Zinc-containing MFI type zeolite formed body, method for producing same, catalyst for producing aromatic hydrocarbon compound, and method for producing aromatic hydrocarbon compound

Abstract

Provided is a zinc-containing MFI type zeolite formed body with which an aromatic hydrocarbon compound is easily produced even when a reaction for producing an aromatic hydrocarbon compound from an aliphatic hydrocarbon is continued.　The zinc-containing MFI type zeolite formed body is characterized by containing an inorganic binder and an MFI type zeolite, and satisfying the characteristics of following (i)-(iii). (i) The contained amount of the inorganic binder is 5-50 mass%. (ii) When a reduction treatment test is performed under test conditions comprising a test temperature of 600°C, a test atmosphere provided with hydrogen in an amount of 50 mL / minute and nitrogen in an amount of 50 mL / minute, and a test period of 16 hours, the proportion of the zinc content that has decreased due to the reduction treatment test with respect to the zinc content before the reduction treatment test is 30% or less. (iii) The ratio of the zinc content with respect to the acid amount, expressed as Zinc content (mass%) / acid amount (mmol / g), is 1-15.

Description

Zinc-containing MFI zeolite molded body, its production method, catalyst for producing aromatic hydrocarbon compounds, and production method for aromatic hydrocarbon compounds

[0001] The present invention relates to a novel zinc-containing MFI zeolite shaped body. More specifically, the present invention relates to a zinc-containing MFI zeolite shaped body having excellent resistance to reduction and volatilization, which contains MFI zeolite, an inorganic binder, and zinc resistant to reduction and volatilization, and is characterized in that the balance between the zinc content and the acid amount is within a specific range, and to a method for producing an aromatic hydrocarbon compound using the same.

[0002] MFI zeolite is used as a highly selective catalyst that utilizes the uniform pores derived from the zeolite framework structure. Examples of the use of MFI zeolite as a catalyst include the disproportionation of toluene (see, for example, Patent Document 1) and the isomerization of xylene (see, for example, Patent Document 2). These reactions mainly utilize the characteristics of the micropores of MFI zeolite. The micropores of MFI zeolite have an entrance diameter of approximately 0.5 nm, and are thought to provide an effective reaction field for molecules with molecular diameters close to this pore diameter (hereinafter also referred to as "pore diameter").

[0003] Aromatic hydrocarbon compounds such as benzene, toluene, and xylene are often obtained by cracking feedstock oil (e.g., naphtha) obtained through petroleum refining in a thermal cracking reactor, and separating and purifying the aromatic hydrocarbon compounds from the resulting thermal cracking products by distillation or extraction. In the production of aromatic hydrocarbon compounds by these production methods, aliphatic hydrocarbon compounds (including paraffinic, olefinic, acetylenic, and alicyclic hydrocarbons) are also produced as thermal cracking products in addition to the aromatic hydrocarbon compounds. Thus, in the production of aromatic hydrocarbon compounds by cracking feedstock oil, aliphatic hydrocarbon compounds are simultaneously produced, and therefore the production amount of aromatic hydrocarbon compounds is adjusted in accordance with the production amount of aliphatic hydrocarbon compounds, which naturally limits the production amount.

[0004] On the other hand, another method for producing aromatic hydrocarbon compounds is also known, in which an aliphatic hydrocarbon compound is used as a raw material and brought into contact with a catalyst containing mainly medium pore size zeolite at a temperature of about 400°C to about 800°C (see, for example, Non-Patent Documents 1 to 4). Compared with the method for producing aromatic hydrocarbon compounds by thermal cracking, this production method has lower added value and has the advantage that aromatic hydrocarbon compounds can be produced from excess aliphatic hydrocarbon raw materials.

[0005] For this reason, in recent years, catalysts for producing aromatic hydrocarbon compounds from aliphatic hydrocarbon compounds (hereinafter also referred to as "catalysts for producing aromatic hydrocarbon compounds") have been developed. Among these, efforts have been made to improve catalytic activity and selectivity by incorporating metals into zeolites. For example, zinc-containing MFI zeolites are known to exhibit high catalytic activity in the reaction for producing aromatic hydrocarbon compounds from aliphatic hydrocarbon compounds (see, for example, Patent Document 3). Furthermore, a medium pore size zeolite catalyst containing zinc and zinc aluminate has been reported as a catalyst for producing aromatic hydrocarbon compounds using hydrocarbons containing paraffins, olefins, and naphthenes as raw materials (see, for example, Patent Document 4).

[0006] Furthermore, when producing aromatic hydrocarbon compounds using a catalyst for producing aromatic hydrocarbon compounds, it is possible to easily co-produce light hydrocarbon compounds such as ethane and ethylene, which are useful as basic chemical raw materials, which will contribute to the promotion of inclusive and sustainable industrialization and is one of the technologies necessary for a sustainable society, such as the SDGs that have been called for in recent years.

[0007] Patent No. 4014279 Patent No. 2598127 US Patent No. 4157293 Japanese Patent Publication No. 10-33987

[0008] 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).

[0009] However, the zinc-containing zeolite catalyst proposed in Patent Document 3 has an issue of deterioration in catalytic performance due to a decrease in the zinc content, since zinc species are reduced to metallic zinc by hydrogen generated in the process of producing aromatic hydrocarbon compounds from aliphatic hydrocarbon compounds, and the metallic zinc volatilizes due to its high vapor pressure.

[0010] Furthermore, the method proposed in Patent Document 4 aims to maintain catalytic performance for a long period of time by incorporating zinc aluminate, which is difficult to reduce, into the catalyst. However, this method requires the incorporation of an excess amount of zinc aluminate, making it difficult to reduce the absolute amount of zinc that volatilizes.

[0011] Therefore, there is a demand for a zinc-containing MFI zeolite shaped body that can easily maintain its catalytic activity for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons even when the reaction for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons is continued.

[0012] As a result of intensive research conducted by the present inventors to solve the above-mentioned problems, they found that a zinc-containing MFI zeolite shaped body that selectively contains zinc that is resistant to reduction and volatilization (zinc that is difficult to volatilize in a reducing atmosphere) and has a specific balance between the zinc content and the acid amount is likely to maintain catalytic activity for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons even when the reaction for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons is continued, and thus they have completed the present invention.

[0013] The present invention relates to the following inventions. [1] A zinc-containing MFI zeolite shaped body, comprising an inorganic binder and MFI zeolite, and satisfying the following properties (i) to (iii): (i) the inorganic binder content is 5 to 50 mass %. (ii) When a reduction treatment test is conducted under test conditions of a test temperature of 600°C, a test atmosphere of 50 mL / min of hydrogen and 50 mL / min of nitrogen, and a test time of 16 hours, the ratio of the zinc content reduced by the reduction treatment test to the zinc content before the reduction treatment test is 30% or less. (iii) The zinc content (mass %) / acid amount (mmol / g), expressed as the ratio of the zinc content to the acid amount, is 1 to 15. [2] A zinc-containing MFI zeolite shaped body according to [1], characterized by satisfying the following properties (iv) to (v): (iv) the zinc content is 0.2 to 3.0 mass %. (V) The acid amount is 0.05 to 0.85 mmol / g. [3] A zinc-containing MFI zeolite shaped body according to [1] or [2], characterized in that, in the relationship between pore diameter and cumulative pore volume measured by mercury intrusion porosimetry, the cumulative pore volume of pores having a pore diameter in the range of 0.011 to 0.090 μm is 0.040 to 0.800 cc / g. [4] A zinc-containing MFI zeolite shaped body according to any one of [1] to [3], characterized in that, in the relationship between pore diameter and cumulative pore volume measured by mercury intrusion porosimetry, the cumulative pore volume of pores having a pore diameter in the range of 0.090 to 200 μm is 0.100 to 0.800 cc / g. [5] A zinc-containing MFI zeolite shaped body according to any one of [1] to [4], characterized in that the shape of the zeolite is a cylindrical shape, a spherical shape, an oval shape, or a polygonal pillar shape. [6] A catalyst for producing aromatic hydrocarbon compounds, comprising the zinc-containing MFI zeolite shaped body according to any one of [1] to [5]. [7] A method for producing aromatic hydrocarbon compounds, comprising contacting the catalyst for producing aromatic hydrocarbon compounds according to [6] with aliphatic hydrocarbons having 30 or less carbon atoms at 400 to 800°C. [8] A method for producing aromatic hydrocarbon compounds according to [7], wherein the aliphatic hydrocarbons having 30 or less carbon atoms include aliphatic hydrocarbons derived from plants and / or chemical recycling.[9] A method for producing a zeolite shaped article, comprising: a packing step (1) of packing a plurality of MFI zeolite shaped articles into a packing section having a length L in the supply direction of the aqueous zinc solution; a zinc-containing step (2) of supplying an aqueous zinc solution having a zinc concentration of 10 to 2000 mM to the packing section and bringing the plurality of MFI zeolite shaped articles into contact with the aqueous zinc solution; and a washing step (3) of supplying a washing liquid to the packing section and bringing the plurality of MFI zeolite shaped articles that have been contacted with the aqueous zinc solution into contact with the washing liquid, wherein in the zinc-containing step (2), a method for producing a zinc-containing MFI zeolite shaped body, the method comprising: bringing the plurality of MFI zeolite shaped bodies into contact with the zinc aqueous solution until a contact time T1 between the shaped bodies and the zinc aqueous solution satisfies the following formula (A); and in the washing step (3), bringing the plurality of MFI zeolite shaped bodies into contact with the washing solution so that when the MFI zeolite shaped bodies that have been contacted with the washing solution are tested for 60 minutes in contact with 2 parts by mass of water per 1 part by mass of the MFI zeolite shaped bodies, the pH of the water used in the test is 2.5 or higher: T1≧L×1.5 (A) In the above formula (A), T1 is the contact time [hr] between the plurality of MFI zeolite shaped bodies and the zinc aqueous solution, and L is the length [m] of the packed section in the supply direction of the zinc aqueous solution.

[10] The method for producing a zinc-containing MFI zeolite shaped body according to [9], wherein the MFI zeolite shaped bodies have an inorganic binder content of 5 to 50% by mass.

[11] The method for producing a zinc-containing shaped MFI zeolite body according to [9] or

[10] , characterized in that the MFI zeolite shaped body is obtained by a production method comprising the steps of drying a mixture containing at least MFI zeolite, an inorganic binder, and water, and separating aluminum from the framework structure of the MFI zeolite contained in the dried mixture.

[12] The method for producing a zinc-containing MFI zeolite shaped body according to any one of [9] to

[11] , characterized in that the MFI zeolite shaped body has a cylindrical, cylindrical, spherical, spheroidal, or polygonal prism shape.

[13] The method for producing a zinc-containing MFI zeolite shaped body according to any one of [9] to

[12] , wherein the packed section has a cylindrical shape in which the length L in the supply direction is 0.5 m or more and the cross section in a plane perpendicular to the supply direction is a circle with a diameter of 10 cm or more.

[14] The method for producing a zinc-containing MFI zeolite shaped body according to any one of [9] to

[13] , wherein the aqueous zinc solution is circulated through a circulation flow path formed by the packed section and a flow path connected to the packed section.

[15] The method for producing a zinc-containing MFI zeolite shaped body according to any one of [9] to

[14] , wherein the aqueous zinc solution is supplied to the packed section from below upward in the vertical direction.

[16] The method for producing a zinc-containing MFI zeolite shaped body according to any one of [9] to

[15] , further comprising: a drying step (4) of drying the plurality of MFI zeolite shaped bodies that have been brought into contact with the cleaning liquid; and a dealumination step (6) of removing aluminum from the framework structure of MFI zeolite contained in the plurality of dried MFI zeolite shaped bodies.

[0014] An object of the present invention is to provide a zinc-containing MFI zeolite shaped body that is likely to maintain its catalytic activity for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons even when the reaction for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons is continued.

[0015] 1 is a diagram showing an example of a filling section; 2 is a diagram showing an example of a circulation flow path; 3 is a graph showing the yield when a hydrocarbon compound is produced using a catalyst for producing a hydrocarbon compound of an example; and 4 is a graph showing the yield when a hydrocarbon compound is produced using a catalyst for producing a hydrocarbon compound of a comparative example.

[0016] The present invention is described in detail below. The present invention includes any combination of the configurations and parameters disclosed herein, and also includes any combination of the upper and lower limits of the values ​​disclosed herein.

[0017] The zinc-containing MFI zeolite shaped body of the present invention has (i) an inorganic binder content of 5 to 50% by mass, and preferably an inorganic binder content of 10 to 40% by mass, since this provides particularly excellent molding stability. The aforementioned inorganic binder content is the content relative to 100% by mass of the zinc-containing MFI zeolite shaped body. The inorganic binder contained in the zinc-containing MFI zeolite shaped body of the present invention may be any binder that contains an inorganic element such as silicon or aluminum and is capable of binding zeolite particles together, and examples thereof include silica, silica alumina, and alumina. When the inorganic binder content is 5% by mass or more, the resulting shaped body will have excellent strength. On the other hand, when the inorganic binder content is 50 mass% or less, even if the reaction for producing aromatic hydrocarbon compounds (e.g., benzene, toluene, xylene) from aliphatic hydrocarbons is continued, the catalytic activity for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons (hereinafter also referred to as "aromatic production activity") is likely to be maintained, and light hydrocarbons (e.g., ethane, ethylene) are likely to be co-produced together with the aromatic hydrocarbon compounds.

[0018] The zinc-containing MFI zeolite shaped body of the present invention may be composed only of MFI zeolite and an inorganic binder, or may further contain, in addition to these, one or more molding aids selected from the group consisting of cellulose and other such molding aids, decomposition products thereof, and water. Examples of molding aids that can be contained in the zinc-containing MFI zeolite shaped body of the present invention include at least one selected from the group consisting of cellulose, guar gum, hydroxypropyl guar gum, xanthan gum, welan gum, gellan gum, polyethyleneimine derivatives, polyvinylpyrrolidone, glycerin, polyvinyl alcohol, ethylene glycol, surfactants, aqueous urethane, and polyacrylic acid derivatives, with cellulose being preferred.

[0019] In the zinc-containing MFI zeolite shaped body of the present invention, the average particle size of the inorganic binder is preferably 5 nm or more, 10 nm or more, or 20 nm or more, and is preferably 1 μm or less, 500 nm or less, or 200 nm or less, because aromatic production activity is more easily maintained. The upper and lower limits of the average particle size of the inorganic binder may be any combination of the above-mentioned upper and lower limits, but the average particle size of the inorganic binder is preferably 5 nm or more and 1 μm or less, more preferably 10 nm or more and 500 μm or less, and even more preferably 20 nm or more and 200 μm or less, because catalytic activity for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons is more easily maintained.

[0020] The zinc-containing MFI zeolite shaped body of the present invention (ii) has a ratio (hereinafter also referred to as "free zinc rate") of 30% or less of the zinc content reduced by the reduction test (hereinafter also referred to as "free zinc amount") relative to the zinc content before the reduction test when subjected to a reduction test under conditions of a test temperature of 600°C, a test atmosphere of hydrogen at 50 mL / min and nitrogen at 50 mL / min, and a test time of 16 hours. In this specification, the "zinc content" refers to the zinc content relative to 100% by mass of the zinc-containing MFI zeolite shaped body, and can be determined from the amount of zinc in a measurement sample measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES) using a general inductively coupled plasma atomic emission spectrometer (ICP device) (e.g., OPTIMA 3300DV, manufactured by PerkinElmer) and the amount of zinc-containing MFI zeolite shaped body contained in the measurement sample. The measurement sample used in ICP-AES can be a sample solution prepared by dissolving a zinc-containing MFI zeolite shaped body in a mixed aqueous solution of hydrofluoric acid and nitric acid. The "amount of free zinc" can be determined by subtracting the zinc content after the reduction treatment test from the zinc content before the reduction treatment test, and the "free zinc rate" can be determined by expressing the ratio of the amount of free zinc to the zinc content before the reduction treatment test as a percentage.

