Comparative Example 8
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 7 as a catalyst and isobutane as a raw material.

Table 14 shows the gas circulation time in each process.

Table 24 shows the raw material gas flow time, conversion rate, and yield of each product. Until the raw material gas flow time was 9795 minutes, the conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range, and it was difficult to say that the production was stable.

Comparative Example 9
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 7 as a catalyst and n-hexane as a raw material.

Table 14 shows the gas circulation time in each process.

Table 25 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 10495 minutes, and it was difficult to say that the production was stable.

Comparative Example 10
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 7 as a catalyst and methylcyclopentane as a raw material.

Table 14 shows the gas circulation time in each process.

Table 26 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 9995 minutes, and it was difficult to say that the production was stable.

Comparative Example 11
Aluminum hydroxide was dissolved in an aqueous solution of TPA hydroxide and sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. By-product ethanol was removed by evaporation.

In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 59, TPA / Si molar ratio = 0.20, Na / Si molar ratio = 0.06, OH / Si molar ratio = 0.26, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 9 to obtain an MFI-type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 42 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 49. The total pore volume of the mesopores present in the obtained MFI-type zeolite was 0.20 ml / g, and the half width of the peak of the uniform mesopores in the pore distribution curve was 3 nm and μ = 6 nm. .. The pore volume of the uniform mesopores was 0.04 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 23%. Table 1 shows the physical properties of the obtained MFI-type zeolite.

The conversion reaction was carried out under the above conditions using the obtained MFI-type zeolite as a catalyst and n-butane as a raw material.

Table 14 shows the gas circulation time in each process.

Table 27 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 9995 minutes, and it was difficult to say that the production was stable.

Comparative Example 12
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 11 as a catalyst and isobutane as a raw material.

Table 14 shows the gas circulation time in each process.

Table 28 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 9795 minutes of raw material gas flow time, the conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range, and it was difficult to say that the production was stable.

Comparative Example 13
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 11 as a catalyst and n-hexane as a raw material.

Table 14 shows the gas circulation time in each process.

Table 29 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 10495 minutes, and it was difficult to say that the production was stable.

Comparative Example 14
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 11 as a catalyst and methylcyclopentane as a raw material.

Table 14 shows the gas circulation time in each process.

Table 30 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 9995 minutes, and it was difficult to say that the production was stable.

Example 13
Amorphous aluminosilicate gel was added to an aqueous solution of tetrapropylammonium (hereinafter sometimes abbreviated as TPA) hydroxide and sodium hydroxide and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. The amount of the seed crystal added at that time was 0.7% by weight with respect to the weight of Al ₂ O ₃ and SiO _{2 in} the raw material composition. In addition, the by-produced ethanol was removed by evaporation.

The composition of the raw material composition is as follows.
SiO ₂ / Al ₂ O ₃ molar ratio = 44, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.16, OH / Si molar ratio = 0.21, H ₂ O / Si molar ratio = 10
The obtained raw material composition was sealed in a stainless steel autoclave and crystallized for 4 days with stirring at 115 ° C. to obtain a slurry-like mixed solution. The slurry-like mixed solution after crystallization was solid-liquid separated by a centrifugal sedimentation machine, and then the solid particles were washed with a sufficient amount of pure water and dried at 110 ° C. to obtain a dry powder.

10 g of the obtained dry powder was calcined at 550 ° C. for 1 hour, then exchanged, filtered and washed in 100 ml of a 20 wt% ammonium chloride aqueous solution at 60 ° C. for 20 hours to obtain an ammonium type MFI type zeolite. Then, the ammonium type MFI type zeolite was calcined at 550 ° C. for 1 hour to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 28 nm, a SiO ₂ / Al ₂ O ₃ molar ratio of 40, and an aggregation diameter of 46 μm. The total pore volume of the mesopores present in the obtained MFI-type zeolite was 0.38 ml / g. The mesopore distribution curve in the pore distribution curve had a peak, and the half width of the peak of the uniform mesopore was 9 nm and μ = 16 nm. The pore volume of the uniform mesopores was 0.30 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 78%. The physical properties of the obtained MFI-type zeolite are shown in Table 31. Further, in the powder X-ray diffraction of the obtained MFI-type zeolite, there was no peak in the range of 0.1 to 3 degrees, and it was shown that the mesopores were irregularly connected.

