JP2021030175A - Pb-CONTAINING ZEOLITE CATALYST FOR ETHYLATION - Google Patents

Abstract

To provide a catalyst that has excellent reaction selectivity and/or catalyst life while having a certain catalytic activity to the ethylation of an aromatic hydrocarbon in which an aromatic hydrocarbon and ethane are used as source materials.SOLUTION: A Pb-containing zeolite catalyst for the ethylation of an aromatic hydrocarbon contains MFI zeolite, and Pb supported on the MFI zeolite.SELECTED DRAWING: None

Description

The present disclosure relates to Pb-containing zeolite catalysts, particularly Pb-containing zeolite catalysts used for ethylation of aromatic hydrocarbons and ethane-based aromatic hydrocarbons.

Ethylation of aromatic hydrocarbons is important in the industrial production of various useful compounds. For example, ethylbenzene obtained by ethylizing benzene is useful as a polystyrene raw material. As a method of ethylating an aromatic hydrocarbon, there is a method of reacting ethylene with an aromatic hydrocarbon. However, dehydrogenation of ethane is required to industrially produce ethylene, and a decrease in selectivity due to carbon precipitation can be a problem. Therefore, if ethylation of aromatic hydrocarbons can be achieved from ethane and aromatic hydrocarbons without using ethylene as a raw material, it may be industrially advantageous from the viewpoint of total cost. Also, from the viewpoint of the amount of raw materials supplied, it is desirable that ethane and aromatic hydrocarbons can be directly reacted to achieve ethylation. Non-Patent Document 1 describes that the combination of Pt and MFI is active in the reaction of ethane and benzene.

D. Lukyanov et al., J. Catal., 257, 382 (2008)

However, in order to put the catalyst into practical use, the reaction selectivity and / or the catalyst life is required at a high level, and the performance of the conventional catalyst is not always sufficient.

This disclosure has been made in view of such circumstances. A main object of the present disclosure is to provide a catalyst having a certain catalytic activity for the ethylation reaction of aromatic hydrocarbons and ethane-based aromatic hydrocarbons, while having excellent reaction selectivity and / or catalytic life. To provide.

One embodiment of the present disclosure is:
[Item 1]
MFI-type zeolite and Pb supported on the MFI-type zeolite
A Pb-containing zeolite catalyst for an ethylation reaction using ethane and an aromatic hydrocarbon as a raw material, wherein the aromatic hydrocarbon has the following formula (I):
C ₆ (CH ₃ ) _x (C ₂ H ₅ ) _y (H) _{6- (x + y)} (I)
(In the formula, C ₆ is a hexavalent group obtained by removing 6 hydrogen atoms from benzene, x is an integer of 0 to 5, y is an integer of 0 to 5, and x + y is 0 to 0. (It is an integer of 5)
Pb-containing zeolite catalyst represented by.
[Item 2]
Item 2. The Pb-containing zeolite catalyst according to Item 1, wherein the product of the ethylation reaction contains ethylbenzene.
[Item 3]
Item 2. The Pb-containing zeolite catalyst according to Item 1 or 2, wherein the Al content is 0.1 mol / kg or more.
[Item 4]
Item 2. The Pb-containing zeolite catalyst according to any one of Items 1 to 3, wherein the Pb content is 0.1 mol / kg or more.
[Item 5]
Item 2. The Pb-containing zeolite catalyst according to any one of Items 1 to 4, wherein the molar ratio of Pb to Al (Pb / Al (mol%)) is 25 mol% or more and 80 mol% or less.
[Item 6]
Item 8. The method for producing a Pb-containing zeolite catalyst according to any one of Items 1 to 5, wherein Pb is supported by an impregnation method or an ion exchange method.
[Item 7]
Pb respect NH ₄ type MFI zeolite is supported, the production method of the Pb-containing zeolite catalyst according to claim 6.
[Item 8]
A method for producing a product by an ethyling reaction, using the Pb-containing zeolite catalyst according to any one of Items 1 to 5 or the Pb-containing zeolite catalyst produced by the production method according to Item 6 or 7.