[0021] Here, when a reduction treatment test is performed on a zinc-containing MFI zeolite shaped body, free zinc from the zinc contained in the zinc-containing MFI zeolite shaped body volatilizes. Free zinc refers to zinc species that have not been stabilized against reductive volatilization by the MFI zeolite shaped body, and examples thereof include zinc species that exist in an oxide state in voids that form between zeolite primary particles or between zeolite primary particles and a binder. Such free zinc volatilizes after being reduced to metallic zinc in a reduction treatment test. Since the zinc-containing MFI zeolite shaped body of the present invention has a free zinc ratio of 30% or less, zinc is less likely to volatilize in a reducing atmosphere, and aromatic hydrocarbon production activity is easily maintained even when a reaction for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons is continued. Furthermore, since the zinc-containing MFI zeolite shaped body of the present invention has a free zinc ratio of 30% or less, light hydrocarbons are more likely to be co-produced along with aromatic hydrocarbon compounds.

[0022] Since aromatics production activity is more likely to be maintained, the free zinc rate of the zinc-containing MFI zeolite shaped body of the present invention is preferably 20% or less, more preferably 15% or less, even more preferably 10% or less, and particularly preferably 0%. From the viewpoint of reducing the energy required for producing the zeolite shaped body, the free zinc rate is preferably 0.01% or more, and more preferably 0.5% or more. The upper and lower limit values ​​of the free zinc rate can be arbitrarily combined, but since aromatics production activity is more likely to be maintained, the free zinc rate of the zinc-containing MFI zeolite shaped body of the present invention is preferably 0% or more and 20% or less, more preferably 0% or more and 15% or less, and even more preferably 0% or more and 10% or less.

[0023] In the zinc-containing MFI zeolite shaped body of the present invention, the amount of free zinc is not particularly limited, but is preferably 0.5% by mass or less, 0.2% by mass or less, or 0.1% by mass or less, since aromatics production activity is more easily maintained. The lower limit of the amount of free zinc is not particularly limited, but can be, for example, 0% by mass or more, 0.01% by mass or more, or 0.03% by mass or more. The upper and lower limit values ​​of the amount of free zinc can be combined arbitrarily, but since aromatics production activity is more easily maintained, the amount of free zinc in the zinc-containing MFI zeolite shaped body of the present invention is preferably 0% by mass or more and 0.5% by mass or less, more preferably 0% by mass or more and 0.2% by mass or less, and even more preferably 0% by mass or more and 0.1% by mass or less. In this specification, 0% by mass means that the component is substantially not contained, and substantially not containing the component means that the component is not detected (below the measurement limit).

[0024] The state of the zinc contained in the zinc-containing MFI zeolite shaped body of the present invention is not particularly limited, and examples thereof include metal, compound (e.g., oxide or metal salt), ion, alloy, or two or more of these states. In other words, the zinc contained in the zinc-containing MFI zeolite shaped body of the present invention does not necessarily refer only to zinc in a metallic state, but also includes zinc in a non-metallic state. The zinc contained in the zinc-containing MFI zeolite shaped body of the present invention is preferably in an ionic state, since this makes it easier to maintain aromatics production activity. Note that the zinc content in this specification is the content assuming that all of the supported metal elements are in a metallic (element) state.

[0025] The zinc-containing MFI zeolite shaped body of the present invention has (iii) a zinc content (mass%) / acid amount (mmol / g) ratio, expressed as the ratio of the zinc content to the acid amount, of 1 to 15. In particular, since the shaped body exhibits excellent catalytic activity for producing light hydrocarbons from aliphatic hydrocarbons in addition to aromatic production activity, the zinc content (mass%) / acid amount (mmol / g) ratio, expressed as the ratio of the zinc content to the acid amount, is preferably 1 to 10. When the zinc content (mass%) / acid amount (mmol / g) ratio is 1 or more, the amount of zinc necessary for the catalytic reaction is maintained, resulting in an excellent effect of improving activity by zinc, or the amount of acid is not excessive relative to the amount of zinc, resulting in excellent maintenance of catalytic activity. Furthermore, when the zinc content (mass%) / acid amount (mmol / g) ratio is 15 or less, the amount of acid necessary for the catalytic reaction is ensured, or the amount of zinc is not excessive relative to the amount of acid, resulting in excellent maintenance of catalytic activity. When the zinc content (mass %) / acid amount (mmol / g) is within the range of 1 or more and 15 or less, it is believed that the effect of the zinc species that dehydrogenates the aliphatic hydrocarbons that are the raw material and converts them into highly reactive hydrocarbons having unsaturated bonds, and the effect of the acid sites that cyclize the hydrocarbons and their oligomers thus produced, are exerted in a well-balanced manner, thereby promoting the production of aromatic compounds and light hydrocarbons over a long period of time.

[0026] The zinc content (mass%) / acid amount (mmol / g) can be determined by dividing the zinc content (mass%) in the zinc-containing MFI zeolite shaped article of the present invention by the acid amount (mmol / g). The acid amount (mmol / g) of the zinc-containing MFI zeolite shaped article of the present invention can be measured by a method based on the ammonia-TPD method (see "Measurement of Solid Acidity by Ammonia Temperature Programmed Desorption Method," Catalysts, Vol. 42, p. 218 (2000)"). Specifically, a zinc-containing MFI zeolite shaped body that has been saturated with ammonia adsorbed at room temperature (25°C) is heated in an inert gas at 100°C for one hour to remove ammonia that has not been adsorbed on the zinc-containing MFI zeolite shaped body from the treatment atmosphere, and then the temperature is increased from 100°C to 700°C at a rate of 10°C / min to obtain an ammonia temperature-programmed desorption spectrum that indicates the amount of ammonia released from the zinc-containing MFI zeolite shaped body during the temperature increase process (hereinafter also referred to as the "released ammonia amount") [mmol]. The amount of desorbed ammonia [mmol] indicated by the highest temperature peak (hereinafter also referred to as the "H peak") in the obtained ammonia temperature programmed desorption spectrum is considered to be the amount of solid acid [mmol] present in the zinc-containing MFI zeolite shaped body (the amount of ammonia [mmol] adsorbed to the solid acid of the zinc-containing MFI zeolite shaped body), and the amount of acid [mmol / g] can be determined from the amount of solid acid [mmol] and the mass [g] of the zinc-containing MFI zeolite shaped body used for ammonia adsorption. Examples of the inert gas used in the ammonia-TPD method include at least one gas selected from helium and argon, with helium being preferred.

[0027] For peak separation of the H peak, known methods can be used, and are not particularly limited. For example, a method of curve fitting (peak separation) by the least squares method based on an assumed function representing the peak can be used. Examples of the function representing the peak include a Gaussian function, a Lorentzian function, a mixed function of a Gaussian function and a Lorentzian function (Gauss-Lorentz), and a Voigt function. Peak separation of the H peak may be performed using ChemMaster manufactured by MicrotracBell.

[0028] The MFI zeolite contained in the zinc-containing MFI zeolite shaped body of the present invention is a zeolite having a skeletal structure identified as "MFI" in the skeletal code defined by the International Zeolite Association. Any zeolite may be used as the MFI zeolite contained in the MFI zeolite shaped body as long as it has an MFI skeletal structure. However, since aromatics production activity is more easily maintained, a zeolite in which skeletal atoms (hereinafter also referred to as "T atoms") are substantially composed of aluminum (Al) and silicon (Si) is preferred. Here, "T atoms substantially composed of aluminum (Al) and silicon (Si)" does not only mean that the T atoms are composed only of aluminum (Al) and silicon (Si), but also means that the T atoms may contain T atoms other than aluminum (Al) and silicon (Si) as long as the effects of the present invention are achieved. Hereinafter, a zeolite in which the T atoms are substantially composed of aluminum (Al) and silicon (Si) will also be referred to as a crystalline aluminosilicate.

[0029] The MFI zeolite contained in the zinc-containing MFI zeolite shaped article of the present invention is more likely to maintain its aromatics production activity, and therefore, alumina (Al ２ O ３ ) relative to aluminum (SiO ２ ) molar ratio of silicon (hereinafter referred to as "SiO ２ / Al ２ O ３ The molar ratio (SiO 2 ) is preferably 10 or more, or 20 or more, and is preferably 200 or less, 150 or less, or 100 or less. ２ / Al ２ O ３ The upper and lower limit values ​​of the molar ratio may be any combination of the upper and lower limit values ​​described above. However, it is preferable to use a molar ratio of SiO of MFI zeolite because this makes it easier to maintain aromatics production activity. ２ / Al ２ O ３ The molar ratio is preferably 10 or more and 200 or less, more preferably 20 or more and 200 or less, and even more preferably 20 or more and 100 or less.

[0030] The MFI zeolite contained in the zinc-containing MFI zeolite shaped article of the present invention preferably has an average particle size of 0.02 μm or more or 0.04 μm or more, and preferably 10 μm or less or 5 μm or less, because aromatics production activity is more easily maintained. The upper and lower limits of the average particle size may be any combination of the above-mentioned upper and lower limits, but the average particle size of the MFI zeolite is preferably 0.02 μm or more and 10 μm or less, more preferably 0.02 μm or more and 5 μm or less, because aromatics production activity is more easily maintained.

[0031] In this specification, the average particle size refers to the average particle size of primary particles and is different from the average particle size of aggregates formed by aggregating multiple primary particles. To measure the average particle size, first, 300 primary particles whose contours are observed without interruption are randomly selected from a transmission electron microscope (hereinafter also referred to as "TEM") image obtained by observation under the following conditions. The particle diameter is calculated by averaging the longest diameter of each extracted primary particle and the diameter in the perpendicular direction at its midpoint, and then averaging the particle diameters of the 300 primary particles. The longest diameter of a primary particle is the distance between the longest parallel lines when sandwiched between two parallel lines tangent to the contour. The number of TEM images may be any number sufficient to observe the above-mentioned number of primary particles, and one or more TEM images may be used. TEM observation may be performed using a general transmission electron microscope (e.g., JEM-2100, manufactured by JEOL Ltd.). The specimen for microscopic examination may be prepared by lightly crushing a zinc-containing MFI zeolite body in a mortar, ultrasonically dispersing it in acetone, dropping the resulting dispersion onto a plastic support film, and allowing it to dry naturally. Acceleration voltage: 200 kV Magnification: 30,000 times

[0032] The content of MFI zeolite relative to 100% by mass of the zinc-containing MFI zeolite shaped body of the present invention (hereinafter also referred to as "MFI zeolite content") is preferably 40% by mass or more, 50% by mass or more, or 60% by mass or more, and preferably 95% by mass or less, or 90% by mass or less, because aromatics production activity is more easily maintained. The upper and lower limits of the MFI zeolite content may be any combination of the above-mentioned upper and lower limits, but the MFI zeolite content is preferably 50% by mass or more and 95% by mass or less, and more preferably 60% by mass or more and 90% by mass or less, because aromatics production activity is more easily maintained.

[0033] The MFI zeolite contained in the zinc-containing MFI zeolite shaped article of the present invention may be an MFI zeolite produced by a conventionally known production method, or a commercially available MFI zeolite may be used. Examples of commercially available MFI zeolites include at least one selected from the group consisting of (trade name) HSZ-822HOA (manufactured by Tosoh Corporation), (trade name) HSZ-840HOA (manufactured by Tosoh Corporation), (trade name) HSZ-890HOA (manufactured by Tosoh Corporation), (trade name) HSZ-891HOA (manufactured by Tosoh Corporation), (trade name) HSZ-820NHA (manufactured by Tosoh Corporation), (trade name) HSZ-840NHA (manufactured by Tosoh Corporation), and (trade name) HSZ-930NHA (manufactured by Tosoh Corporation).

[0034] The inorganic binder contained in the zinc-containing MFI zeolite shaped article of the present invention may be an inorganic binder produced by a conventionally known production method, or may be a commercially available inorganic binder. Examples of commercially available inorganic binders (silica) include (trade name: Snowtex N30G, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm), (trade name: Snowtex N, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm), (trade name: Snowtex 30, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm), (trade name: Snowtex O, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm), (trade name: Snowtex C, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm), (trade name: Snowtex AK, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm), (trade name: Snowtex N-40, manufactured by Nissan Chemical Industries, Ltd., average particle size 22 nm), (trade name: Snowtex 50-T, manufactured by Nissan Chemical Industries, Ltd., average particle size 22 nm), (trade name: Snowtex O-40, manufactured by Nissan Chemical Industries, Ltd., average particle size 22 nm), (trade name:

[0033] Examples of the solubility enhancer include at least one selected from the group consisting of (trade name) Snowtex CM, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 22 nm), ((trade name) Snowtex 30L, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 45 nm), ((trade name) Snowtex OL, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 45 nm), ((trade name) Snowtex AK-L, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 45 nm), ((trade name) Snowtex YL, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 60 nm), ((trade name) Snowtex OYL, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 60 nm), ((trade name) Snowtex AK-YL, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 60 nm), ((trade name) Snowtex ZL, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 80 nm), and ((trade name) MP-1040, manufactured by Nissan Chemical Industries, Ltd., average particle diameter 100 nm).

[0035] The MFI zeolite contained in the zinc-containing MFI zeolite shaped article of the present invention is preferably one that is substantially free of a structure-directing agent such as a tetrapropylammonium salt within its pores, since this makes it easier to maintain aromatics production activity. Note that "substantially free of a specified component" means that the component is not detectable (below the detection limit).

[0036] The method for synthesizing the MFI zeolite contained in the zinc-containing MFI zeolite shaped article of the present invention is not particularly limited, and the following method can be mentioned, for example.

[0037] Amorphous aluminosilicate gel is added to an aqueous solution of tetrapropylammonium (hereinafter, sometimes referred to as "TPA") hydroxide and sodium hydroxide to form a suspension, MFI zeolite is added to the resulting suspension as seed crystals to form a raw material composition, and the resulting raw material composition is crystallized and calcined to obtain MFI zeolite.

[0038] The acid amount of the zinc-containing MFI zeolite shaped product of the present invention is not particularly limited as long as the ratio of zinc content (% by mass) / acid amount (mmol / g) is 1 to 15. However, because aromatics production activity is more likely to be maintained, the acid amount is preferably 0.05 to 0.85 mmol / g, particularly preferably 0.10 to 0.70 mmol / g, and even more preferably 0.10 to 0.50 mmol / g.

[0039] In the zinc-containing MFI zeolite shaped body of the present invention, in terms of the relationship between pore diameter and cumulative pore volume as determined by mercury intrusion porosimetry, the cumulative pore volume of pores having a pore diameter in the range of 0.011 to 0.090 μm is preferably 0.040 to 0.800 cc / g, more preferably 0.040 to 0.600 cc / g, and even more preferably 0.090 to 0.400 cc / g. When the cumulative pore volume of pores having a diameter in the range of 0.011 to 0.090 μm is 0.040 cc / g or more, reactants (reaction substrates) such as aliphatic hydrocarbons are more likely to diffuse within the voids (or pores) of the zinc-containing MFI zeolite shaped body, thereby further improving the adsorption performance and, when used as a catalyst, the catalytic performance. When the cumulative pore volume of pores in the diameter range of 0.011 to 0.090 μm is 0.800 cc / g or less, the macroscopic void ratio of the molded body is small, so that the crushing strength of the molded body is high and it is difficult to collapse.