Using the obtained MFI-type zeolite as a catalyst, an aromatic compound was produced using a mixture of 1-butene 50 mol% and 2-butene 50 mol% as a raw material. The conditions on the reaction side and the regeneration side of the swing reactor at that time were as follows.

(Reaction side)
The raw material gas was circulated through the reaction tube heated at 600 ° C. for 500 minutes, and then the raw material gas feed was immediately switched toward the reaction tube on the regeneration side.

(Playback side)
At the same time as the raw material gas feed of the reaction tube on the reaction side starts, nitrogen purge (1) is started on the reaction tube on the regeneration side heated at 600 ° C., and nitrogen purge is performed for 30 minutes to make the inside of the reaction tube sufficiently nitrogen atmosphere. Replaced. Then, the supply gas was immediately switched from nitrogen to air, and air was purged for 10 minutes to sufficiently replace the inside of the reaction tube with an air atmosphere. Next, air was circulated for 60 minutes to regenerate the catalyst. Then, the supply gas was immediately switched from air to nitrogen, and nitrogen purge (2) was performed for 10 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, nitrogen purging (3) was carried out for 390 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Then, the nitrogen gas feed line was immediately switched to the reaction tube on the reaction side, and at the same time, the raw material gas feed was started on the reaction tube on the regeneration side. After that, the same series of processing as above was repeated to continuously obtain a product feed. In the reactions described in the following Examples and Comparative Examples, the operation was carried out in the same procedure, and only the raw material gas flow time, the regeneration treatment time and the nitrogen purge (3) time were changed. Table 32 shows the gas circulation time in each step.

Table 33 shows the raw material gas flow time, conversion rate, and yield of each product. Up to a raw material gas flow time of 4995 minutes, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 14
Using the MFI-type zeolite obtained in Example 13 as a catalyst for producing an aromatic compound, a mixture of 1-butene 20 mol%, 2-butene 20 mol%, isobutene 20 mol%, n-butane 20 mol%, and isobutane 20 mol% was used as a raw material. The conversion reaction to an aromatic compound was carried out under the above conditions.

Table 32 shows the gas circulation time in each step. Table 34 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 5995 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 15
Using the MFI-type zeolite described in Example 13 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 29 mol%, 2-butene 17 mol%, isobutene 47 mol%, n-butane 5 mol% and isobutane 2 mol% as raw materials. The raw material composition used in this example assumes a mixture obtained by removing 1,3-butadiene from the C4 distillate obtained by ordinary naphtha decomposition.

Table 32 shows the gas circulation time in each step. Table 35 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 5995 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 16
Using the MFI-type zeolite described in Example 13 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 49 mol%, 2-butene 29 mol%, isobutene 10 mol%, n-butane 9 mol% and isobutane 3 mol% as raw materials. The raw material composition used in this example is assumed to be a mixture obtained by removing a part of 1,3-butadiene and isobutylene from the C4 distillate obtained by ordinary naphtha decomposition.

Table 32 shows the gas circulation time in each step. Table 36 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 5995 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 17
Aluminum hydroxide was dissolved in an aqueous solution of TPA bromide and sodium hydroxide. After adding tetraethoxysilane to the obtained aqueous solution, MFI-type zeolite was added to the aqueous solution as a seed crystal to prepare a raw material composition. The generated ethanol was removed by evaporation.

In the above raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 28, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.17, OH / Si molar ratio = 0.17, H ₂ O / Si molar ratio = 10
This raw material composition was reacted and treated in the same manner as in Example 13 to obtain an MFI-type zeolite. The average particle size of the obtained MFI-type zeolite was 27 nm, and the SiO ₂ / Al ₂ O ₃ molar ratio was 26. The total pore volume of the mesopores present in the obtained MFI-type zeolite was 0.41 ml / g.

The half width of the peak of the uniform mesopores in the pore distribution curve of the obtained MFI-type zeolite was 15 nm, and the center value was 17 nm. The pore volume of the uniform mesopores was 0.38 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 92%.

The physical properties of the obtained MFI-type zeolite are shown in Table 31.

Using the obtained MFI-type zeolite as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 50 mol% and 2-butene 50 mol% as a raw material.

Table 2 shows the gas circulation time in each process. Table 37 shows the raw material gas flow time, conversion rate, and yield of each product. Up to a raw material gas flow time of 4995 minutes, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 18
Using the MFI-type zeolite described in Example 17 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 20 mol%, 2-butene 20 mol%, isobutene 20 mol%, n-butane 20 mol% and isobutane 20 mol% as raw materials.