The catalyst in the present disclosure is excellent in reaction selectivity and / or catalyst life while having a certain catalytic activity for the ethylation reaction of aromatic hydrocarbons and ethane-based aromatic hydrocarbons. Further, the catalyst in the present disclosure does not require a noble metal catalyst and can be produced at low cost.

The schematic diagram of the catalytic reaction apparatus in one Embodiment of this disclosure is shown. The average yield when different supported metals are used in one embodiment of the present disclosure is shown. The time course of the yield when Pt-MFI or Pb-MFI is used in one embodiment of the present disclosure is shown. The average yield when carriers having different skeletal structures are used in one embodiment of the present disclosure is shown. In one embodiment of the present disclosure, the average yield when the Al content is changed by using different carriers of _{SiO 2} / Al ₂ O _{3 under a constant Pb / Al is shown.} In one embodiment of the present disclosure, the average yield when the amount of Pb supported is changed under a constant Al content is shown. Shown as MFI-type zeolite, in the case of using NH ₄ form, the average yield of the case of using the Na type.

<Pb-containing zeolite catalyst>
The Pb-containing zeolite catalyst in the present disclosure includes an MFI-type zeolite and Pb supported on the zeolite.

[MFI type zeolite]
“MFI-type zeolite” refers to an aluminosilicate compound belonging to the structure code MFI defined by the International Zeolite Society. Examples of MFI-type zeolites include ZSM-5, TS-1, TSZ, SSI-10, USC-4 and NU-4. The method for producing MFI-type zeolite is not limited, and it can be produced by a known method. Commercially available MFI-type zeolite may be used.

[Supported Pb]
The Pb supported on the MFI-type zeolite in the present disclosure is a cation, preferably Pb ²⁺ . The Pb cation may form an ion pair with the anion center in the zeolite skeleton. The Pb cation may be supported on the zeolite without forming an ion pair with the anion center in the zeolite skeleton. In this case, the Pb-containing zeolite catalyst may have an anion other than the anion center in the zeolite skeleton.

[Al content]
From the viewpoint of catalytic activity, the Al content of the Pb-containing zeolite catalyst is 0.1 mol / kg or more, 0.3 mol / kg or more, 0.5 mol / kg or more, 0.7 mol / kg or more, 0.9 mol / kg or more, It may be 1.1 mol / kg or more, 1.3 mol / kg or more, or 1.5 mol / kg or more, preferably 0.2 mol / kg or more, more preferably 0.6 mol / kg or more, still more preferably 1.0 mol. / Kg or more. The Al content of the Pb-containing zeolite catalyst may be 5 mol / kg, 2.5 mol / kg or less, or 1.5 mol / kg or less. In addition, Al here means Al in a zeolite skeleton.

[Pb content]
From the viewpoint of catalytic activity, the Pb content of the Pb-containing zeolite catalyst is 0.1 mol / kg or more, 0.3 mol / kg or more, 0.5 mol / kg or more, 0.7 mol / kg or more, 0.9 mol / kg or more, It may be 1.1 mol / kg or more, preferably 0.25 mol / kg or more, and more preferably 0.55 mol / kg or more. The Pb content of the Pb-containing zeolite catalyst may be 4 mol / kg or less, 2.0 mol / kg or less, and 1.5 mol / kg or less from the viewpoint of catalytic activity. When the Pb content is in the above range, better catalytic activity can be obtained.

[Pb / Al]
The molar ratio (Pb / Al (mol%)) of Pb to Al of the Pb-containing zeolite catalyst may be 10 mol% or more, 20 mol% or more, 30 mol% or more, or 35 mol% or more, preferably 25 mol% or more, and more. It is preferably 30 mol% or more. Further, Pb / Al may be 300 mol% or less, 250 mol% or less, 200 mol% or less, 150 mol% or less, 100 mol% or 75 mol% or less, preferably 120 mol% or less, more preferably 80 mol% or less, still more preferably. It is 60 mol% or less. In addition, Al here means Al in a zeolite skeleton. When Pb / Al is in the above range, better catalytic activity can be obtained.