[0040] The zinc-containing MFI zeolite shaped article of the present invention is particularly excellent in the diffusion of reactants (reaction substrates) within its pores, and is excellent in adsorption performance and, when used as a catalyst, catalytic performance, etc. Therefore, in the relationship between pore diameter and cumulative pore volume as determined by mercury intrusion porosimetry, the cumulative pore volume of pores having diameters in the range of 0.090 μm to 200 μm is preferably 0.100 to 0.800 cc / g, more preferably 0.200 to 0.700 cc / g, and even more preferably 0.200 to 0.600 cc / g.

[0041] Here, the relationship between pore diameter and cumulative pore volume determined by mercury intrusion porosimetry can be obtained by applying the Washburn equation: PD=−4σ cos θ (where P is pressure, D is pore diameter, σ is the surface tension of mercury, and θ is the contact angle of mercury) to a mercury intrusion curve (a curve showing the relationship between pressure and the amount of mercury intrusion) obtained by injecting mercury into a zinc-containing MFI zeolite shaped body while changing the pressure using a mercury porosimeter (for example, POREMASTER GT, manufactured by Quantachrome Instruments).

[0042] The measurement of the mercury intrusion amount using a mercury porosimeter may be performed after pretreating a sample (the zinc-containing MFI zeolite shaped body of the present invention) by heat-treating it at 450°C for 3 hours and then cooling it to room temperature. The measurement of the mercury intrusion amount using a mercury porosimeter may be performed by filling the pretreated sample into a measurement cell, reducing the pressure to 6.7 PaA or less for 15 minutes, and gradually increasing the mercury pressure from 0.00738 MPaA to 245.1342 MPaA. The mercury intrusion curve to which the Washburn equation is applied may be a curve showing the relationship between the mercury intrusion amount (base-corrected mercury intrusion amount) and pressure (mercury intrusion curve), which is obtained by subtracting the mercury intrusion amount measured using a blank cell (the mercury intrusion amount measured using a measurement cell not filled with a sample) as a base from the mercury intrusion amount of the zinc-containing MFI zeolite shaped body (the actually measured mercury intrusion amount). In addition, in the Washburn equation applied to the mercury intrusion curve, the surface tension σ of mercury is 480 erg / cm ２and the contact angle θ of mercury is set to 140°. From the relationship between pore diameter and cumulative pore volume, the cumulative pore volume of pores having a pore diameter in a predetermined range (0.011 μm or more and 0.090 μm or less, or 0.090 μm or more and 200 μm or less) can be calculated by subtracting the cumulative pore volume at the maximum diameter in the predetermined range from the cumulative pore volume at the minimum diameter in the predetermined range.

[0043] The zinc content of the zinc-containing MFI zeolite shaped article of the present invention is not particularly limited, but is preferably 0.2 to 3.0 mass%, more preferably 0.4 to 3.0 mass%, and particularly preferably 0.7 to 3.0 mass%.

[0044] The shape of the zinc-containing MFI zeolite shaped article of the present invention is not particularly limited, and examples thereof include cylindrical, cylindrical, spherical, spheroidal, and polygonal prism shapes.

[0045] The zinc-containing MFI zeolite shaped body of the present invention can be produced, for example, by a production method including at least three steps: a filling step (1), a zinc-containing step (2), and a washing step (3) (hereinafter also referred to as the "first production method").

[0046] First, the packing step (1) included in the first production method will be described. The packing step (1) is a step of packing a plurality of MFI zeolite shaped bodies into a packing section having a length L (m) in the supply direction of the aqueous zinc solution.

[0047] The MFI zeolite shaped body used in the filling step is a shaped body obtained by shaping MFI zeolite into a predetermined shape, and contains at least MFI zeolite and an inorganic binder.

[0048] The MFI zeolite and inorganic binder contained in the MFI zeolite shaped article are the same as the MFI zeolite and inorganic binder contained in the zinc-containing MFI zeolite shaped article of the present invention, and therefore detailed description thereof will be omitted.

[0049] The content of MFI zeolite relative to 100% by mass of the MFI zeolite shaped body (MFI zeolite content) is preferably 40% by mass or more, 50% by mass or more, or 60% by mass or more, and preferably 95% by mass or less, or 90% by mass or less, because this makes it easier to produce a zinc-containing MFI zeolite shaped body that is more likely to maintain its aromatics-producing activity. In the MFI zeolite shaped body, the upper and lower limit values ​​of the MFI zeolite content may be any combination of the above-mentioned upper and lower limit values, but because this makes it easier to produce a zinc-containing MFI zeolite shaped body that is more likely to maintain its aromatics-producing activity, the MFI zeolite content is preferably 50% by mass or more and 95% by mass or less, and more preferably 60% by mass or more and 90% by mass or less.

[0050] The content of the inorganic binder relative to 100% by mass of the MFI zeolite shaped body (inorganic binder content) is preferably 5% by mass or more or 10% by mass or more, and preferably 50% by mass or less, 45% by mass or less, or 40% by mass or less, because a zinc-containing MFI zeolite shaped body that is more likely to maintain its aromatics-producing activity is more easily produced. In the MFI zeolite shaped body, the upper limit and lower limit of the inorganic binder content may be any combination of the above-mentioned upper limit and lower limit values, but because a zinc-containing MFI zeolite shaped body that is more likely to maintain its aromatics-producing activity is more easily produced, the inorganic binder content is preferably 5% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, and even more preferably 10% by mass or more and 40% by mass or less.

[0051] The MFI zeolite shaped body used in the filling step (1) may be composed only of MFI zeolite and an inorganic binder, or may further contain, in addition to these, one or more selected from the group consisting of a molding aid, a decomposition product thereof, and water. The molding aid that can be contained in the MFI zeolite shaped body is the same as the molding aid that can be contained in the zinc-containing MFI zeolite shaped body of the present invention, and therefore a detailed description thereof will be omitted.

[0052] The MFI zeolite shaped body used in the filling step (1) may have a cylindrical, cylindrical, spherical, spheroidal, or polygonal columnar shape, and is preferably a cylindrical shape having a diameter of 1.0 mm or more and 10.0 mm or less and a length of 1.0 mm or more and 20.0 mm or less, and more preferably a cylindrical shape having a diameter of 1.0 mm or more and 5.0 mm or less and a length of 2.0 mm or more and 10.0 mm or less.

[0053] The MFI zeolite shaped body used in the filling step (1) has a density of 0.8 g / cm3 from the viewpoint of making it easier to contain zinc, which is difficult to volatilize in a reducing atmosphere. ３ Above, 0.85g / cm ３ or more, or 0.9 g / cm ３ It is preferable that the density is 1.2 g / cm or more. ３ Below, 1.1g / cm ３ or less, or 1.0 g / cm ３ The upper and lower limit values ​​of the density may be any combination of the above-mentioned upper and lower limit values, but from the viewpoint of making it easier to contain zinc, which is difficult to volatilize in a reducing atmosphere, it is preferable that the density of the MFI zeolite shaped body is 0.8 g / cm or less. ３ 1.2g / cm or more ３ It is preferable that the density is 0.85 g / cm or less. ３ 1.1g / cm or more ３ More preferably, it is 0.9 g / cm or less. ３ 1.0g / cm or more ３ It is even more preferable that the density of the MFI zeolite shaped body is not more than 1 / 2 of the mass of the MFI zeolite shaped body. In this specification, the density of the MFI zeolite shaped body is a bulk density determined by dividing the mass of the MFI zeolite shaped body by the bulk volume occupied by the MFI zeolite shaped body (that is, the volume including voids and pores formed inside the MFI zeolite shaped body), and can be determined by the Archimedes method in accordance with JIS R 1634. In measuring the density (bulk density) in accordance with JIS R 1634, ion-exchanged water can be used as the solvent for saturating (absorbing water into) the MFI zeolite shaped body, and a boiling method can be used to saturate (absorb water into) the MFI zeolite shaped body.

[0054] The MFI zeolite shaped body used in the filling step (1) can be produced by a production method including a step of drying a mixture containing MFI zeolite, an inorganic binder, and water (hereinafter also referred to as a "raw material mixture") (hereinafter also referred to as a "raw material drying step").

[0055] The raw material mixture may be composed only of MFI zeolite, an inorganic binder, and water, but may also contain other substances (hereinafter simply referred to as "other substances"). Examples of such other substances include molding aids. The inclusion of a molding aid in the raw material mixture further improves the moldability of the raw material mixture.

[0056] The raw material mixture can be obtained by mixing MFI zeolite, an inorganic binder, water, and other substances that are contained as necessary. The raw material composition may be molded into a predetermined shape taking into consideration the shape of the MFI zeolite shaped article to be produced. The content of each raw material contained in the raw material mixture can be set appropriately taking into consideration the composition of the MFI zeolite shaped article to be produced.

[0057] In the raw material drying step, the raw material mixture is dried. The raw material mixture may be dried by any method, but a method of heat-treating the raw material composition can be used. Heat treatment conditions include, for example, heat treatment in an air atmosphere at 15°C to 300°C for 1 hour to 72 hours, and preferably heat treatment in an air atmosphere at 50°C to 300°C for 2 hours to 24 hours.

[0058] The method for producing a shaped MFI zeolite body may include only the raw material drying step described above, or may further include, in addition to the raw material drying step described above, either a step of calcining the dried raw material mixture (shaped MFI zeolite body) (hereinafter also referred to as a "raw material calcining step") or a step of removing aluminum from the skeletal structure of MFI zeolite contained in the dried raw material mixture (shaped MFI zeolite body) (hereinafter also referred to as a "raw material dealumination step"). Among these, the method for producing a shaped MFI zeolite body preferably includes the raw material drying step and the raw material dealumination step. Note that, when the method for producing a shaped MFI zeolite body includes the raw material drying step and the raw material dealumination step, it may further include a step (raw material calcining step) of calcining the raw material mixture (shaped MFI zeolite body) from which aluminum has been removed from the skeletal structure of MFI zeolite. Furthermore, when the method for producing an MFI zeolite shaped body includes a raw material drying step and a raw material calcining step, the method may further include a step of removing aluminum from the framework structure of MFI zeolite contained in the calcined raw material mixture (MFI zeolite shaped body) (raw material dealumination step).

[0059] In the raw material calcination step, the dried raw material mixture is calcined under the conditions of, for example, an air atmosphere at 350° C. to 700° C. for 1 hour to 24 hours, and preferably an air atmosphere at 400° C. to 600° C. for 2 hours to 24 hours.

[0060] In the raw material dealumination step, aluminum is removed from the skeletal structure of MFI zeolite contained in the dried raw material mixture (MFI zeolite shaped body). By including this raw material dealumination step in the method for producing MFI zeolite shaped body, the acid amount can be adjusted. In order to remove aluminum from the skeletal structure of MFI zeolite in the raw material dealumination step, a steam treatment can be used in which the dried raw material mixture (MFI zeolite shaped body) is brought into contact with a gas containing water vapor (hereinafter also referred to as "steam").

[0061] The steam to be brought into contact with the dried raw material mixture (MFI zeolite shaped body) may be composed of water vapor alone, but may also contain a diluent gas for diluting the water vapor in addition to the water vapor. Examples of the diluent gas include an inert gas such as nitrogen, air, oxygen, carbon monoxide, carbon dioxide, or a mixture thereof. The water vapor concentration in the steam is preferably 0.01% by volume or more and 100% by volume or less, and more preferably 10% by volume or more and 60% by volume or less.

[0062] The temperature of the steam brought into contact with the dried raw material mixture (MFI zeolite shaped body) is preferably 400°C or higher and 900°C or lower, more preferably 450°C or higher and 800°C or lower, and even more preferably 500°C or higher and 700°C or lower. The time for which the steam is brought into contact with the dried raw material mixture (MFI zeolite shaped body) is not particularly limited, and may be appropriately adjusted so that the acidity of the MFI zeolite contained in the dried raw material mixture (MFI zeolite shaped body) becomes a desired value, but is preferably 1 hour or higher and 100 hours or lower, and more preferably 2 hours or higher and 24 hours or lower. The pressure of the steam brought into contact with the calcined raw material mixture (MFI zeolite shaped body) is preferably 0.001 MPa or higher and 5 MPa or lower, more preferably 0.01 MPa or higher and 0.5 MPa or lower, and even more preferably 0.05 MPa or higher and 0.2 MPa or lower, in terms of the partial pressure of water vapor.

[0063] In the packing step (1), a plurality of the above-described MFI zeolite shaped bodies are prepared and packed into the packing section. The plurality of MFI zeolite shaped bodies packed into the packing section may have the same or different shapes and sizes.

[0064] The filling section in which a plurality of MFI zeolite shaped bodies are filled is a space for accommodating a plurality of MFI zeolite shaped bodies, and an aqueous zinc solution and a cleaning liquid flow through the space filled with a plurality of MFI zeolite shaped bodies.

[0065] As shown in Fig. 1, the length of the packed section in which the plurality of MFI zeolite shaped bodies are packed is L (m) in the supply direction of the aqueous zinc solution supplied to the packed section F. The supply direction of the aqueous zinc solution is as shown in Fig. 1 from the inlet H of the aqueous zinc solution in the packed section F. ｉｎ From outlet H ｏｕｔ The length L of the packed part F is the direction toward the inlet H of the zinc aqueous solution in the packed part F. ｉｎ From outlet H ｏｕｔ It is the shortest distance to

[0066] The length L of the filling section F is determined taking into consideration the volume of the filling section F, but from the viewpoint of making it easier to contain zinc that is difficult to volatilize in a reducing atmosphere, it is preferably 0.5 m or more, 1.0 m or more, or 1.5 m or more, and preferably 6 m or less, 5 m or less, or 4 m or less. The upper and lower limit values ​​of the length L of the filling section F may be any combination of the above-mentioned upper and lower limit values, but from the viewpoint of making it easier to contain zinc that is difficult to volatilize in a reducing atmosphere, the length L of the filling section F is preferably 0.5 m or more and 6 m or less, more preferably 1.0 m or more and 5 m or less, and even more preferably 1.5 m or more and 4 m or less.

[0067] The shape of the filling section F is not particularly limited, and can be exemplified by a cylindrical shape or a polygonal column shape as shown in Fig. 1, and is preferably a cylindrical shape with a length L of 0.5 m or more and a diameter D of 10 cm or more, more preferably a cylindrical shape with a length L of 0.5 m or more and a diameter D of 10 cm or more and a diameter D of 500 cm or less, and even more preferably a cylindrical shape with a length L of 0.5 m or more and a diameter D of 10 cm or more and a diameter D of 100 cm or less. Note that the diameter D is the diameter of the cross section when the filling section F is cut on a plane perpendicular to the supply direction of the zinc aqueous solution.

[0068] The packed portion F, which is packed with a plurality of MFI zeolite shaped bodies, can be formed of a cylindrical member (for example, a reaction tube), as shown in Fig. 1. The material of the cylindrical member which forms the packed portion F may be any material as long as it does not inhibit the MFI zeolite shaped bodies from containing zinc, and for example, one or more materials selected from the group consisting of glass, polyvinyl chloride, and stainless steel can be used.