Table 32 shows the gas circulation time in each step. Table 38 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 5995 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 19
Using the MFI-type zeolite described in Example 17 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 29 mol%, 2-butene 17 mol%, isobutene 47 mol%, n-butane 5 mol% and isobutane 2 mol% as raw materials. The raw material composition used in this example is assumed to be a mixture obtained by removing 1,3-butadiene from the C4 distillate of normal naphtha decomposition.

Table 32 shows the gas circulation time in each step. Table 39 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 5995 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 20
Using the MFI-type zeolite described in Example 17 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 49 mol%, 2-butene 29 mol%, isobutene 10 mol%, n-butane 9 mol% and isobutane 3 mol% as raw materials. The raw material composition used in this example is assumed to be a mixture obtained by removing a part of 1,3-butadiene and isobutylene from the C4 distillate of normal naphtha decomposition.

Table 32 shows the gas circulation time in each step. Table 40 shows the raw material gas flow time, conversion rate, and yield of each product. Up to 5995 minutes of raw material gas flow time, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Comparative Example 15
Aluminum hydroxide was dissolved in an aqueous solution of sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. The generated ethanol was removed by evaporation.

In the above raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 48, Na / Si molar ratio = 0.18, OH / Si molar ratio = 0.18, H2O / Si molar ratio = 18
This raw material composition was reacted and treated in the same manner as in Example 1 except that the crystallization temperature was set to 180 ° C. to obtain an MFI-type zeolite. The average particle size of the obtained MFI-type zeolite was 115 nm, and the SiO ₂ / Al ₂ O ₃ molar ratio was 42. The total pore volume of the mesopores present in the obtained MFI-type zeolite was 0.05 ml / g.

The half width of the peak of the uniform mesopores in the pore distribution curve of the obtained MFI-type zeolite was 0.3 nm, and the center value was 4 nm. The pore volume of the uniform mesopores was 0.01 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 26%.

The physical properties of the obtained MFI-type zeolite are shown in Table 31.

Using the obtained MFI-type zeolite as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 50 mol% and 2-butene 50 mol% as a raw material.

Table 32 shows the gas circulation time in each step.

Table 41 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 4995 minutes, and it was difficult to say that the production was stable.

Comparative Example 16
Using the MFI-type zeolite described in Comparative Example 15 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 20 mol%, 2-butene 20 mol%, isobutene 20 mol%, n-butane 20 mol% and isobutane 20 mol% as raw materials.

Table 32 shows the gas circulation time in each step.

Table 42 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 5995 minutes, and it was difficult to say that the production was stable.

Comparative Example 17
Using the MFI-type zeolite described in Comparative Example 15 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 29 mol%, 2-butene 17 mol%, isobutene 47 mol%, n-butane 5 mol% and isobutane 2 mol% as raw materials.

Table 32 shows the gas circulation time in each step.

The raw material gas flow time, conversion rate, and yield of each product are shown in Table 43. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 5995 minutes, and it was difficult to say that the production was stable.

Comparative Example 18
Using the MFI-type zeolite described in Comparative Example 15 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 49 mol%, 2-butene 29 mol%, isobutene 10 mol%, n-butane 9 mol% and isobutane 3 mol% as raw materials.

Table 32 shows the gas circulation time in each step.

Table 44 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 5995 minutes, and it was difficult to say that the production was stable.

Comparative Example 19
Aluminum hydroxide was dissolved in an aqueous solution of TPA hydroxide and sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. The generated ethanol was removed by evaporation.

In the above raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 59, TPA / Si molar ratio = 0.20, Na / Si molar ratio = 0.06, OH / Si molar ratio = 0.26, H ₂ O / Si molar ratio = 10
This raw material composition was reacted and treated in the same manner as in Example 13 to obtain an MFI-type zeolite. The average particle size of the obtained MFI-type zeolite was 42 nm, and the SiO ₂ / Al ₂ O ₃ molar ratio was 49. The total pore volume of the mesopores present in the obtained MFI-type zeolite was 0.20 ml / g.

The half width of the peak of the uniform mesopores in the pore distribution curve of the obtained MFI-type zeolite was 3 nm, and the center value was 6 nm. The pore volume of the uniform mesopores was 0.04 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 23%.

The physical properties of the obtained MFI-type zeolite are shown in Table 31.