[SiO ₂ / Al ₂ O ₃ ]
The molar ratio _{of SiO 2} to Al ₂ O _{3 (SiO 2} / Al ₂ O ₃ (mol%)) in the Pb-containing zeolite catalyst may be 1 or more, 5 or more, or 10 or more. _{Further, the SiO 2} / Al ₂ O ₃ in the Pb-containing zeolite catalyst may be 2000 or less, 1000 or less, 100 or less, 75 or less, 50 or less or 20 or less, and preferably 200 or less or 30 or less. Further, SiO ₂ / Al ₂ O ₃ may be 2000 or less, 1000 or less, 100 or less, 75 or less, 50 or less or 20 or less, and preferably 200 or less or 30 or less. When SiO ₂ / Al ₂ O ₃ is in the above range, better catalytic activity can be obtained.

[Other ionic components]
The Pb-containing zeolite catalyst may contain other cations other than the Pb cation. The other cation may be a cation supported on the MFI-type zeolite before supporting Pb. Other cations may be from the point of view of catalytic activity contain NH ₄ ⁺ or H ⁺ and the like proton cation. The Pb-containing zeolite catalyst may contain Bronsted acid points. Cation after ion exchange treatment in general NH ₄ ^+, by sintering, NH ₃ is desorbed zeolite is a proton type as a gas. When the zeolite contains protons, the protons are bonded to oxygen ions crosslinked with Al and Si and are present on the solid surface as crosslinked hydroxy groups. This crosslinked hydroxy group can be the Bronsted acid point. The amount of the protonic cation may be 30 mol% or more, 50 mol% or more, 70 mol% or more, or 90 mol% or more with respect to the total amount of other cations. The Pb-containing zeolite catalyst may contain anions other than the anion center in the zeolite skeleton, but may be anions in the Pb salt solution at the time of zeolite preparation. Specific examples of the anion contained in the Pb-containing zeolite catalyst include hydroxide ion, nitrate ion and halide ion.

[Shape of Pb-containing zeolite catalyst]
The particle size of the Pb-containing zeolite catalyst may be 1 cm or less, 1 mm or less, or 100 μm or less. The particle size referred to here may be a volume-based center particle size (D ₅₀ ) obtained by using a laser diffraction type particle size distribution measuring device. The shape of the Pb-containing zeolite catalyst may be beads, pellets, powder, or the like.

[Other ingredients]
The Pb-containing zeolite catalyst is an inorganic binder containing alumina, silica, zirconia, zeolite and the like; an organic binder containing a carbide-based, hydrocarbon-based, and polymer-based compound; and other additives as long as the effects of the present disclosure are not impaired. It may be used in combination.

<Preparation method of Pb-containing zeolite catalyst>
The Pb-containing zeolite catalyst can be prepared by supporting Pb on an MFI-type zeolite. Examples of the method for supporting Pb include an impregnation method (IMP method) or an ion exchange method (IE method). Generally, when prepared by the impregnation method, a metal is supported not only at the ion exchange site but also at the ion exchange site. On the other hand, in the catalyst prepared by the ion exchange method, the metal is basically supported only on the ion exchange site. By adjusting the concentration of the Pb salt solution, it is possible to adjust the Pb content in the Pb-containing zeolite catalyst.

[Immersion method]
As the impregnation method, a known method can be used. For example, an aqueous solution containing Pb salts of nitrates (e.g., concentration of 0.01 wt% to 10 wt%) was added Na-type zeolite or NH ₄ form or the like of the zeolite, 25 to 100 ° C. (e.g., 50 to 95 ° C. ), Stir until the water is gone. Then, for example, it is dried by heating at 100 to 200 ° C. for 1 to 10 hours. In the Pb-containing catalyst prepared by the impregnation method, it is presumed that the Pb cation is present in other than the ion exchange site.