[0069] From the viewpoint of making it easier to incorporate zinc, which is difficult to volatilize in a reducing atmosphere, the filling of the plurality of MFI zeolite shaped bodies into the filling section F is preferably carried out so that the porosity of the filling section F is 10% or more, 20% or more, or 25% or more, and preferably 50% or less, 45% or less, or 40% or less. The upper and lower limit values ​​of the porosity described above may be any combination of the upper and lower limit values ​​described above, but from the viewpoint of making it easier to incorporate zinc, which is difficult to volatilize in a reducing atmosphere, the filling of the plurality of MFI zeolite shaped bodies into the filling section F is preferably carried out so that the porosity of the filling section F is 10% or more and 50% or less, more preferably 20% or more and 45% or less, and even more preferably 25% or more and 40% or less.

[0070] The porosity of the packed portion F is the ratio (%) of the area in the packed portion F that is not packed with the MFI zeolite shaped body, and can be calculated from the following formula (I). ＭＦＩ (Volume of MFI zeolite molded body [cm ３ ]) can be calculated from the following formula (II): ｆ = (1 - V ＭＦＩ / V ｆ ) × 100 (I) (In the above formula (I), P ｆ indicates the porosity [%] of the filling part F, and V ｆ is the volume of the filling part F [cm ３ ], and V ＭＦＩ is the volume of the MFI zeolite molded body [cm ３ ] indicates.) V ＭＦＩ =M ＭＦＩ / D ＭＦＩ... (II) (In the above formula (II), V ＭＦＩ is the volume of the MFI zeolite molded body [cm ３ ], and M ＭＦＩ indicates the mass [g] of the MFI zeolite molded body, and D ＭＦＩ is the density of the MFI zeolite molded body [g / cm ３ ] is shown.)

[0071] Next, the zinc-containing step (2) included in the first production method will be described. The zinc-containing step (2) is a step of supplying an aqueous zinc solution having a zinc concentration of 10 to 2000 mM to a packing section packed with a plurality of MFI zeolite shaped bodies, and bringing the plurality of MFI zeolite shaped bodies into contact with the aqueous zinc solution. In the zinc-containing step, by bringing the plurality of MFI zeolite shaped bodies into contact with the aqueous zinc solution, the zinc contained in the aqueous zinc solution is incorporated into the MFI zeolite shaped bodies. It is preferable that the zinc contained in the MFI zeolite shaped bodies not be at an excessively high concentration, because this makes it difficult for the contained zinc to volatilize during reduction.

[0072] In the zinc-containing step, the aqueous zinc solution brought into contact with the multiple MFI zeolite shaped bodies is an aqueous solution in which zinc and at least one of its salts are dissolved in water. Examples of zinc salts that can be dissolved in the aqueous zinc solution include one or more selected from the group consisting of zinc oxide, zinc hydroxide, zinc acetate, zinc nitrate, zinc chloride, zinc carbonate, and zinc sulfate. From the viewpoint of making it easier to incorporate zinc, which is difficult to volatilize through reduction, the zinc salt that can be dissolved in the aqueous zinc solution is preferably one or more selected from the group consisting of zinc nitrate, zinc acetate, and zinc chloride.

[0073] In the zinc-containing step, the zinc aqueous solution that is brought into contact with the multiple MFI zeolite shaped bodies has a zinc concentration of 10 mM or more and 2000 mM or less. By having the zinc concentration of the zinc aqueous solution be 10 mM or more and 2000 mM or less, zinc that is difficult to reduce and volatilize can be contained in the zeolite shaped bodies. On the other hand, if the zinc concentration of the zinc aqueous solution is less than 10 mM, zinc that is difficult to reduce and volatilize will be difficult to contain in the MFI zeolite shaped bodies, and if the zinc concentration of the zinc aqueous solution exceeds 2000 mmol / L, excessive zinc will be contained in the MFI zeolite shaped bodies, and the proportion of zinc that is easily reduced and volatilized will increase.

[0074] From the viewpoint of making it easier for the MFI zeolite shaped bodies to incorporate zinc, which is difficult to volatilize through reduction, into the MFI zeolite shaped bodies, the zinc concentration of the aqueous zinc solution to be brought into contact with the multiple MFI zeolite shaped bodies is preferably 20 mM or more, 25 mM or more, or 30 mM or more, and preferably 1000 mM or less, 500 mM or less, or 200 mM or less. The upper and lower limits of the zinc concentration may be any combination of the upper and lower limits described above, but the zinc concentration in the aqueous zinc solution is preferably 10 mM or more and 1000 mM or less, more preferably 10 mM or more and 500 mM or less, and even more preferably 20 mM or more and 200 mM or less. The zinc concentration in the aqueous zinc solution can be determined by calculation from the amount of water contained in the aqueous zinc solution and the molar amount of zinc contained in the zinc and / or a salt thereof contained in the aqueous zinc solution.

[0075] The amount of the aqueous zinc solution to be brought into contact with the plurality of MFI zeolite shaped bodies is preferably 1 part by mass or more or 2 parts by mass or more, and preferably 10 parts by mass or less, 7 parts by mass or less, or 6 parts by mass or less, relative to 1 part by mass of the MFI zeolite shaped bodies, from the viewpoint of making it easier for the MFI zeolite shaped bodies to incorporate zinc, which is difficult to volatilize through reduction. The combination of the upper and lower limits for the amount of the aqueous zinc solution is arbitrary, but from the viewpoint of excellent zinc loading efficiency, the amount of the aqueous zinc solution is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 7 parts by mass or less, and even more preferably 2 parts by mass or more and 6 parts by mass or less, relative to 1 part by mass of the MFI zeolite shaped bodies.

[0076] The linear flow velocity of the aqueous zinc solution coming into contact with the multiple MFI zeolite shaped bodies is preferably 5 cm / min or more, or 10 cm / min or more, and preferably 50 cm / min or less, 40 cm / min or less, or 35 cm / min or less, since this tends to suppress pulverization of the MFI zeolite shaped bodies. The upper and lower limit values ​​for the linear flow velocity of the aqueous zinc solution may be combined arbitrarily, but since this tends to suppress pulverization of the MFI zeolite shaped bodies, the linear flow velocity is preferably 5 cm / min or more and 50 cm / min or less, more preferably 5 cm / min or more and 40 cm / min or less, and even more preferably 10 cm / min or more and 35 cm / min or less. The linear flow velocity of the aqueous zinc solution coming into contact with the MFI zeolite shaped bodies can be determined by dividing the flow rate in the packed section by the cross-sectional area of ​​the packed section. The cross-sectional area of ​​the packed section is the area of ​​a cross section obtained by cutting the packed section along a plane perpendicular to the supply direction of the liquid.

[0077] The temperature of the aqueous zinc solution to be brought into contact with the multiple MFI zeolite shaped bodies can be set as appropriate within the range in which zinc is contained in the MFI zeolite shaped bodies, but from the viewpoint of making it easier for zinc that is difficult to volatilize through reduction to be contained in the MFI zeolite shaped bodies, the temperature is preferably 15° C. or higher or 20° C. or higher, and preferably 60° C. or lower, or 40° C. or lower. The combination of the upper and lower limits of the temperature of the aqueous zinc solution described above is arbitrary, but from the viewpoint of making it easier for zinc that is difficult to volatilize through reduction to be contained in the MFI zeolite shaped bodies, the temperature of the aqueous zinc solution is preferably 15° C. or higher and 60° C. or lower, and more preferably 20° C. or higher and 40° C. or lower.

[0078] The contact of the plurality of MFI zeolite shaped bodies with the aqueous zinc solution can be carried out by supplying the aqueous zinc solution to a packed section in which the plurality of MFI zeolite shaped bodies are packed. The supply direction of the aqueous zinc solution to the packed section is not particularly limited, but from the viewpoint of improving the contact efficiency between the MFI zeolite shaped bodies and the aqueous zinc solution, it is preferable to supply the aqueous zinc solution to the packed section from below to above in the vertical direction.

[0079] The aqueous zinc solution supplied to the filling section can be circulated through the circulation flow path so that it is discharged from the filling section and then supplied to the filling section again. As shown in Figure 2, the circulation flow path for circulating the aqueous zinc solution is composed of the filling section F and a flow path P connected to the filling section F. The flow path P connected to the filling section F is connected to the outlet H of the filling section F. ｏｕｔ and a flow path P1 connected to the inlet H of the filling section F. ｉｎ 2, the zinc aqueous solution discharged from the filling section F is sent to the pump Pp via the flow path P1, and is pressurized by the pump Pp and supplied again to the filling section F via the flow path P2.

[0080] In the zinc-containing step (2) included in the first production method, a plurality of MFI zeolite shaped bodies are brought into contact with the aqueous zinc solution until the contact time T1 between the plurality of MFI zeolite shaped bodies and the aqueous zinc solution satisfies the following formula (A). When the contact time T1 satisfies the following formula (A), the MFI zeolite shaped bodies and the aqueous zinc solution can be in sufficient contact with each other, and zinc that is difficult to reduce and volatilize can be incorporated into the MFI zeolite shaped bodies. On the other hand, when the contact time T1 does not satisfy the following formula (A), the contact between the MFI zeolite shaped bodies and the aqueous zinc solution becomes insufficient, and zinc that is easy to reduce and volatilize becomes more likely to be incorporated into the MFI zeolite shaped bodies. T1≧L×1.5 (A) In the above formula (A), T1 is the contact time [hr] between the plurality of MFI zeolite shaped bodies and the aqueous zinc solution, and L is the length [m] of the packed section in the supply direction of the aqueous zinc solution.

[0081] The contact time T1 between the multiple MFI zeolite shaped bodies and the aqueous zinc solution may be any time as long as it satisfies the above formula (A), but from the viewpoint of making it easier for zinc, which is difficult to volatilize through reduction, to be contained in the MFI zeolite shaped bodies, it preferably satisfies the following formula (A-1), more preferably satisfies the following formula (A-2), and even more preferably satisfies the following formula (A-3): 150≧T1≧L×1.5 (A-1) 150≧T1≧L×2.0 (A-2) 150≧T1≧L×2.5 (A-3) In the above formulas (A-1), (A-2), and (A-3), T1 and L are synonymous with T1 and L in the above formula (A), respectively.

[0082] Next, the washing step (3) included in the first production method will be described. The washing step (3) is a step of bringing a washing liquid into contact with the plurality of MFI zeolite shaped bodies that have been contacted with the aqueous zinc solution.

[0083] In the washing step (3), the washing liquid to be brought into contact with the multiple MFI zeolite shaped bodies may be any liquid capable of removing acidic components (acidic components derived from the aqueous zinc solution) adhering to the MFI zeolite shaped bodies, and is not particularly limited, but examples thereof include at least one of water and an alkaline aqueous solution, with water being preferred. Examples of alkaline aqueous solutions that can be used as the washing liquid include at least one selected from the group consisting of ammonia water, sodium carbonate water, sodium bicarbonate water, calcium carbonate water, calcium bicarbonate water, sodium tetraborate water, potassium hydroxide water, and barium hydroxide water.

[0084] In the washing step (3), the contact of the multiple MFI zeolite shaped bodies with the washing liquid is carried out so that when a test (hereinafter also referred to as a "washed MFI zeolite shaped bodies") is conducted in which the MFI zeolite shaped bodies that have been contacted with the washing liquid are contacted with 2 parts by mass of water per 1 part by mass of the zeolite shaped bodies for 60 minutes (hereinafter also referred to as a "washing confirmation test"), the pH of the water used in the washing confirmation test (hereinafter also referred to as "water after the washing confirmation test") is 2.5 or higher. By contacting the MFI zeolite shaped bodies with the washing liquid so that the pH of the water after the washing confirmation test is 2.5 or higher, the MFI zeolite shaped bodies are sufficiently washed, and zinc that is difficult to volatilize through reduction can be incorporated into the MFI zeolite shaped bodies. On the other hand, if the pH of the water after the cleaning confirmation test is only less than 2.5 even when the MFI zeolite shaped body is brought into contact with the cleaning liquid, the MFI zeolite shaped body has not been sufficiently cleaned, and zinc, which is easily reduced and volatilized, ends up being contained in the MFI zeolite shaped body.

[0085] In the washing step (3), the contact of the multiple MFI zeolite shaped bodies with the washing liquid may be carried out so that the pH of the water after the washing confirmation test is 2.5 or higher. From the viewpoint of making it easier for the MFI zeolite shaped bodies to contain zinc, which is difficult to volatilize by reduction, the washing step is preferably carried out so that the pH of the water after the washing confirmation test is 2.5 or higher and 9.0 or lower, more preferably so that the pH of the water after the washing confirmation test is 2.5 or higher and 8.0 or lower, and even more preferably so that the pH of the water after the washing confirmation test is 3.0 or higher and 8.0 or lower.

[0086] The cleaning confirmation test using the washed MFI zeolite shaped body can be carried out by placing 10.0 g of the washed MFI zeolite shaped body and 20.0 g of pure water in a predetermined container (for example, a 100 mL beaker) and leaving the mixture to stand for 60 minutes at 25° C. Furthermore, the MFI zeolite shaped body used in the cleaning confirmation test (washed MFI zeolite shaped body) can be an MFI zeolite shaped body containing a cleaning solution, and the MFI zeolite shaped body that has been contacted with the cleaning solution (the MFI zeolite shaped body immediately after contact with the cleaning solution has been stopped) can be collected in a container (for example, a beaker) separate from the container in which the cleaning confirmation test is carried out and left to stand in the air for 5 minutes, and then transferred to a container for the cleaning confirmation test, before the cleaning confirmation test is carried out.

[0087] In the washing step (3), the contact of the plurality of MFI zeolite shaped bodies with the washing liquid is preferably carried out so that the pH of the water after the cleaning confirmation test is 2.5 or higher for all of the plurality of MFI zeolite shaped bodies that have been contacted with the washing liquid, but it is sufficient that the contact of the plurality of MFI zeolite shaped bodies with the washing liquid is carried out so that the pH of the water after the cleaning confirmation test is 2.5 or higher for at least some of the plurality of MFI zeolite shaped bodies that have been contacted with the washing liquid. MFI zeolite shaped bodies that have a pH of 2.5 or higher after the cleaning confirmation test are zinc-containing MFI zeolite shaped bodies that are resistant to reduction and volatilization of zinc, and therefore it is sufficient that the contact of the plurality of MFI zeolite shaped bodies with the washing liquid in the washing step (3) is carried out so that the pH of the water after the cleaning confirmation test is 2.5 or higher for at least some of the plurality of MFI zeolite shaped bodies that have been contacted with the washing liquid.

[0088] In the washing step (3), the contact between the MFI zeolite shaped bodies and the washing liquid is carried out by supplying the washing liquid to the packed section. The supply direction of the washing liquid is not particularly limited and may be the same as or different from the supply direction of the zinc aqueous solution. From the viewpoint of improving the contact efficiency between the MFI zeolite shaped bodies and the washing liquid, it is preferable that the washing liquid be supplied to the packed section from below to above in the vertical direction. The washing liquid supplied to the packed section may be circulated through a circulation flow path in which the washing liquid discharged from the packed section is supplied again to the packed section, or may be passed through an open flow path in which new washing liquid is continuously supplied to the packed section (the washing liquid discharged from the packed section is continuously discarded). Furthermore, when the washing liquid is circulated through the circulation flow path, part or all of the washing liquid may be replaced with new washing liquid after a predetermined period of time has elapsed since the washing liquid was circulated. The number of times the washing liquid is replaced may be appropriately adjusted so that the pH of the water after the cleaning confirmation test is 2.5 or higher.