Using the obtained MFI-type zeolite as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 50 mol% and 2-butene 50 mol% as a raw material.

Table 32 shows the gas circulation time in each step.

The raw material gas flow time, conversion rate, and yield of each product are shown in Table 45. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 4995 minutes, and it was difficult to say that the production was stable.

Comparative Example 20
Using the MFI-type zeolite described in Comparative Example 19 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 20 mol%, 2-butene 20 mol%, isobutene 20 mol%, n-butane 20 mol% and isobutane 20 mol% as raw materials.

Table 32 shows the gas circulation time in each step.

The raw material gas flow time, conversion rate, and yield of each product are shown in Table 46. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 5995 minutes, and it was difficult to say that the production was stable.

Comparative Example 21
Using the MFI-type zeolite described in Comparative Example 19 as a catalyst, a conversion reaction was carried out using a mixture of 1-butene 29 mol%, 2-butene 17 mol%, isobutene 47 mol%, n-butane 5 mol% and isobutane 2 mol% as raw materials.

Table 32 shows the gas circulation time in each step.

The raw material gas flow time, conversion rate, and yield of each product are shown in Table 47. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 5995 minutes, and it was difficult to say that the production was stable.

Comparative Example 22
Using the MFI-type zeolite described in Comparative Example 19 as a catalyst, a conversion reaction was carried out using a mixture of 49 mol% of 1-butene, 29 mol% of 2-butene, 10 mol% of isobutene, 9 mol% of n-butane and 3 mol% of isobutane as raw materials.

Table 32 shows the gas circulation time in each step.

Table 48 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 5995 minutes, and it was difficult to say that the production was stable.

Example 21
Amorphous aluminosilicate gel was added to an aqueous solution of tetrapropylammonium (hereinafter sometimes abbreviated as TPA) hydroxide and sodium hydroxide and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. The amount of the seed crystal added at that time was 0.7% by weight with respect to the weight of Al ₂ O ₃ and SiO _{2 in} the raw material composition. In addition, the by-produced ethanol was removed by evaporation.

The composition of the raw material composition is as follows.
SiO ₂ / Al ₂ O ₃ molar ratio = 44, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.16, OH / Si molar ratio = 0.21, H ₂ O / Si molar ratio = 10
The obtained raw material composition was sealed in a stainless steel autoclave and crystallized for 4 days with stirring at 115 ° C. to obtain a slurry-like mixed solution. The slurry-like mixed solution after crystallization was solid-liquid separated by a centrifugal sedimentation machine, and then the solid particles were washed with a sufficient amount of pure water and dried at 110 ° C. to obtain a dry powder.

10 g of the obtained dry powder was calcined at 550 ° C. for 1 hour, then exchanged, filtered and washed in 100 ml of a 20 wt% ammonium chloride aqueous solution at 60 ° C. for 20 hours to obtain an ammonium type MFI type zeolite. Then, the ammonium type MFI type zeolite was calcined at 550 ° C. for 1 hour to obtain an MFI type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 26 nm, a SiO ₂ / Al ₂ O ₃ molar ratio of 40, and an aggregation diameter of 46 μm. The total pore volume of the mesopores present in the obtained MFI-type zeolite was 0.39 ml / g. The mesopore distribution curve in the pore distribution curve had a peak, and the half width of the peak of the uniform mesopore was 9 nm and μ = 16 nm. The pore volume of the uniform mesopores was 0.31 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 79%. The physical properties of the obtained MFI-type zeolite are shown in Table 49. Further, in the powder X-ray diffraction of the obtained MFI-type zeolite, there was no peak in the range of 0.1 to 3 degrees, and it was shown that the mesopores were irregularly connected.

Using the obtained MFI-type zeolite as a catalyst for producing an aromatic compound and using 50 mol% of 1-hexene and 50 mol% of 2-hexene as raw materials, an aromatic compound was produced under the above conditions. The conditions on the reaction side and the regeneration side of the swing reactor at that time are as follows.

(Reaction side)
The raw material gas was circulated for 430 minutes through the reaction tube heated at 600 ° C., and then the raw material gas feed was immediately switched toward the reaction tube on the regeneration side.