[Ion exchange method]
As the ion exchange method, a known method can be used. For example, an aqueous solution containing Pb salts of nitrates (e.g., concentration of 0.01 wt% to 10 wt%) was prepared, added Na-type zeolite or NH ₄ zeolite, temperatures of 25 to 100 ° C. (e.g., 50 After stirring at (~ 95 ° C.) for a predetermined time (for example, 1 minute to 30 hours, preferably 30 minutes to 6 hours), ion exchange can be performed by filtering, washing with ion-exchanged water, and removing excess salts and the like. it can. Then, for example, it is dried by heating at 100 to 200 ° C. for 1 to 10 hours.

<Ethylation reaction of aromatic hydrocarbons>
The catalyst in the present disclosure is useful for the ethylation reaction of aromatic hydrocarbons and ethane-based aromatic hydrocarbons. "Ethylation of aromatic hydrocarbons" as used in the present disclosure means that at least one aromatic ring hydrogen contained in an aromatic hydrocarbon is substituted with an ethyl group. The Pb-containing zeolite catalyst in the present disclosure has good reaction selectivity and catalyst life in the ethylation reaction of an aromatic compound using ethane and an aromatic compound as raw materials.

The aromatic hydrocarbon has the following formula (I):
C ₆ (CH ₃ ) _x (C ₂ H ₅ ) _y (H) _{6- (x + y)} (I)
(In the formula, C ₆ is a hexavalent group obtained by removing 6 hydrogen atoms from benzene, x is an integer of 0 to 5, y is an integer of 0 to 5, and x + y is 0 to 0. (It is an integer of 5)
It is represented by. x is preferably an integer from 0 to 3. y is preferably an integer from 0 to 3.
Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and ethylbenzene.

The reaction product is an ethylened aromatic hydrocarbon in which at least one (for example, one) of aromatic ring hydrogen is substituted with an ethyl group. Specific examples of ethylated aromatic hydrocarbons include ethylbenzene, ethyltoluene, ethylxylene and diethylbenzene. It should be noted that the ethylened aromatic hydrocarbons can be dehydrogenated to produce ethenylated aromatic hydrocarbons (eg, styrene and divinylbenzene). Ethenylated aromatic hydrocarbons are also useful as raw materials for industrial products (eg polystyrene). Reactions using the catalysts of the present disclosure are also useful for the production of ethenylated aromatic hydrocarbons. The catalyst-based reaction products of the present disclosure may contain ethenylated aromatic hydrocarbons.

Conventionally known conditions can be adopted as the conditions for the ethylation reaction of aromatic hydrocarbons. For example, a flow-type catalytic reaction device such as the fixed-bed flow device shown in FIG. 1 can be used. The distribution amount of raw materials, reaction temperature, reaction pressure, etc. can be appropriately adjusted.

The reaction temperature may be 300 ° C. or higher, 400 ° C. or higher, 450 ° C. or higher or 500 ° C. or higher, preferably 350 ° C. or higher, more preferably 450 ° C. or higher, from the viewpoint of enhancing the catalytic activity. The reaction temperature may be 800 ° C. or lower, 750 ° C. or lower, 700 ° C. or lower, 650 ° C. or lower, or 600 ° C. or lower, preferably 720 ° C. or lower, and more preferably 620 ° C. or lower, from the viewpoint of energy efficiency. ..

The total pressure in the reaction vessel (total of ethane partial pressure and an aromatic hydrocarbon partial pressure) may be above atmospheric pressure (1.0 × ¹⁰ 5 Pa or more), for example 1~20atm, 1~15atm, 1 It is 10 atm or 1 to 5 atm. The pressure ratio of the ethane partial pressure to the aromatic hydrocarbon partial pressure (ethane partial pressure / aromatic hydrocarbon partial pressure) may be 99.5 / 0.5 to 70/30.

<Example>
Hereinafter, the present disclosure will be described in more detail with reference to Examples and Comparative Examples, but the present disclosure is not limited to these examples.