[0089] The contact conditions between the MFI zeolite shaped body and the cleaning liquid are not particularly limited, and may be appropriately adjusted so that the pH of the water after the cleaning confirmation test is 2.5 or higher, but the greater the amount of cleaning liquid relative to the MFI zeolite shaped body, the more likely the pH of the water after the cleaning confirmation test will increase, and the longer the contact time between the MFI zeolite shaped body and the cleaning liquid, the more likely the pH of the water after the cleaning confirmation test will increase. Therefore, in order to make the pH of the water after the cleaning confirmation test 2.5 or higher, it is preferable to adjust the amount of cleaning liquid relative to the MFI zeolite shaped body and the contact time between the MFI zeolite shaped body and the cleaning liquid, taking into consideration the above-mentioned characteristics.

[0090] In the washing step (3), by bringing multiple MFI zeolite shaped bodies into contact with a washing solution so that the pH of the water after the washing confirmation test is 2.5 or higher, it is possible to obtain a zinc-containing MFI zeolite shaped body of the present invention in which zinc is less likely to be reduced and volatilized.

[0091] The first production method may include at least three steps, namely, the filling step (1), the zinc-containing step (2), and the washing step (3), as described above. In addition to these steps, the first production method may further include a step of drying the washed MFI zeolite shaped body (zinc-containing MFI zeolite shaped body) (hereinafter also referred to as a "drying step (4)"). Furthermore, in addition to the filling step (1), the zinc-containing step (2), the washing step (3), and the drying step (4), the first production method may further include either a step of calcining the dried MFI zeolite shaped body (hereinafter also referred to as a "calcining step (5)") or a step of removing aluminum from the framework structure of the MFI zeolite contained in the dried MFI zeolite shaped body (hereinafter also referred to as a "dealuminization step (6)"). Among these, the first production method preferably includes the filling step (1), the zinc-containing step (2), the washing step (3), the drying step (4), and the dealumination step (6).

[0092] When the first production method includes the filling step (1), the zinc-containing step (2), the washing step (3), the drying step (4), and the dealumination step (6), it may further include a step of calcining the MFI zeolite shaped body in which aluminum has been separated from the skeletal structure of the MFI zeolite (calcination step (5)). When the first production method includes the filling step (1), the zinc-containing step (2), the washing step (3), the drying step (4), and the calcination step (5), it may further include a step of separating aluminum from the skeletal structure of the MFI zeolite contained in the calcined MFI zeolite shaped body (dealuminization step (6)).

[0093] The drying step (4) is a step of drying the washed MFI zeolite shaped body (zinc-containing MFI zeolite shaped body). Any method may be used to dry the zinc-containing MFI zeolite shaped body, but a method of heat-treating the zinc-containing MFI zeolite shaped body can be used. Examples of heat-treatment conditions include heat treatment in an air atmosphere at 60°C or higher and 300°C or lower for 5 hours or longer and 30 hours or shorter, and heat treatment in an air atmosphere at 80°C or higher and 200°C or lower for 6 hours or longer and 25 hours or shorter is preferred.

[0094] The calcination step (5) is a step of calcining the dried MFI zeolite shaped body (zinc-containing MFI zeolite shaped body). Examples of the calcination conditions include calcination in an air atmosphere at 450° C. or higher and 600° C. or lower for 1 hour or longer and 12 hours or shorter, and preferably calcination in an air atmosphere at 450° C. or higher and 550° C. or lower for 1 hour or longer and 12 hours or shorter.

[0095] The dealumination step (6) is a step of removing aluminum from the skeletal structure of MFI zeolite contained in the dried MFI zeolite shaped body (zinc-containing MFI zeolite shaped body). By including the dealumination step (6) in the first production method, it is possible to adjust the acidity of MFI zeolite contained in the zinc-containing MFI zeolite shaped body. In order to remove aluminum from the skeletal structure of MFI zeolite, a steam treatment can be used in which the zinc-containing MFI zeolite shaped body is brought into contact with steam. The steam treatment method is the same as the steam treatment that can be carried out in the production process of an MFI zeolite shaped body, except that a dried MFI zeolite shaped body (zinc-containing MFI zeolite shaped body) is used instead of a dried raw material mixture (MFI zeolite shaped body), and therefore a detailed description thereof will be omitted.

[0096] The zinc-containing MFI zeolite shaped body of the present invention can be produced by the above-mentioned first production method, but the production method is not limited to the first production method. For example, the zinc-containing MFI zeolite shaped body of the present invention may be produced by a production method (hereinafter also referred to as a "second production method") including at least two steps: a step of contacting the MFI zeolite shaped body with an aqueous zinc solution, and a step of contacting the MFI zeolite shaped body that has been contacted with the aqueous zinc solution with a cleaning solution. The MFI zeolite shaped body, aqueous zinc solution, and cleaning solution used in the second production method are the same as those used in the first production method, and therefore detailed description thereof will be omitted.

[0097] In the second production method, if the contact time between the MFI zeolite shaped body and the aqueous zinc solution is short, the contact time between the MFI zeolite shaped body and the washing solution is short, the amount of aqueous zinc solution brought into contact with the MFI zeolite shaped body is small, the amount of washing solution brought into contact with the MFI zeolite shaped body is small, or the number of times the washing solution is replaced is insufficient, the free zinc percentage of the zinc-containing MFI zeolite shaped body produced will exceed 30%. Therefore, in order to produce the zinc-containing MFI zeolite shaped body of the present invention by the second production method, it is necessary to adjust the contact time between the MFI zeolite shaped body and the aqueous zinc solution, the contact time between the MFI zeolite shaped body and the washing solution, the amount of the aqueous zinc solution, the amount of the washing solution, and the number of times the washing solution is replaced, taking into consideration the above-mentioned characteristics, so as to obtain a zinc-containing MFI zeolite shaped body (the zinc-containing MFI zeolite shaped body of the present invention) that satisfies the features (i) to (iii).

[0098] In the second production method, similar to the first production method, the acid amount of the MFI zeolite shaped body may be adjusted by steaming the MFI zeolite shaped body before it is brought into contact with the aqueous zinc solution. In the second production method, similar to the first production method, the acid amount of the MFI zeolite shaped body (zinc-containing MFI zeolite shaped body) may be adjusted by steaming the washed MFI zeolite shaped body (zinc-containing MFI zeolite shaped body) after it has been dried.

[0099] The zinc-containing MFI zeolite shaped article of the present invention can be used as a catalyst for producing aromatic hydrocarbon compounds, which are used to produce aromatic hydrocarbon compounds from aliphatic hydrocarbon compounds.

[0100] A catalyst for producing aromatic hydrocarbon compounds in which the zinc-containing MFI zeolite shaped article of the present invention is used (hereinafter also referred to as the "catalyst for producing aromatic hydrocarbon compounds of the present invention") contains at least the zinc-containing MFI zeolite shaped article of the present invention. The catalyst for producing aromatic hydrocarbon compounds of the present invention may be composed solely of the zinc-containing MFI zeolite shaped article of the present invention, or it may be a mixture of the zinc-containing MFI zeolite shaped article of the present invention with a diluent or the like. Examples of diluents that can be contained in the catalyst for producing aromatic hydrocarbon compounds of the present invention include one or more components selected from the group consisting of silica, silica-alumina, alumina, titania, carbon, and ceramic-carbon. There are no limitations on the shape of the diluent, and it may have various shapes, such as spherical, granular, cylindrical, columnar, polygonal cylinder, polygonal pillar, and elliptical shape.

[0101] The production of aromatic hydrocarbon compounds using the catalyst for producing aromatic hydrocarbon compounds of the present invention can be carried out by contacting the catalyst for producing aromatic hydrocarbon compounds of the present invention with an aliphatic hydrocarbon compound.

[0102] The aliphatic hydrocarbon compound brought into contact with the catalyst for producing aromatic hydrocarbon compounds of the present invention is preferably an aliphatic hydrocarbon having 30 or less carbon atoms, as this makes it easier to maintain aromatic production activity. From the viewpoint of making it easier to co-produce light hydrocarbons together with aromatic hydrocarbon compounds, the aliphatic hydrocarbon compound brought into contact with the catalyst for producing aromatic hydrocarbon compounds of the present invention is preferably an aliphatic hydrocarbon having 4 to 30 carbon atoms, more preferably an aliphatic hydrocarbon having 4 to 15 carbon atoms, and even more preferably an aliphatic hydrocarbon having 4 to 6 carbon atoms. Aliphatic hydrocarbons to be brought into contact with the catalyst for producing aromatic hydrocarbon compounds of the present invention include, for example, paraffinic, olefinic, acetylenic, and alicyclic hydrocarbons, and specific examples thereof include propane, butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, icosane, henicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, and octacosane. and nonacosane; olefinic systems such as butene, isobutene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, icosene, eicosene, henicosene, docosene, tricosene, tetracosene, pentacosene, hexacosene, heptacosene, octacosene, and nonacosene; alicyclic systems such as cyclohexane, methylcyclohexane, dimethylcyclohexane, and decahydronaphthalene, and mixtures thereof.

[0103] The aliphatic hydrocarbons to be brought into contact with the catalyst for producing aromatic hydrocarbon compounds of the present invention may be aliphatic hydrocarbons derived from plants and / or chemically recycled. For example, aliphatic hydrocarbons produced by the thermal decomposition of plastics such as polyethylene may be used as the aliphatic hydrocarbons to be brought into contact with the catalyst for producing aromatic hydrocarbon compounds of the present invention.

[0104] The temperature (reaction temperature) at which the catalyst for producing aromatic hydrocarbon compounds of the present invention is brought into contact with aliphatic hydrocarbons is not particularly limited as long as it allows the production of aromatic hydrocarbon compounds. In particular, from the viewpoints of more easily maintaining aromatic production activity and more easily co-producing light hydrocarbon compounds together with aromatic hydrocarbon compounds, the temperature is preferably in the range of 400 to 800°C, and more preferably 400 to 700°C.

[0105] The pressure (reaction pressure) under which the catalyst for producing aromatic hydrocarbon compounds of the present invention is brought into contact with an aliphatic hydrocarbon is not particularly limited, and can be set to, for example, a pressure range of 0.05 MPa to 5 MPa (absolute pressure) or 0.05 MPa to 1 MPa (absolute pressure). Note that the absolute pressure is a pressure obtained by taking atmospheric pressure as 0.101 MPa.

[0106] The time (reaction time) for contacting the catalyst for producing aromatic hydrocarbon compounds of the present invention with aliphatic hydrocarbons may be appropriately set depending on the amount of aromatic hydrocarbon compounds to be produced.

[0107] The hourly space velocity (GHSV) of the aliphatic hydrocarbon to be brought into contact with the catalyst for producing aromatic hydrocarbon compounds of the present invention is not particularly limited. －１ ~50,000h －１ The GHSV of aliphatic hydrocarbons is a parameter that represents the amount of aliphatic hydrocarbons supplied per hour per unit volume occupied when the catalyst for producing aromatic hydrocarbon compounds of the present invention is packed into a reactor. The GHSV of aliphatic hydrocarbons can be calculated by dividing the amount of aliphatic hydrocarbons supplied per hour ([cc (aliphatic hydrocarbons) / h]) by the volume ([cc (catalyst layer)]) of the region occupied by the catalyst for producing aromatic hydrocarbon compounds (hereinafter also referred to as the "catalyst layer") (=[h-1]). The volume of the catalyst layer used to calculate the space velocity (GHSV) can be calculated from the product of the cross-sectional area of ​​the reaction tube packed with the catalyst for producing aromatic hydrocarbon compounds and the length of the catalyst layer (catalyst packed length). The cross-sectional area of ​​the reaction tube can be calculated by cutting the reaction tube in a direction perpendicular to the feed direction of the aliphatic hydrocarbons, and the length of the catalyst layer can be calculated by the average length of the catalyst layer in the feed direction of the aliphatic hydrocarbons.

[0108] The aliphatic hydrocarbon to be contacted with the catalyst for producing aromatic hydrocarbon compounds of the present invention may be in the form of a liquid, a gas, or a mixture of a liquid and a gas. However, from the viewpoint of more easily maintaining the aromatic production activity, the aliphatic hydrocarbon is preferably in the form of a gas.

[0109] The aliphatic hydrocarbon may be contacted with the catalyst for producing aromatic hydrocarbon compounds of the present invention as a single aliphatic hydrocarbon, or may be contacted with the catalyst for producing aromatic hydrocarbon compounds of the present invention as a mixed fluid in which the aliphatic hydrocarbon is mixed with other components other than the aliphatic hydrocarbon. Examples of other substances to be mixed with the aliphatic hydrocarbon include one or more substances selected from the group consisting of inert gases such as nitrogen, hydrogen, carbon monoxide, and carbon dioxide. Among these, it is preferable that the aliphatic hydrocarbon is contacted with the catalyst for producing aromatic hydrocarbon compounds of the present invention as a mixed fluid in which the aliphatic hydrocarbon is mixed with an inert gas such as nitrogen. The mixed fluid of the aliphatic hydrocarbon and other substance may be any of a liquid, a gas, and a mixture of a liquid and a gas, but is preferably a gas from the viewpoint of more easily maintaining the aromatic hydrocarbon production activity.

[0110] The mode (reaction mode) of contacting the catalyst for producing aromatic hydrocarbon compounds of the present invention with an aliphatic hydrocarbon is not limited, and for example, a fixed bed, transport bed, fluidized bed, moving bed, or multi-tubular reactor can be used, as well as a continuous flow reactor, an intermittent flow reactor, and a swing reactor, etc. A specific example is a mode in which the catalyst for producing aromatic hydrocarbon compounds of the present invention is packed into a fixed-bed flow reactor, and a fluid containing an aliphatic hydrocarbon is passed through the reactor to bring the catalyst for producing aromatic hydrocarbon compounds of the present invention into contact with the aliphatic hydrocarbon.

[0111] The aromatic hydrocarbon compound produced by contacting the catalyst for producing an aromatic hydrocarbon compound of the present invention with an aliphatic hydrocarbon is not particularly limited as long as it belongs to the category called an aromatic hydrocarbon compound, and examples thereof include one or more compounds selected from the group consisting of benzene, toluene, xylene, trimethylbenzene, ethylbenzene, propylbenzene, butylbenzene, naphthalene, and methylnaphthalene. One or more compounds selected from the group consisting of benzene, toluene, and xylene are preferred, and benzene is more preferred.

[0112] The substance produced by contacting the catalyst for producing aromatic hydrocarbon compounds of the present invention with an aliphatic hydrocarbon is not limited to aromatic hydrocarbon compounds; other substances may be co-produced together with the aromatic hydrocarbon compounds, and it is preferable that light hydrocarbon compounds are co-produced together with the aromatic hydrocarbon compounds. The light hydrocarbon compounds co-produced together with the aromatic hydrocarbon compounds are substances different from the aliphatic hydrocarbons used as the raw material, and are preferably aliphatic hydrocarbons having 3 or less carbon atoms, and are preferably hydrocarbon compounds having 2 carbon atoms (C2) such as ethane and ethylene, with ethylene being particularly preferred. The mass ratio of the light hydrocarbon compounds to the co-produced aromatic hydrocarbon compounds (light hydrogen compounds / aromatic hydrocarbon compounds) is preferably 10 / 100 to 40 / 100, since this method for producing aromatic hydrocarbon compounds has an excellent balance between the production of light hydrocarbon compounds and aromatic hydrocarbon compounds.