(Playback side)
At the same time as the raw material gas feed of the reaction tube on the reaction side starts, nitrogen purge (1) is started on the reaction tube on the regeneration side heated at 600 ° C., and nitrogen purge is performed for 30 minutes to make the inside of the reaction tube sufficiently nitrogen atmosphere. Replaced. Then, the supply gas was immediately switched from nitrogen to air, and air was purged for 10 minutes to sufficiently replace the inside of the reaction tube with an air atmosphere. Next, air was circulated for 60 minutes to regenerate the aromatic compound production catalyst. Then, the supply gas was immediately switched from air to nitrogen, and nitrogen purge (2) was performed for 10 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Subsequently, nitrogen purging (3) was carried out for 320 minutes to sufficiently replace the inside of the reaction tube with a nitrogen atmosphere. Then, the nitrogen gas feed line was immediately switched to the reaction tube on the reaction side, and at the same time, the raw material gas feed was started on the reaction tube on the regeneration side. After that, the same series of processing as above was repeated to continuously obtain a product feed. In the reactions described in the following Examples and Comparative Examples, the operation was carried out in the same procedure, and only the raw material gas flow time and the nitrogen purge (3) time were changed. Table 50 shows the gas circulation time in each process.

The raw material gas flow time, conversion rate, and yield of each product are shown in Table 51. Up to a raw material gas flow time of 4295 minutes, it was possible to obtain a stable product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 22
Using the MFI-type zeolite obtained in Example 21 as a catalyst for producing an aromatic compound and using a mixture of 1-hexene 50 mol% and 3-hexene 50 mol% as a raw material, a conversion reaction to an aromatic compound was carried out under the above conditions. It was.

Table 50 shows the gas circulation time in each process. Table 52 shows the raw material gas flow time, conversion rate, and yield of each product. Up to a raw material gas flow time of 4195 minutes, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 23
Using the MFI-type zeolite obtained in Example 21 as a catalyst for producing an aromatic compound and using a mixture of 50 mol% 1-hexene and 50 mol% n-hexane as a raw material, a conversion reaction to an aromatic compound was carried out under the above conditions. It was.

Table 50 shows the gas circulation time in each process. Table 53 shows the raw material gas flow time, conversion rate, and yield of each product. Up to the raw material gas flow time of 7295 minutes, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 24
Using the MFI-type zeolite obtained in Example 21 as a catalyst for producing an aromatic compound and using a mixture of 50 mol% n-hexane and 50 mol% cyclohexane as a raw material, a conversion reaction to an aromatic compound was carried out under the above conditions.

Table 50 shows the gas circulation time in each process. The raw material gas flow time, conversion rate, and yield of each product are shown in Table 54. Up to a raw material gas flow time of 8895 minutes, it was possible to stably obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 25
Aluminum hydroxide was dissolved in an aqueous solution of TPA bromide and sodium hydroxide. After adding tetraethoxysilane to the obtained aqueous solution, MFI-type zeolite was added to the aqueous solution as a seed crystal to prepare a raw material composition, and ethanol produced as a by-product was removed by evaporation.

In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 28, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.17, OH / Si molar ratio = 0.17, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 21 to obtain MFI-type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 26 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 26. The total pore volume of the mesopores present in the obtained MFI-type zeolite is 0.42 ml / g, the mesopore distribution curve in the pore distribution curve has a peak, and the peak of the uniform mesopores. The half width was 15 nm and μ = 17 nm. The pore volume of the uniform mesopores was 0.39 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 91%. Table 1 shows the physical properties of the obtained MFI-type zeolite. Further, in the powder X-ray diffraction of the obtained MFI-type zeolite, there was no peak in the range of 0.1 to 3 degrees, and it was shown that the mesopores were irregularly connected.

The obtained MFI-type zeolite was used as a catalyst for producing an aromatic compound, and a mixture of 1-hexene 50 mol% and 2-hexene 50 mol% was used as a raw material, and a conversion reaction to an aromatic compound was carried out under the above conditions.

Table 50 shows the gas circulation time in each process.

Table 55 shows the raw material gas flow time, conversion rate, and yield of each product. Up to a raw material gas flow time of 4295 minutes, it was possible to obtain a stable product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 26
Using the MFI-type zeolite obtained in Example 25 as a catalyst for producing an aromatic compound, a conversion reaction to an aromatic compound was carried out using a mixture of 1-hexene 50 mol% and 3-hexene 50 mol% as a raw material. The reaction was carried out under the above conditions.