[material]
The zeolites used in the test are as follows.
NH _4- MFI (HSZ-820NHA, SiO ₂ / Al ₂ O ₃ = 22.1, [Al] = 1.3 mol / kg): Tosoh Corporation
NH ₄ -MFI (JRC-Z5-30NH4 (1), SiO2 / Al2O3 = 30, [Al] = 1.0 mol / kg): Mizusawa Industrial Chemicals Co., Ltd.
Na-MFI (MT-50, SiO ₂ / Al ₂ O ₃ = 48, [Al] = 0.66 mol / kg): Mizusawa Industrial Chemicals Co., Ltd.
NH ₄ -MFI (CBV5524G, SiO ₂ / Al ₂ O ₃ = 61, [Al] = 0.52 mol / kg): ZEOLYST
Na-MFI (JRC-Z5-90NA, SiO ₂ / Al ₂ O ₃ = 90, [Al] = 0.36 mol / kg): Clariant Catalyst Co., Ltd.
Na-MFI (MT-2000, SiO ₂ / Al ₂ O ₃ = 2000, [Al] = 0.017 mol / kg): Mizusawa Industrial Chemicals Co., Ltd.
Na-MOR (JRC-Z-M15 (1), SiO ₂ / Al ₂ O ₃ = 15, [Al] = 1.9 mol / kg): Tosoh Corporation
Na-BEA (JRC-Z-B25 (1), SiO ₂ / Al ₂ O ₃ = 25, [Al] = 1.2 mol / kg): Clariant Catalyst Co., Ltd.
Na-FAU (JRC-Z-Y4.8, SiO ₂ / Al ₂ O ₃ = 4.8, [Al] = 4.5 mol / kg): Catalytic Chemical Industry Co., Ltd.
NH _4- FER (HSZ-720NHA, SiO ₂ / Al ₂ O ₃ = 18.5, [Al] = 1.6 mol / kg): Tosoh Corporation

[Measurement of Pb / Al]
When a catalyst was prepared using the ion exchange method, the mol ratio (metal / Al (mol%)) of the supported metal to aluminum was measured using inductively coupled plasma emission spectrometry (ICP-AES). Specifically, it is as follows.

30 mg of the catalyst to be measured was placed in a Teflon beaker, and 10 mL of hydrofluoric acid was slowly added thereto to dissolve the catalyst. Then 5 mL of nitric acid was added slowly. Then, it was heated for 2 hours on a hot stirrer whose set temperature was set to 200 ° C. After heating, 3 mL of nitric acid and 9 mL of hydrochloric acid were added, and after confirming that all were dissolved, heated deionized water was added. Then, this was washed in a 100 mL volumetric flask with deionized water, and deionized water was added to make 100 mL. Then, this solution was measured using a 10 mL volumetric pipette, placed in a 100 mL volumetric flask, and deionized water was added to prepare a sample solution.

A calibration curve of Al and the supported metal was prepared by measuring the emission intensity of the prepared standard solution and the deionized water (0 mgL ^{-1) used.} Using the prepared calibration curve, the concentrations of Al and the supporting metal were determined from the emission intensity of each of the measured samples, and the metal / Al ratio (mol%) was determined. As the emission intensity, the average value of the values measured three times was used. The following was used for the measurement.
Equipment: Agilent 5110 ICP-OES
Torch: Quartz torch