[0113] According to the present invention as described above, it is possible to provide a zinc-containing MFI zeolite shaped body that is likely to maintain its aromatics production activity even when a reaction for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons is continued. Furthermore, according to one embodiment of the present invention, it is also possible to provide a zinc-containing MFI zeolite shaped body that is likely to maintain its aromatics production activity even when a reaction for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons is continued, and that is capable of co-producing light hydrocarbons along with aromatic hydrocarbon compounds.

[0114] The present invention will be specifically described below with reference to examples.

[0115] The performance of the MFI zeolite used in the examples as a catalyst for producing aromatic hydrocarbon compounds was measured and defined by the following methods.

[0116] ~ Measurement of Zinc Content ~ The zinc content of the zinc-containing MFI zeolite shaped body was determined by the following method. 50 mg of the zinc-containing MFI zeolite shaped body was dissolved in 100 mL of a mixed aqueous solution of hydrofluoric acid and nitric acid while heating to obtain a measurement sample. The measurement sample was measured by inductively coupled plasma atomic emission spectrometry (ICP-AES) using a general ICP device ((trade name) OPTIMA3300DV, manufactured by PerkinElmer) to determine the amount of zinc in the measurement sample. The zinc content was determined from the amount of zinc in the measurement sample and the amount of zinc-containing MFI zeolite shaped body dissolved in the measurement sample.

[0117] Calculation of the Amount of Free Zinc 500 mg of the zinc-containing MFI zeolite shaped body whose zinc content had been measured was packed into a reaction tube. A reduction treatment test was carried out in which hydrogen was passed through the reaction tube packed with the zinc-containing MFI zeolite shaped body at 50 mL / min and nitrogen was passed through the reaction tube at 50 mL / min, and the reaction was carried out at 600°C for 16 hours. The zinc content of the zinc-containing MFI zeolite shaped body that had been subjected to the reduction treatment test was measured by the method described above. The amount of free zinc was calculated by subtracting the zinc content after the reduction treatment test from the zinc content before the reduction treatment test.

[0118] - Calculation of Free Zinc Ratio - The ratio of the amount of free zinc to the zinc content of the zinc-containing MFI zeolite shaped body (zinc content before the reduction treatment test) was determined, and the free zinc ratio was calculated by expressing this as a percentage.

[0119] Measurement of Acidity The acidity of the MFI zeolite shaped body (zinc-containing MFI zeolite shaped body) was measured using a general catalyst analyzer (device name: BELCAT II, ​​manufactured by Microtrack-Bell Corporation) in accordance with the ammonia-TPD method (see Measurement of Solid Acidity by Ammonia Temperature Programmed Desorption Method, Catalysts, Vol. 42, p. 218 (2000)). Specifically, 50 mg of the MFI zeolite shaped body was first pretreated by standing in a helium gas flow at 500°C for 1 hour, and this was used as a measurement sample. A mixed gas containing 10% by volume of ammonia and 90% by volume of helium was passed through the pretreated measurement sample at room temperature (25°C) for 1 hour to saturatedly adsorb ammonia onto the measurement sample. The mixed gas was changed to helium gas, and the MFI zeolite shaped body saturated with ammonia was heated in helium gas at 100°C for 1 hour to remove the ammonia remaining in the measurement atmosphere (ammonia not adsorbed in the MFI zeolite shaped body). The temperature was then increased from 100°C to 700°C at a rate of 10°C / min, and an ammonia thermal desorption spectrum was obtained, showing the amount of ammonia [mmol] released from the zinc-containing MFI zeolite shaped body during the temperature increase. After the temperature increase from 100°C to 700°C was completed, a mixed gas of ammonia and helium (hereinafter referred to as "NH") with a known ammonia content was measured. ３ The spectrum for sensitivity correction of the detector was obtained by passing a first NH 3 gas (also referred to as "NH 3 -He mixed gas") through a route (a separate line) that did not pass through the zinc-containing MFI zeolite shaped body. ３ -He mixed gas and a second NH ３ -He mixed gas and a third NH ３ The four gases obtained were three types of NH -He mixed gas and one type of helium gas. ３ The -He mixed gas and the helium gas alone were each passed at a flow rate of 30 mL / min for a flow time of 15 minutes at a temperature of 100°C.

[0120] The amount of ammonia desorbed [mmol] indicated by the H peak on the highest temperature side in the obtained ammonia temperature programmed desorption spectrum was considered to be the amount of solid acid [mmol] present in the MFI zeolite shaped body (the amount of ammonia adsorbed to the solid acid of the MFI zeolite shaped body [mmol]), and the amount of acid [mmol / g] was calculated from the amount of solid acid [mmol] and the mass [g] of the MFI zeolite shaped body used to adsorb ammonia. The amount of ammonia desorbed [mmol] indicated by the H peak was calculated by multiplying the integral value of the peak intensity of the peak contained in the spectrum for sensitivity correction by the amount of NH ３ The relationship between the integral value of the peak intensity and the amount of ammonia was determined from the amount of ammonia contained in the -He mixed gas, and the integral value of the peak intensity of the H peak was converted into the amount of ammonia based on this relationship.

[0121] For peak separation of the H peak, a method of curve fitting (peak separation) by the least squares method was used, assuming a function representing the peak. A Gaussian function was used as the function representing the peak. Peak separation of the H peak was performed using ChemMaster manufactured by MicrotracBell. Furthermore, background correction of the ammonia temperature-programmed desorption spectrum was performed by multi-point correction. Specifically, a point immediately before the start of heating from 100°C to 700°C (100°C point), a point immediately after the completion of heating from 100°C to 700°C (700°C point), and a point immediately after the completion of heating from 100°C to 700°C (700°C point) were used. ３ The correction was made by connecting a total of four points: the point immediately before the flow of the -He mixed gas started and the point immediately before the flow of the helium gas alone ended.

[0122] Calculation of Zinc Content / Acid Amount The zinc content (mass %) of the zinc-containing MFI zeolite shaped body was divided by the acid amount (mmol / g) to determine the zinc content / acid amount.

[0123] Measurement of Average Particle Size The average particle size (primary particle size) of the MFI zeolite contained in the MFI zeolite shaped body (zinc-containing MFI zeolite shaped body) was measured by TEM. A transmission electron microscope (JEM-2100, manufactured by JEOL Ltd.) was used for the TEM. First, the MFI zeolite shaped body was lightly crushed in a mortar and ultrasonically dispersed in acetone. The dispersion was dropped onto a plastic support film and allowed to air-dry to prepare a microscopic sample. In a TEM image obtained by observing the microscopic sample under the following conditions, 300 primary particles of MFI zeolite whose outlines were observed without interruption were randomly extracted. The particle size was determined by averaging the longest diameter of each extracted primary particle and the diameter in the direction perpendicular to its midpoint, and the particle diameters of the 300 primary particles were then averaged to determine the average particle size. Note that the longest diameter of a primary particle was determined by the distance between the longest parallel lines when the particle was sandwiched between two parallel lines tangent to the outline. Acceleration voltage: 200 kV Magnification: 30,000 times

[0124] Measurement of Density The density of the MFI zeolite shaped body (zinc-containing MFI zeolite shaped body) was determined by the Archimedes method in accordance with JIS R 1634. In the measurement of density (bulk density) in accordance with JIS R 1634, ion-exchanged water was used as the solvent for saturating (absorbing) the MFI zeolite shaped body with water, and a boiling method was used as the method for saturating (absorbing) the MFI zeolite shaped body with water.

[0125] - Hydrocarbon compound production apparatus and performance test method thereof - Using an MFI zeolite molded body (zinc-containing MFI zeolite molded body) as it is as a catalyst for producing aromatic hydrocarbon compounds, an aromatic hydrocarbon compound production test was carried out by the following method, and the results were evaluated.

[0126] A fixed-bed gas-phase flow reactor using stainless steel reaction tubes (inner diameter 16 mm, length 600 mm) was used. A catalyst for producing aromatic hydrocarbon compounds (MFI zeolite molded body) was packed into the middle section of each stainless steel reaction tube, and pretreatment was carried out at 530°C for 1 hour while flowing dry air. After pretreatment, an aromatic hydrocarbon compound production test was carried out under any of the following production conditions 1 to 4. The catalyst temperature was controlled by heating the catalyst layer using a ceramic tubular furnace.

[0127] (Production Condition 1) Catalyst temperature (reaction temperature): 530°C. Flowing gas: mixed gas of 1-butene 10 ml / min, 2-butene 6 ml / min, isobutene 18 ml / min, normal butane 4 ml / min, isobutane 2 ml / min, and dry nitrogen 40 ml / min. Aliphatic hydrocarbon gas weight flow rate: 100 mg / min. Aliphatic hydrocarbon hourly space velocity (GHSV): 259 h －１ Catalyst mass: 5.0 g. Reaction pressure (absolute pressure): 0.1 MPa. Reaction time: 48 hours

[0128] (Production Condition 2) Catalyst temperature (reaction temperature): 530°C. Reaction raw materials: a mixture of n-dodecane (45.8 wt%), n-eicosane (2.1 wt%), n-octacosane (2.1 wt%), 1-dodecene (9.3 wt%), 1-tetradecene (7.3 wt%), 1-hexadecene (9.5 wt%), 1-octadecene (7.2 wt%), 1-eicosene (8.4 wt%), 1-docosene (6.2 wt%), and 1-tetracosene (2.1 wt%). Flowing gas: a mixed gas of reaction raw materials at 100 mg / min and dry nitrogen at 40 ml / min. Space velocity (GHSV) of aliphatic hydrocarbons: 81 h －１ Catalyst mass: 5.0 g. Reaction pressure (absolute pressure): 0.1 MPa. Reaction time: 48 hours. The reaction raw material under Production Condition 2 was a raw material simulating the thermal decomposition product of a typical polyethylene (decomposition temperature: 400 to 450°C) (see Polymer, 1996, Vol. 45, No. 5, pp. 331-315).

[0129] (Production Condition 3) Catalyst temperature (reaction temperature): 530°C. Reactant: a mixture of n-dodecane (94.2 wt%), n-eicosane (3.9 wt%), and n-octacosane (1.9 wt%). Flowing gas: a mixed gas of reactant at 100 mg / min and dry nitrogen at 40 ml / min. Aliphatic hydrocarbon space velocity (GHSV): 99 h －１ Catalyst mass: 5.0 g. Reaction pressure (absolute pressure): 0.1 MPa. Reaction time: 48 hours

[0130] (Production Condition 4) Catalyst temperature (reaction temperature): 530°C. Flowing gas: mixed gas of triisobutylene 100 mg / min and dry nitrogen 40 ml / min. Aliphatic hydrocarbon gas weight flow rate: 100 mg / min. Aliphatic hydrocarbon hourly space velocity (GHSV): 86 h －１ Catalyst mass: 5.0 g. Reaction pressure (absolute pressure): 0.1 MPa. Reaction time: 48 hours

[0131] Two hours and 48 hours after the start of the aromatic hydrocarbon compound production test, the reaction outlet gas and reaction liquid (hereinafter also referred to as "reactants") discharged from the stainless steel reaction tube were sampled, and the gas components (outlet gas) and liquid components (reaction liquid) were analyzed individually using a gas chromatograph. The gas components were analyzed using a gas chromatograph (manufactured by Shimadzu Corporation, (trade name) GC-1700) equipped with a TCD detector. The packing used was PorapakQ (trade name) manufactured by Waters or MS-5A (trade name) manufactured by GL Sciences. The liquid components were analyzed using a gas chromatograph (manufactured by Shimadzu Corporation, (trade name) GC-2015) equipped with an FID detector. A capillary column (manufactured by GL Sciences, (trade name) TC-1) was used as the separation column.

[0132] The yield of each product component contained in the reaction product was calculated by adding the yield of each product component contained in the gas component (outlet gas) and the yield of each product component contained in the liquid component (reaction liquid). The yield of each product component contained in the gas component (outlet gas) was calculated using the external standard method, taking into account the total time the gas was collected, the total volume of the collected gas, and the analytical value obtained by gas chromatography. The yield of each product component contained in the liquid component (reaction liquid) was calculated using the internal standard method, taking into account the total time the solution was collected, the amount of internal standard added, and the analytical value obtained by gas chromatography.

[0133] Measurement of Pore Distribution, Pore Diameter-Pore Volume Using a mercury porosimeter (trade name: POREMASTER GT, manufactured by Quantachrome Instruments), mercury was forced into a measurement sample (a zinc-containing MFI zeolite shaped body) while changing the pressure, to obtain a mercury intrusion curve (a curve showing the relationship between pressure and the amount of mercury intrusion). The measurement of the amount of mercury intrusion using the mercury porosimeter was performed after pretreatment in which 0.6 g or 1.0 g of the sample (a zinc-containing MFI zeolite shaped body) was heat-treated at 450°C for 3 hours and then cooled to room temperature. The mercury intrusion amount was measured using a mercury porosimeter by filling a pretreated sample into a measurement cell (0.5 cc glass cell), decompressing the cell to 6.7 PaA or less for 15 minutes, and then gradually increasing the mercury pressure from 0.00738 MPaA to 245.1342 MPaA. The mercury intrusion amount measured using a blank cell (the mercury intrusion amount measured using a measurement cell not filled with a sample) was subtracted as a base from the mercury intrusion amount of the measured zinc-containing MFI zeolite shaped body (the actual mercury intrusion amount), to obtain a mercury intrusion curve showing the relationship between the base-corrected mercury intrusion amount and pressure. The Washburn equation was applied to the obtained mercury intrusion curve to obtain a curve showing the relationship between pore diameter and cumulative pore volume. In the Washburn equation, the surface tension σ of mercury was 480 erg / cm. ２The contact angle θ of mercury was set to 140°. From the curve showing the relationship between pore diameter and cumulative pore volume, the cumulative pore volume at a pore diameter of 0.011 μm, the cumulative pore volume at a pore diameter of 0.090 μm, and the cumulative pore volume at a pore diameter of 200 μm were calculated. The cumulative pore volume of pores having a pore diameter of 0.011 μm or more and 0.090 μm or less was calculated by subtracting the cumulative pore volume at a pore diameter of 0.090 μm from the cumulative pore volume at a pore diameter of 0.011 μm. In addition, the cumulative pore volume of pores having a pore diameter of 0.090 μm or more and 200 μm or less was calculated by subtracting the cumulative pore volume at a pore diameter of 200 μm from the cumulative pore volume at a pore diameter of 0.090 μm. The relationship between pore diameter and cumulative pore volume (pore distribution) was analyzed using analytical software ((trade name) Poremaster for WindowsR, manufactured by Quantachrome Instruments).

[0134] Preparation Example 1A MFI type zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA(SiO ２ / Al ２ O ３ To 100 parts by weight of the silica (product name Snowtex 50-T, manufactured by Nissan Chemical Industries, Ltd., average particle size 22 nm), 25 parts by weight of silica, 5 parts by weight of cellulose, and 35 parts by weight of pure water were added and kneaded. The kneaded mixture was then formed into a cylindrical molded product having a diameter of 3.0 mm and a length of 1.0 to 7.0 mm (average length 3.4 mm). This was dried at 100°C overnight and then calcined in air at 550°C for 1 hour, thereby obtaining a molded product of MFI zeolite of Preparation Example 1A.