Table 50 shows the gas circulation time in each process. Table 56 shows the raw material gas flow time, conversion rate, and yield of each product. Up to a raw material gas flow time of 4195 minutes, it was possible to continuously obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 27
Using the MFI-type zeolite obtained in Example 25 as a catalyst for producing an aromatic compound, a conversion reaction to an aromatic compound was carried out using a mixture of 50 mol% 1-hexene and 50 mol% n-hexane as a raw material. The reaction was carried out under the above conditions.

Table 50 shows the gas circulation time in each process. The raw material gas flow time, conversion rate, and yield of each product are shown in Table 57. Up to the raw material gas flow time of 7295 minutes, it was possible to continuously obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Example 28
Using the MFI-type zeolite obtained in Example 25 as a catalyst for producing an aromatic compound, a conversion reaction was carried out using 50 mol% of n-hexane and 50 mol% of cyclohexane as raw materials for an aromatic compound. The reaction was carried out under the above conditions.

Table 50 shows the gas circulation time in each process. Table 58 shows the raw material gas flow time, conversion rate, and yield of each product. Up to a raw material gas flow time of 8895 minutes, it was possible to continuously obtain a product feed without significantly reducing the conversion rate, benzene yield, toluene yield, and xylene yield.

Comparative Example 23
Aluminum hydroxide was dissolved in an aqueous solution of sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. By-product ethanol was removed by evaporation.

The composition of the raw material composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 48, Na / Si molar ratio = 0.18, OH / Si molar ratio = 0.18, H2O / Si molar ratio = 18
The raw material composition was reacted and treated in the same manner as in Example 21 except that the crystallization temperature was set to 180 ° C. to obtain an MFI-type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 115 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 42. The total pore volume of the mesopores present in the obtained MFI-type zeolite is 0.05 ml / g, and the half width of the peak of the uniform mesopores in the pore distribution curve is 0.3 nm, μ = 4 nm. there were. The pore volume of the uniform mesopores was 0.01 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 26%. The physical properties of the obtained MFI-type zeolite are shown in Table 49.

Using the obtained MFI-type zeolite as a catalyst and using a mixture of 1-hexene 50 mol% and 2-hexene 50 mol% as a raw material, a conversion reaction was carried out under the above conditions.

Table 50 shows the gas circulation time in each process.

Table 59 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 4295 minutes, and it was difficult to say that the production was stable.

Comparative Example 24
The conversion reaction was carried out under the above-mentioned conditions using the MFI-type zeolite obtained in Comparative Example 23 as a catalyst and a mixture of 1-hexene 50 mol% and 3-hexene 50 mol% as a raw material.

Table 50 shows the gas circulation time in each process.

Table 60 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a range of constant values until the raw material gas flow time was 4195 minutes, and it was difficult to say that the production was stable.

Comparative Example 25
Using the MFI-type zeolite obtained in Comparative Example 23 as a catalyst and a mixture of 1-hexene 50 mol% and n-hexane 50 mol% as a raw material, a conversion reaction was carried out under the above conditions.

Table 50 shows the gas circulation time in each process.

The raw material gas flow time, conversion rate, and yield of each product are shown in Table 61. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 7295 minutes, and it was difficult to say that the production was stable.

Comparative Example 26
The conversion reaction was carried out under the above-mentioned conditions using the MFI-type zeolite obtained in Comparative Example 23 as a catalyst and n-hexane 50 mol% and cyclohexane 50 mol% as raw materials.

Table 50 shows the gas circulation time in each process.

The raw material gas flow time, conversion rate, and yield of each product are shown in Table 62. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 8895 minutes, and it was difficult to say that the production was stable.

Comparative Example 27
Aluminum hydroxide was dissolved in an aqueous solution of TPA hydroxide and sodium hydroxide. Tetraethoxysilane was added to the obtained aqueous solution and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. By-product ethanol was removed by evaporation.

In the raw material composition, the composition is as follows.

SiO ₂ / Al ₂ O ₃ molar ratio = 59, TPA / Si molar ratio = 0.20, Na / Si molar ratio = 0.06, OH / Si molar ratio = 0.26, H ₂ O / Si molar ratio = 10
The raw material composition was reacted and treated in the same manner as in Example 21 to obtain an MFI-type zeolite.