[Ethylation reaction]
The reaction between ethane and benzene was carried out in the fixed bed distribution device shown in FIG. An appropriate amount of glass wool was packed in a Pyrex tube having an inner diameter of 10 mm, and 0.300 g of a catalyst was placed therein. It was connected to the system, the ethane flow rate was ^{stabilized at 30 mL min -1} , and a 4-way cock was operated to bubbling ice-temperature benzene with ethane and left for 30 minutes. Next, after operating the 4-way cock to make the benzene route independent, the supply of ethane was stopped, N ₂ was circulated at a flow rate of 30 mL min ^-1 , and left for 30 min. The reaction tube and the gas sampler were connected, and the temperature of the entire gas sampler ^{was raised to 150 ° C. and the temperature of the electric furnace was raised to 550 ° C. at 15 ° C. min-1} and then left for 1 hour for pretreatment. After the pretreatment, the electric furnace was cooled to 500 ° C. and the distribution of _{N 2 was stopped.} Ethane was circulated and left for 30 minutes. After that, benzene was introduced by operating a four-way cock. The time when benzene was introduced was set as the distribution start time. The reaction was carried out at a total reaction pressure of 101.3 kPa (P _ethane 98.8 kPa, P _{benzene 2.5 kPa).} At the flow time of 0.5, 1.5, 2.5, 3.5, 4.5 h, the outlet gas is collected using a gas sampler and analyzed by a gas chromatograph (GC) equipped with an online FID. It was. The product was quantified using the absolute calibration curve method.

The analysis conditions of GC are shown below.
Equipment: SHIMADZU GC-2014
Column: CP-PoraBOND Q (length: 25 m, inner diameter: 0.32 mm, film thickness: 5 μm)
Column temperature: 60 ° C → 5 ° C min ^-1 to 100 ° C → 10 ° C min ^-1 to 310 ° C (holds 21 min)

The formula for calculating the yield etc. is shown below.

[Example 1 and Comparative Examples 1 to 18: Examination of metal species]
The MFI zeolite-supported catalyst was prepared by the impregnation method. Specifically, it is as follows. NH ₄ form MFI zeolite (manufactured by Tosoh ^{Corporation: HSZ-820NHA, [Al]} = 1.3molkg -1, SiO 2 / Al 2 O 3 = 22.1) 2 days in a sealed container with saturated aqueous ammonium chloride and It was left to stand and was saturated with water. Various metal salts shown in Table 1 and 75 mL of deionized water were placed in a 200 mL beaker, and 1.0 g of saturated water-absorbed zeolite was added thereto. After that, deionized water was added so that the total volume became 100 mL. Next, the mixture was stirred at 70 ° C. and 400 rpm until all the water was removed. Then, the obtained powder was transferred to an evaporating dish and dried at 110 ° C. for 3 hours to obtain an MFI zeolite-supported catalyst containing various metals. The profile of the obtained MFI zeolite-supported catalyst is shown in Table 1.

[Table 1]

The reaction between ethane and benzene was attempted using the catalysts shown in Table 1. Ethylbenzene in the case of using the supported metal according to Table 1, styrene, the light components of toluene and _C 3 -C _6, flow time 0.5h, 1.5 h, 2.5 h, during 3.5h and 4.5h The average yield in (referred to herein as "average yield") is shown in FIG. The metal elements in FIG. 2 are arranged in order of atomic number. In addition, the dotted line in the figure divides the metal element into cycles. From FIG. 2, it was found that the average yield of ethylbenzene + styrene was highest when Pt-MFI was used as a catalyst. The average yield of ethylbenzene + styrene when catalyzed by Zn-MFI and Pb-MFI is also relatively high. However, among these catalysts in which a large amount of ethylbenzene and styrene, which are the target products, are produced, when Pt-MFI and Zn-MFI are used as catalysts, a large amount of toluene and a light component, which are by-products derived from hydrocracking, are also produced. ing. On the other hand, when a Pb-MFI catalyst is used, by-products are suppressed. That is, it can be seen that the Pb-MFI catalyst is excellent not only in activity but also in reaction selectivity.