[0135] Preparation Example 2A MFI type zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA(SiO ２ / Al ２ O ３ To 100 parts by weight of silica (product name Snowtex 50-T, average particle size 22 nm, manufactured by Nissan Chemical Industries, Ltd.), 15 parts by weight of cellulose, and 32 parts by weight of pure water were added and kneaded. A shaped body of MFI zeolite for Preparation Example 2A was obtained in the same manner as in Preparation Example 1A, except that the kneaded product obtained was used instead of the kneaded product used in Preparation Example 1A.

[0136] Preparation Example 3A A shaped body of MFI zeolite of Preparation Example 3A was obtained in the same manner as in Preparation Example 1A, except that the amount of pure water used in Preparation Example 1A (35 parts by weight) was changed to 43 parts by weight.

[0137] Preparation Example 4A MFI type zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA(SiO ２ / Al ２ O ３ To 100 parts by weight of silica (product name Snowtex ZL, average particle size 80 nm, manufactured by Nissan Chemical Industries, Ltd.), 45 parts by weight of cellulose, 5 parts by weight of cellulose, and 50 parts by weight of pure water were added and kneaded. A shaped body of MFI zeolite was obtained in the same manner as in Preparation Example 1A, except that the kneaded product obtained was used instead of the kneaded product used in Preparation Example 1A. The obtained shaped body of MFI zeolite was subjected to steam treatment at 600°C for 2 hours with steam containing 50% by volume of water vapor and 50% by volume of air, to obtain a shaped body of MFI zeolite of Preparation Example 4A.

[0138] Preparation Example 5A MFI type zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA(SiO ２ / Al ２ O ３ To 100 parts by weight of silica (product name Snowtex N-30G, average particle size 12 nm, manufactured by Nissan Chemical Industries, Ltd.), 25 parts by weight, 5 parts by weight of cellulose, and 35 parts by weight of pure water were added and kneaded. A shaped body of MFI zeolite for Preparation Example 5A was obtained in the same manner as in Preparation Example 1A, except that the kneaded product obtained was used instead of the kneaded product used in Preparation Example 1A.

[0139] Preparation Example 6A MFI type zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA(SiO ２ / Al ２ O ３To 100 parts by weight of silica (product name Snowtex ZL, average particle size 80 nm, manufactured by Nissan Chemical Industries, Ltd.), 45 parts by weight of cellulose, 5 parts by weight of cellulose, and 40 parts by weight of pure water were added and kneaded. A shaped body of MFI zeolite was obtained in the same manner as in Preparation Example 1A, except that the kneaded product obtained was used instead of the kneaded product used in Preparation Example 1A. The obtained shaped body of MFI zeolite was subjected to steam treatment at 600°C for 6 hours with steam containing 50% by volume of water vapor and 50% by volume of air, to obtain a shaped body of MFI zeolite of Preparation Example 6A.

[0140] Example 1A (Zn 0.74 / acid amount 0.35) 20 g of the MFI zeolite shaped body obtained in Preparation Example 1A was added to 100 ml of a 97 mmol / L aqueous zinc nitrate solution, stirred at room temperature for 24 hours, and then filtered. The filtered zeolite shaped body was then added to 100 ml of pure water, stirred at room temperature for 1 hour, and then filtered. This stirring and filtration in pure water was repeated five times. The zeolite shaped body was then transferred to a porcelain dish, heated to 110°C, and dried overnight. The temperature was then raised to 550°C and calcined for two hours, yielding a zinc-containing MFI zeolite shaped body. The obtained zinc-containing MFI zeolite shaped body was subjected to steam treatment at 600°C for four hours using steam containing 50% by volume of water vapor and 50% by volume of air, yielding a zinc-containing MFI zeolite shaped body of this example.

[0141] The obtained zinc-containing MFI zeolite shaped body had an acid amount of 0.35 mmol / g, a zinc content of 0.74 mass%, and a ratio of the zinc content to the acid amount of 2.1. Furthermore, the MFI zeolite shaped body had a free zinc amount of 0.01 mass%, and the ratio of the free zinc amount to the zinc content (free zinc rate) was 1%. The properties of the zinc-containing MFI zeolite shaped body of this example are shown in Table 1. It was confirmed that the zinc-containing MFI zeolite shaped body of this example contained zinc in an ionic state. Furthermore, in Tables 1 to 5 below, aromatic hydrocarbon compounds are referred to as aromatic components, and light hydrocarbon compounds are referred to as light components.

[0142] An aromatic hydrocarbon compound production test was conducted under production conditions 1 using the zinc-containing MFI zeolite shaped body of this example. The yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test are shown in Table 1 and Fig. 3. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.0 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 47.4 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 57.4 mass%. After 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.2 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 46.3 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 56.5 mass%.

[0143] Example 2A (Zn1.02 / acid amount 0.19) A zinc-containing MFI zeolite shaped body of this example was obtained in the same manner as in Example 1A, except that the MFI zeolite shaped body obtained in Preparation Example 2A was used instead of the MFI zeolite shaped body obtained in Preparation Example 1A, 100 ml of a 200 mmol / L aqueous zinc acetate solution was used instead of 100 ml of a 97 mmol / L aqueous zinc nitrate solution, and the steam treatment time was changed to 6 hours.

[0144] The obtained zinc-containing MFI zeolite shaped body had an acid amount of 0.19 mmol / g, a zinc content of 1.02 mass%, and a ratio of the zinc content to the acid amount of 5.4. Furthermore, the MFI zeolite shaped body had a free zinc amount of 0.06 mass%, and the ratio of free zinc to the zinc content (free zinc rate) was 6%. The properties of the zinc-containing MFI zeolite shaped body of this example are shown in Table 1. It was confirmed that the zinc-containing MFI zeolite shaped body of this example contained zinc in an ionic state.

[0145] An aromatic hydrocarbon production test was conducted under production conditions 1 using the zinc-containing MFI zeolite shaped body of this example. The yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test are shown in Table 1 and Fig. 3. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.1 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 47.0 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 57.1 mass%. After 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.1 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 46.1 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 56.2 mass%.

[0146] Example 3A (Zn2.51 / acid amount 0.26) 20 g of the MFI zeolite shaped body obtained in Preparation Example 3A was added to 100 ml of a 1460 mM aqueous zinc acetate solution, stirred at 80°C for 30 minutes, and then filtered. Stirring and filtration in this aqueous zinc acetate solution were repeated three times. The filtered zeolite shaped body was then added to 100 ml of pure water, stirred at 80°C for 30 minutes, and then filtered. Stirring and filtration in this pure water solution were repeated five times. The zeolite shaped body was then transferred to a porcelain dish, heated to 110°C, and dried overnight. The temperature was then raised to 550°C and calcined for 6 hours, yielding a zinc-containing MFI zeolite shaped body. The obtained zinc-containing MFI zeolite shaped body was subjected to steam treatment at 600°C for 6 hours with steam containing 50% by volume of water vapor and 50% by volume of air, yielding a zinc-containing MFI zeolite shaped body of this example.

[0147] The obtained zinc-containing MFI zeolite shaped body had an acid amount of 0.26 mmol / g, a zinc content of 2.51 mass%, and a ratio of the zinc content to the acid amount of 9.7. Furthermore, the MFI zeolite shaped body had a free zinc amount of 0.27 mass%, and the proportion of free zinc in the zinc content (free zinc rate) was 11%. The properties of the zinc-containing MFI zeolite shaped body of this example are shown in Table 1. It was confirmed that the zinc-containing MFI zeolite shaped body of this example contained zinc in the form of ions.

[0148] An aromatic hydrocarbon production test was conducted under production conditions 1 using the zinc-containing MFI zeolite shaped body of this example. The yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test are shown in Table 1 and Fig. 3. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.4 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 46.4 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 56.8 mass%. After 48 hours, the yield of light components (the sum of ethane and ethylene) was 10.9 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 45.2 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 56.1 mass%.

[0149] Example 4A (Zn 0.54 / acid amount 0.41) 20 g of the MFI zeolite shaped body obtained in Preparation Example 4A was added to 100 ml of a 1,460 mmol / L aqueous zinc nitrate solution, stirred at room temperature for 24 hours, and then filtered. The filtered zeolite shaped body was then added to 100 ml of pure water, stirred at room temperature for 1 hour, and then filtered. This stirring and filtration in pure water was repeated five times. The zeolite shaped body was then transferred to a porcelain dish, heated to 110°C, and dried overnight. The temperature was then raised to 550°C and calcined for 6 hours, yielding a zinc-containing MFI zeolite shaped body of this example.

[0150] The obtained zinc-containing MFI zeolite shaped body had an acid amount of 0.41 mmol / g, a zinc content of 0.54 mass%, and a ratio of the zinc content to the acid amount of 1.3. Furthermore, the MFI zeolite shaped body had a free zinc amount of 0.04 mass%, and the ratio of free zinc to the zinc content (free zinc rate) was 7%. The properties of the zinc-containing MFI zeolite shaped body of this example are shown in Table 1. It was confirmed that the zinc-containing MFI zeolite shaped body of this example contained zinc in the form of ions.

[0151] Using this zinc-containing MFI zeolite shaped body, an aromatic hydrocarbon production test was conducted under production conditions 1. The yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test are shown in Table 1 and Fig. 3. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.1 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 47.1 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 57.2 mass%. After 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.1 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 46.0 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 56.1 mass%.

[0152] Example 5A (Zn 0.90 / acid amount 0.33) A zinc-containing MFI zeolite shaped body of this example was obtained in the same manner as in Example 1A, except that the MFI zeolite shaped body obtained in Preparation Example 5A was used instead of the MFI zeolite shaped body obtained in Preparation Example 1A, 100 ml of a 150 mmol / L aqueous zinc nitrate solution was used instead of 100 ml of a 97 mmol / L aqueous zinc nitrate solution, and steam treatment was not performed.

[0153] The obtained zinc-containing MFI zeolite shaped body had an acid amount of 0.33 mmol / g, a zinc content of 0.90 mass%, and a ratio of the zinc content to the acid amount of 2.7. Furthermore, the MFI zeolite shaped body had a free zinc amount of 0.05 mass%, and the proportion of free zinc in the zinc content (free zinc rate) was 6%. The properties of the zinc-containing MFI zeolite shaped body of this example are shown in Table 1. It was confirmed that the zinc-containing MFI zeolite shaped body of this example contained zinc in an ionic state.

[0154] Using this zinc-containing MFI zeolite shaped body, an aromatic hydrocarbon production test was conducted under production conditions 1. The yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test are shown in Table 1 and Fig. 3. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 9.9 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 47.4 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 57.3 mass%. After 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 9.8 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 44.9 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 54.7 mass%.

[0155]

[0156] Comparative Example 1A (Acid Amount 0.20) The MFI zeolite shaped body obtained in Preparation Example 1A was subjected to steam treatment at 600°C for 6 hours using steam containing 50% by volume of water vapor and 50% by volume of air, thereby obtaining an MFI zeolite shaped body of this comparative example. The acid amount of the obtained MFI zeolite shaped body was 0.20 mmol / g. The properties of the MFI zeolite shaped body of this comparative example are shown in Table 2.

[0157] Using the MFI zeolite shaped body, an aromatic hydrocarbon production test was conducted under production conditions 1. The yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test are shown in Table 2 and FIG. 4. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 7.4 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 39.8 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 47.2 mass%. In contrast, after 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 8.4 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 39.2 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 47.6 mass%.

[0158] Comparative Example 2A (Zn3.5 / acid amount 0.30) 20 g of the MFI zeolite shaped body obtained in Preparation Example 1A was added to 100 ml of a 3000 mM aqueous zinc acetate solution, stirred at 80°C for 1 hour, and then filtered. This stirring and filtration in the aqueous zinc acetate solution was repeated three times. The filtered zeolite shaped body was then added to 100 ml of pure water, stirred at room temperature for 30 minutes, and then filtered. The zeolite shaped body was then transferred to a porcelain dish, heated to 110°C, and dried overnight. The temperature was then raised to 550°C and calcined for 6 hours, yielding a zinc-containing MFI zeolite shaped body. The zinc-containing MFI zeolite shaped body was subjected to steam treatment at 600°C for 5 hours using steam containing 50% by volume of water vapor and 50% by volume of air, yielding a zinc-containing MFI zeolite shaped body of this comparative example.

[0159] The obtained zinc-containing MFI zeolite shaped body had an acid amount of 0.30 mmol / g, a zinc content of 3.50 mass%, and a ratio of the zinc content to the acid amount of 11.7. Furthermore, the MFI zeolite shaped body had a free zinc amount of 1.50 mass%, and the ratio of free zinc to the zinc content (free zinc rate) was 43%. The properties of the MFI zeolite shaped body of this comparative example are shown in Table 2.

[0160] An aromatic hydrocarbon production test was conducted under production conditions 1 using the zinc-containing MFI zeolite shaped body of this comparative example. The yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test are shown in Table 2 and FIG. 4. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.9 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 46.0 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 56.9 mass%. In contrast, after 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 8.3 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 41.2 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 49.5 mass%.

[0161] Comparative Example 3A (Zn0.52 / acid amount 0.20) The MFI zeolite shaped body obtained in Preparation Example 1A was treated with 50% by volume water vapor at 600°C for 6 hours. 20 g of the obtained MFI zeolite shaped body was added to 100 ml of a 1460 mM aqueous zinc acetate solution, stirred at room temperature for 30 minutes, and then filtered. This stirring and filtration in the aqueous zinc acetate solution was repeated three times. The filtered zeolite shaped body was then added to 100 ml of pure water, stirred at room temperature for 30 minutes, and then filtered. The zeolite shaped body was then transferred to a porcelain dish, heated to 110°C, and dried overnight. The temperature was then raised to 550°C and calcined for 6 hours, yielding a zinc-containing MFI zeolite shaped body of this comparative example.

[0162] The obtained zinc-containing MFI zeolite shaped body had an acid amount of 0.20 mmol / g, a zinc content of 0.52 mass%, and a ratio of the zinc content to the acid amount of 2.6. Furthermore, the MFI zeolite shaped body had a free zinc amount of 0.25 mass%, and the ratio of free zinc to the zinc content (free zinc rate) was 48%. The properties of the MFI zeolite shaped body of this comparative example are shown in Table 2.

[0163] An aromatic hydrocarbon production test was conducted under production conditions 1 using the zinc-containing MFI zeolite shaped body of this comparative example. The yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test are shown in Table 2 and FIG. 4. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 9.8 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 46.9 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 56.7 mass%. In contrast, after 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 9.2 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 40.9 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 50.1 mass%.

[0164] Comparative Example 4A (Zn1.1 / acid amount 0.18) 20 g of the MFI zeolite shaped body obtained in Preparation Example 6A was added to 100 ml of a 1460 mM aqueous zinc acetate solution, stirred at 80°C for 30 minutes, and then filtered. The filtered zeolite shaped body was then added to 100 ml of pure water, stirred at room temperature for 30 minutes, and then filtered. This stirring and filtration in pure water was repeated five times. The zeolite shaped body was then transferred to a porcelain dish, heated to 110°C, and dried overnight. The temperature was then raised to 550°C and calcined for 6 hours, yielding a zinc-containing MFI zeolite shaped body of this comparative example.

[0165] The obtained zinc-containing MFI zeolite shaped body had an acid amount of 0.18 mmol / g, a zinc content of 1.10 mass%, and a ratio of the zinc content to the acid amount of 6.1. Furthermore, the zinc-containing MFI zeolite shaped body had a free zinc amount of 0.65 mass%, and a ratio of free zinc to the zinc content (free zinc rate) of 59%. The properties of the MFI zeolite shaped body of this comparative example are shown in Table 2.