The obtained MFI-type zeolite had an average particle diameter of 42 nm and a SiO ₂ / Al ₂ O ₃ molar ratio of 49. The total pore volume of the mesopores present in the obtained MFI-type zeolite was 0.20 ml / g, and the half width of the peak of the uniform mesopores in the pore distribution curve was 3 nm and μ = 6 nm. .. The pore volume of the uniform mesopores was 0.04 ml / g, and the ratio of the pore volume of the uniform mesopores to the total pore volume of the mesopores was 23%. The physical properties of the obtained MFI-type zeolite are shown in Table 49.

Using the obtained MFI-type zeolite as a catalyst and a mixture of 1-hexene 50 mol% and 2-hexene 50 mol% as a raw material, a conversion reaction was carried out under the above conditions.

Table 50 shows the gas circulation time in each process.

Table 63 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 4295 minutes, and it was difficult to say that the production was stable.

Comparative Example 28
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 27 as a catalyst and a mixture of 1-hexene 50 mol% and 3-hexene 50 mol% as a raw material.

Table 50 shows the gas circulation time in each process.

Table 64 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 4195 minutes, and it was difficult to say that the production was stable.

Comparative Example 29
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 27 as a catalyst and a mixture of 1-hexene 50 mol% and n-hexane 50 mol% as a raw material.

Table 50 shows the gas circulation time in each process.

Table 65 shows the raw material gas flow time, conversion rate, and yield of each product. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas circulation time was 7295 minutes, and it was difficult to say that the production was stable.

Comparative Example 30
The conversion reaction was carried out under the above conditions using the MFI-type zeolite obtained in Comparative Example 27 as a catalyst and n-hexane 50 mol% and cyclohexane 50 mol% as raw materials.

Table 50 shows the gas circulation time in each process.

The raw material gas flow time, conversion rate, and yield of each product are shown in Table 66. The conversion rate, benzene yield, toluene yield, and xylene yield were repeatedly increased and decreased within a certain range until the raw material gas flow time was 8895 minutes, and it was difficult to say that the production was stable.

The catalyst for producing an aromatic compound of the present invention contains an MFI-type zeolite characterized by mesopores, so that an aromatic compound can be obtained from a hydrocarbon raw material such as a lower olefin, a saturated aliphatic hydrocarbon, or an alicyclic hydrocarbon. It is industrially very useful because it exhibits a specific long catalyst life, is excellent in productivity, and enables a stable production method.

Claims (5)

The MFI-type zeolite that satisfies the characteristics shown in the following (i) ~ (iii) in including aromatic compound production catalyst, by contacting a hydrocarbon mixture having 4 carbon atoms and / or 6 of the hydrocarbon mixture carbon, aromatic When the compound is produced, it is characterized in that a plurality of reaction fields having an aromatic compound production catalyst are used, and the aromatic compound is produced by a swing operation in which the aromatic compound production catalyst is regenerated in at least one air-filled reaction field. A method for producing an aromatic compound .
(I) The mesopore distribution curve has a peak, the full width at half maximum (hw) of the peak is hw ≦ 20 nm, and the center value (μ) of the peak is 10 nm ≦ μ ≦ 20 nm, which corresponds to the peak. It has a mesopore group in which the mesopore volume (pv) of the mesopores is 0.05 ml / g ≦ pv.
(Ii) There is no peak in the range of 0.1 to 3 degrees in the powder X-ray diffraction measurement with the diffraction angle set to 2θ.
(Iii) The average particle size (PD) is PD ≦ 100 nm. The characteristic that the aromatic compound production catalyst has a mesopore group in which the ratio (pvr) of the pore volume to the total mesopore volume of pv shown in (i) above is 30% ≤ pvr ≤ 100%. The method for producing an aromatic compound according to claim 1, further comprising MFI-type zeolite that further satisfies the above. A claim comprising contacting a hydrocarbon mixture having 4 carbon atoms and / or a hydrocarbon mixture having 6 carbon atoms at a reaction temperature of 400 to 600 ° C., a reaction pressure of 0.05 to 5 MPa, and a space velocity of ¹ to 50,000 h- ^1. The method for producing an aromatic compound according to 1 or 2. The method for producing an aromatic compound according to any one of claims 1 to 3, wherein the hydrocarbon mixture having 4 carbon atoms and / or the hydrocarbon mixture having 6 carbon atoms is a fraction produced by thermal decomposition of naphtha. .. The method for producing an aromatic compound according to any one of claims 1 to 4, wherein the aromatic compound contains at least one of the group consisting of benzene, toluene, and xylene .