In addition, Pt-MFI and Pb-MFI, which produced the most target products, ethylbenzene and styrene, were compared in terms of catalyst life. FIG. 3 shows the change over time in the product yield. When Pt-MFI was used as a catalyst, the yield of ethylbenzene decreased sharply from the flow time of 2.5 h, and decreased to 60% of the initial activity at the flow time of 4.5 h, and remarkable catalyst deterioration was observed. It is considered that the reason for this is that ethylene is produced by the dehydrogenation reaction of ethane, and the ethylene is further dehydrogenated or polymerized to cause caulking. Also, the progress of dehydrogenation of ethane not only cause catalyst deterioration, the hydrogen generated during the hydrocracking of benzene becomes more easily proceeds, light components of toluene and C ₃ -C ₆ It is thought that this will cause a large amount of hydrogen to be generated. This does not mean that ethane can be used effectively. On the other hand, when Pb-MFI was used as a catalyst, stable catalytic activity was exhibited up to a flow time of 4.5 hours. From the above, it can be seen that Pb-MFI exhibits high activity, high selectivity, and long catalyst life. The zeolite-supported Pb catalyst was further investigated below.

[Comparative Examples 19 to 24: Examination of Carrier]
Pb catalysts supported on various carriers by the same impregnation method as in Example 1 except that the carriers shown in Table 2 were used and the amounts of Pb (NO ₃ ) _{2 shown in Table 2 were used.} It was prepared and its activity was evaluated. The profile of the obtained catalyst is shown in Table 2.

In the case of using the Na-type zeolite as a starting material, ion exchange into NH ₄ zeolite, it was supported Pb in NH ₄ zeolite obtained. Ion exchange from Na zeolite to NH ₄ zeolite was carried out as follows. The Na-type zeolite was left in a sealed container containing a saturated aqueous solution of ammonium chloride for 2 days to allow saturated water absorption. 10 equivalents of ammonium nitrate and 75 mL of deionized water were placed in a 200 mL beaker with respect to the amount of Al contained in 5.00 g of Na-type zeolite, and 5.00 g of saturated water-absorbed zeolite was added thereto. Then, deionized water was added so that the total volume became 100 mL. Next, the lid was lightly covered with plastic wrap, and the mixture was stirred at 80 ° C. and 400 rpm for 4 hours. Then, suction filtration and washing were performed a total of 3 times. Secondly, a total of three times by repeating the operations underlined, resulting powder was transferred to an evaporating dish, and dried overnight at 110 ° C., to obtain a NH ₄ zeolite.
[Table 2]

Ethane and benzene were reacted using the catalysts shown in Table 2. The average yields of ethylbenzene, styrene and toluene are shown in FIG. From FIG. 4, it was found that when a carrier other than MFI was used, almost no ethylbenzene was produced. It was found that the combination of Pb and MFI exhibited specific catalytic performance.

[Examples 2 to 5 and Comparative Example 25: Examination of Al content]
Using MFI zeolite having an Al content of MFI of 1.0 mol / kg, 0.66 mol / kg, 0.52 mol / kg, 0.36 mol / kg or 0.017 mol / kg, the amounts of Pb shown in Table 3 are used. An MFI-supported Pb catalyst having a Pb / Al ratio of 60% was prepared in the same manner as in Example 1 except that (NO ₃ ) _{2 was used.} The profile of the obtained catalyst is shown in Table 3.
[Table 3]

Ethane and benzene were reacted using the catalysts shown in Table 3. The average yield of ethylbenzene + styrene is shown in FIG. It was found that the average yield increased as the Al content increased.

[Examples 6 to 15: Examination of Pb content]
An MFI-supported Pb catalyst having a Pb / Al ratio having the values shown in Table 4 was prepared in the same manner as in Example 1 except that the amounts of Pb (NO ₃ ) _{2 shown in Table 4 were used.} The profile of the obtained catalyst is shown in Table 4.

In addition, an MFI-supported Pb catalyst was prepared using the ion exchange method. The production procedure is specifically as follows. The NH _4- MFI zeolite was left in a sealed container containing a saturated aqueous solution of ammonium chloride for 2 days for saturated water absorption. _{Lead nitrate (Pb (NO 3} ) ₂ ) and 75 mL of deionized water were placed in a 200 mL beaker in the amounts shown in Table 4, _{and 1.00 g of saturated water-absorbed NH 4-} MFI was added thereto. After that, deionized water was added so that the total volume became 100 mL. Next, the lid was lightly covered with plastic wrap, and the mixture was stirred at 70 ° C. and 400 rpm for 4 hours. Then, suction filtration and washing were performed a total of 3 times, and the obtained powder was transferred to an evaporating dish and dried at 110 ° C. for 3 hours to obtain Pb-MFI. The profile of the obtained MFI-supported Pb catalyst is shown in Table 4.
[Table 4]

Ethane and benzene were reacted using the catalysts shown in Table 4. The average yield of ethylbenzene + styrene is shown in FIG. It was found that the yield increased to 0.6 for Pb / Al and decreased when Pb / Al was 0.6 or more. It was also found that the catalyst produced by the ion exchange method exhibited superior performance to that produced by the impregnation method. It is presumed that this is because Pb on the ion exchange site particularly contributes to the activity. Further, when Pb / Al is 60 mol% or more, the yield decreases because not only active Pb species but also inactive Pb species are produced when the amount of Pb is too large, and active Pb species are produced. It is presumed that this is due to the inhibition of.

[Example 16: Examination of MFI-supported Pb catalyst using Na-type MFI]
The Na-MFI zeolite was left in a sealed container containing a saturated aqueous solution of ammonium chloride for 2 days to allow saturated water absorption. 3.9 g of lead nitrate (Pb (NO ₃ ) ₂ ) and 75 mL of deionized water were placed in a 200 mL beaker, and 1.00 g of saturated water-absorbed Na-MFI was added thereto. After that, deionized water was added so that the total volume became 100 mL. Next, the lid was lightly covered with plastic wrap, and the mixture was stirred at 70 ° C. and 400 rpm for 4 hours. Then, suction filtration and washing were performed a total of 3 times, and the obtained powder was transferred to an evaporating dish and dried at 110 ° C. for 3 hours to obtain Pb-MFI. The profile of the obtained catalyst is shown in Table 5.
[Table 5]

Ethane and benzene were reacted using the catalysts shown in Table 5. The average yields of ethylbenzene, styrene and toluene are shown in FIG. Lower average yield than Pb-MFI impregnated into NH ₄ form MFI of Example 1 but with the catalytic activity in the case of using the Na-type MFI.

The catalysts of the present disclosure are useful in the manufacturing process of various products in the petrochemical industry.

Claims (8)

MFI-type zeolite and Pb supported on the MFI-type zeolite
Contains,
A Pb-containing zeolite catalyst for an ethylation reaction using ethane and an aromatic hydrocarbon as raw materials, wherein the aromatic hydrocarbon has the following formula (I):
C ₆ (CH ₃ ) _x (C ₂ H ₅ ) _y (H) _{6- (x + y)} (I)
(In the formula, C ₆ is a hexavalent group obtained by removing 6 hydrogen atoms from benzene, x is an integer of 0 to 5, y is an integer of 0 to 5, and x + y is 0 to 0. (It is an integer of 5)
A Pb-containing zeolite catalyst represented by. The Pb-containing zeolite catalyst according to claim 1, wherein the product of the ethylation reaction contains ethylbenzene. The Pb-containing zeolite catalyst according to claim 1 or 2, wherein the Al content is 0.1 mol / kg or more. The Pb-containing zeolite catalyst according to any one of claims 1 to 3, wherein the Pb content is 0.1 mol / kg or more. The Pb-containing zeolite catalyst according to any one of claims 1 to 4, wherein the molar ratio of Pb to Al (Pb / Al (mol%)) is 25 mol% or more and 80 mol% or less. The method for producing a Pb-containing zeolite catalyst according to any one of claims 1 to 5, wherein Pb is supported by an impregnation method or an ion exchange method. Pb respect NH ₄ type MFI zeolite is supported, the production method of the Pb-containing zeolite catalyst according to claim 6. A method for producing a product by an ethylation reaction, using the Pb-containing zeolite catalyst according to any one of claims 1 to 5 or the Pb-containing zeolite catalyst produced by the production method according to claim 6 or 7.