[0166] An aromatic hydrocarbon production test was conducted under production conditions 1 using the zinc-containing MFI zeolite shaped body of this comparative example. The yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test are shown in Table 2 and FIG. 4. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.1 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 46.5 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 56.6 mass%. In contrast, after 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 8.1 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 42.1 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 50.2 mass%.

[0167] Comparative Example 5A (Zn 0.72 / acid amount 1.06) 20 g of the MFI zeolite shaped body obtained in Preparation Example 1A was added to 100 ml of a 97 mmol / L aqueous zinc acetate solution, stirred at room temperature for 24 hours, and then filtered. The filtered zeolite shaped body was then added to 100 ml of pure water, stirred at room temperature for 1 hour, and then filtered. This stirring and filtration in pure water was repeated five times. The zeolite shaped body was then transferred to a porcelain dish, heated to 110°C, and dried overnight. The temperature was then raised to 550°C and calcined for 6 hours, yielding a zinc-containing MFI zeolite shaped body of this comparative example.

[0168] The obtained zinc-containing MFI zeolite shaped body had an acid amount of 1.06 mmol / g, a zinc content of 0.72 mass%, and a ratio of the zinc content to the acid amount of 0.7. Furthermore, the zinc-containing MFI zeolite shaped body had a free zinc amount of 0.08 mass%, and a ratio of free zinc to the zinc content (free zinc rate) of 11%. The properties of the MFI zeolite shaped body of this comparative example are shown in Table 2.

[0169] An aromatic hydrocarbon production test was conducted under production conditions 1 using the zinc-containing MFI zeolite shaped body of this comparative example. The yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test are shown in Table 2 and FIG. 4. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 7.2 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 50.2 mass%, and the yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 57.4 mass%. In contrast, after 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 6.7 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 33.8 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 40.5 mass%.

[0170] Comparative Example 6A (Zn1.8 / acid amount 0.08) 20 g of the MFI zeolite shaped body obtained in Preparation Example 1A was added to 100 ml of a 1,460 mmol / L aqueous zinc nitrate solution, stirred at room temperature for 24 hours, and then filtered. The filtered zeolite shaped body was then added to 100 ml of pure water, stirred at room temperature for 1 hour, and then filtered. This stirring and filtration in pure water was repeated five times. The zeolite shaped body was then transferred to a porcelain dish, heated to 110°C, and dried overnight. The temperature was then raised to 550°C and calcined for 6 hours, yielding a zinc-containing MFI zeolite shaped body. The obtained lead-containing MFI zeolite shaped body was steam-treated at 600°C for 30 hours with steam containing 50% by volume of water vapor and 50% by volume of air, yielding a zinc-containing MFI zeolite shaped body of this comparative example.

[0171] The obtained zinc-containing MFI zeolite shaped body had an acid amount of 0.08 mmol / g, a zinc content of 1.80 mass%, and a ratio of the zinc content to the acid amount of 22.5. Furthermore, the MFI zeolite shaped body had a free zinc amount of 0.15 mass%, and the ratio of free zinc to the zinc content (free zinc rate) was 8%. The properties of the MFI zeolite shaped body of this comparative example are shown in Table 2.

[0172] An aromatic hydrocarbon production test was conducted under production conditions 1 using the zinc-containing MFI zeolite shaped body of this comparative example. The yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test are shown in Table 2 and FIG. 4. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 9.8 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 46.5 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 56.3 mass%. In contrast, after 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 8.2 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 36.4 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 44.6 mass%.

[0173]

[0174] As shown in Table 1, Table 2, FIGS. 3 and 4, the yield of aromatic hydrocarbon compounds 48 hours after the start of the production test under production condition 1 was higher in Examples 1A to 5A than in Comparative Examples 1A to 6A. From these results, it was understood that the zinc-containing MFI zeolite shaped bodies of Examples 1A to 5A are more likely to maintain aromatic production activity even when the reaction for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons is continued, compared to Comparative Examples 1A to 6A. Furthermore, as shown in Table 1, Table 2, FIGS. 3 and 4, the yield of light hydrocarbons 48 hours after the start of the production test under production condition 1 was also higher in Examples 1A to 5A than in Comparative Examples 1A to 6A. From these results, it was understood that the zinc-containing MFI zeolite shaped bodies of Examples 1A to 5A are more likely to co-produce light hydrocarbons along with aromatic hydrocarbon compounds, compared to Comparative Examples 1A to 6A.

[0175] Example 6A (Zn 0.74 / acid amount 0.35) The zinc-containing MFI zeolite shaped body of Example 1A was used as the zinc-containing MFI zeolite shaped body of this example. An aromatic hydrocarbon production test was conducted under production conditions 2 using the zinc-containing MFI zeolite shaped body of this example. Table 3 shows the yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.1 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 44.4 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 54.5 mass%. After 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.3 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 46.2 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 56.5 mass%.

[0176] Comparative Example 7A (Acid Amount 0.20) The MFI zeolite shaped body of Comparative Example 1A was used as the MFI zeolite shaped body of this Comparative Example. An aromatic hydrocarbon production test was conducted under production conditions 2 using the MFI zeolite shaped body of this Comparative Example. Table 3 shows the yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 7.1 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 36.6 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 43.7 mass%. In contrast, after 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 8.3 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 38.8 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 47.1 mass%.

[0177]

[0178] As shown in Table 3, the yield of aromatic hydrocarbon compounds 48 hours after the start of the production test under production conditions 2 was higher in Example 6A than in Comparative Example 7A. From this result, it was understood that the zinc-containing MFI zeolite shaped body of Example 6A is more likely to maintain aromatic production activity even when the reaction for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons is continued, compared to Comparative Example 7A. Furthermore, as shown in Table 3, the yield of light hydrocarbons 48 hours after the start of the production test under production conditions 2 was also higher in Example 6A than in Comparative Example 7A. From this result, it was understood that the zinc-containing MFI zeolite shaped body of Example 6A is more likely to co-produce light hydrocarbons along with aromatic hydrocarbon compounds, compared to Comparative Example 7A.

[0179] Example 7A (Zn 0.74 / acid amount 0.35) The zinc-containing MFI zeolite shaped body of Example 1A was used as the zinc-containing MFI zeolite shaped body of this example. An aromatic hydrocarbon production test was conducted under production conditions 3 using the zinc-containing MFI zeolite shaped body of this example. Table 4 shows the yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 10.3 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 41.5 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 51.8 mass%. After 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 11.1 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 43.5 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 54.6 mass%.

[0180] Comparative Example 8A (Acid Amount 0.20) The MFI zeolite shaped body of Comparative Example 1A was used as the MFI zeolite shaped body of this Comparative Example. An aromatic hydrocarbon production test was conducted under production conditions 3 using the MFI zeolite shaped body of this Comparative Example. Table 4 shows the yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 6.3 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 30.3 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 36.6 mass%. In contrast, after 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 7.3 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 32.6 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 39.9 mass%.

[0181]

[0182] As shown in Table 4, the yield of aromatic hydrocarbon compounds 48 hours after the start of the production test under production conditions 3 was higher in Example 7A than in Comparative Example 8A. From this result, it was understood that the zinc-containing MFI zeolite shaped body of Example 7A is more likely to maintain aromatic production activity even when the reaction for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons is continued, compared to Comparative Example 8A. Furthermore, as shown in Table 4, the yield of light hydrocarbons 48 hours after the start of the aromatic hydrocarbon production test under production conditions 3 was also higher in Example 7A than in Comparative Example 8A. From this result, it was understood that the zinc-containing MFI zeolite shaped body of Example 7A is more likely to co-produce light hydrocarbons along with aromatic hydrocarbon compounds, compared to Comparative Example 8A.

[0183] Example 8A (Zn 0.74 / acid amount 0.35) The zinc-containing MFI zeolite shaped body of Example 1A was used as the zinc-containing MFI zeolite shaped body of this example. An aromatic hydrocarbon production test was conducted under production conditions 4 using the zinc-containing MFI zeolite shaped body of this example. Table 5 shows the yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 9.0 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 52.0 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 61.0 mass%. After 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 9.4 mass%, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 51.5 mass%, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 60.9 mass%.

[0184] Comparative Example 9A (Acid Amount 0.20) The MFI zeolite shaped body of Comparative Example 1A was used as the MFI zeolite shaped body of this Comparative Example. An aromatic hydrocarbon production test was conducted under production conditions 4 using the MFI zeolite shaped body of this Comparative Example. Table 5 shows the yields of each product component 2 hours and 48 hours after the start of the aromatic hydrocarbon production test. After 2 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 6.5% by mass, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 42.5% by mass, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 49.0% by mass. In contrast, after 48 hours, the yield of light hydrocarbon compounds (the sum of ethane and ethylene) was 7.9% by mass, the yield of aromatic hydrocarbon compounds (the sum of benzene, toluene, and xylene) was 43.7% by mass, and the total yield of light hydrocarbon compounds and aromatic hydrocarbon compounds was 51.6% by mass.

[0185]

[0186] As shown in Table 5, the yield of aromatic hydrocarbon compounds 48 hours after the start of the production test under production conditions 4 was higher in Example 8A than in Comparative Example 9A. From this result, it was understood that the zinc-containing MFI zeolite shaped body of Example 8A is more likely to maintain aromatic production activity even when the reaction for producing aromatic hydrocarbon compounds from aliphatic hydrocarbons is continued, compared to Comparative Example 9A. Furthermore, as shown in Table 5, the yield of light hydrocarbons 48 hours after the start of the aromatic hydrocarbon production test under production conditions 4 was also higher in Example 8A than in Comparative Example 9A. From this result, it was understood that the zinc-containing MFI zeolite shaped body of Example 8A is more likely to co-produce light hydrocarbons along with aromatic hydrocarbon compounds, compared to Comparative Example 9A.

[0187] Preparation Example 1B (Preparation of Cylindrical Zeolite Molded Body) MFI type zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA (Si / Al ２ O ３To 100 parts by weight of silica (product name Snowtex 50-T, manufactured by Nissan Chemical Industries, Ltd., average particle size 22 nm), 24 parts by weight of silica, 5 parts by weight of cellulose, and 35 parts by weight of pure water were added and kneaded to obtain a raw material mixture. The obtained raw material mixture was formed into a cylindrical molded body having a diameter of 3.0 mm and a length of 1.0 to 7.0 mm (average length 3.5 mm). This was dried overnight at 100°C and then calcined in an air atmosphere at 550°C for 1 hour. The calcined molded body was contacted with steam containing 50% by volume of water vapor and 50% by volume of air at 600°C for 4 hours to obtain a molded body of MFI zeolite of Preparation Example 1B. The density of the molded MFI zeolite of Preparation Example 1B was 0.96 g / cm ３ It was.

[0188] Preparation Example 2B (Preparation of Cylindrical Zeolite Molded Body) MFI type zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA (Si / Al ２ O ３ To 100 parts by weight of silica (product name Snowtex 50-T, manufactured by Nissan Chemical Industries, Ltd., average particle size 22 nm), 30 parts by weight of silica, 5 parts by weight of cellulose, and 50 parts by weight of pure water were added and kneaded, to obtain a raw material mixture. The obtained raw material mixture was formed into a cylindrical molded body having an outer diameter of 3.0 mm, an inner diameter of 2.0 mm, and a length of 1.0 to 7.0 mm (average length 3.5 mm). This was dried overnight at 100°C and then calcined in an air atmosphere at 500°C for 6 hours. The calcined molded body was contacted with steam containing 50% by volume of water vapor and 50% by volume of air at 550°C for 8 hours, to obtain a molded body of MFI zeolite of Preparation Example 2B. The density of the molded MFI zeolite of Preparation Example 2B was 0.94 g / cm ３ It was.

[0189] Preparation Example 3B (Preparation of Cylindrical Zeolite Molded Body) MFI type zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA (Si / Al ２ O ３To 100 parts by weight of silica (product name Snowtex ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm), 45 parts by weight of silica, 5 parts by weight of cellulose, and 50 parts by weight of pure water were added and kneaded to obtain a raw material mixture. The obtained raw material mixture was formed into a cylindrical molded body having a diameter of 4.0 mm and a length of 2.0 to 9.0 mm (average length 4.5 mm). This was dried overnight at 150°C and then calcined in an air atmosphere at 540°C for 4 hours to obtain a molded body of MFI zeolite of Preparation Example 3B. The density of the molded MFI zeolite of Preparation Example 3B was 0.94 g / cm ３ It was.

[0190] Preparation Example 4B (Preparation of Cylindrical Zeolite Molded Body) MFI type zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA (Si / Al ２ O ３ To 100 parts by weight of silica (product name Snowtex ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm), 38 parts by weight of silica, 5 parts by weight of cellulose, and 55 parts by weight of pure water were added and kneaded to obtain a raw material mixture. The obtained raw material mixture was formed into a cylindrical molded body having a diameter of 3.0 mm and a length of 1.0 to 7.0 mm (average length 3.6 mm). This was dried overnight at 120°C and then calcined in an air atmosphere at 500°C for 8 hours to obtain a molded body of MFI zeolite of Preparation Example 4B. The density of the molded body of MFI zeolite of Preparation Example 4B was 0.95 g / cm ３ It was.

[0191] Preparation Example 5B (Preparation of Cylindrical Zeolite Molded Body) MFI type zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA (Si / Al ２ O ３To 100 parts by weight of silica (product name Snowtex N-30G, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm), 25 parts by weight of silica, 5 parts by weight of cellulose, and 37 parts by weight of pure water were added and kneaded together to obtain a raw material mixture. The obtained raw material mixture was formed into a cylindrical molded body having a diameter of 3.0 mm and a length of 1.0 to 7.0 mm (average length 3.5 mm). This was dried overnight at 120°C and then calcined in an air atmosphere at 500°C for 8 hours. The calcined molded body was contacted with steam containing 30% by volume of water vapor and 70% by volume of air at 620°C for 4 hours to obtain a molded body of MFI zeolite of Preparation Example 5B. The density of the molded MFI zeolite of Preparation Example 5B was 0.95 g / cm ３ It was.

[0192] Preparation Example 6B (Preparation of Cylindrical Zeolite Molded Body) MFI type zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-840HOA (Si / Al ２ O ３ To 100 parts by weight of silica (product name Snowtex 50-T, manufactured by Nissan Chemical Industries, Ltd., average particle size 22 nm), 24 parts by weight of silica, 5 parts by weight of cellulose, and 35 parts by weight of pure water were added and kneaded to obtain a raw material mixture. The obtained raw material mixture was formed into a cylindrical molded body having a diameter of 3.0 mm and a length of 1.0 to 7.0 mm (average length 3.5 mm). This was dried overnight at 100°C and then calcined in an air atmosphere at 550°C for 1 hour. The calcined molded body was contacted with steam containing 50% by volume of water vapor and 50% by volume of air at 600°C for 4 hours to obtain a molded body of MFI zeolite of Preparation Example 6B. The density of the molded MFI zeolite of Preparation Example 6B was 0.96 g / cm ３ It was.

[0193] Preparation Example 7B (Preparation of Cylindrical Zeolite Molded Body) Amorphous aluminosilicate gel was added to an aqueous solution of tetrapropylammonium (hereinafter also referred to as "TPA") hydroxide and sodium hydroxide, and the mixture was suspended to obtain a raw material composition. The composition of the raw material composition was as follows: SiO ２ / Al ２ O ３ Molar ratio = 46 TPA / Si molar ratio = 0.06 Na / Si molar ratio = 0.18 OH / Si molar ratio = 0.21 H ２O / Si molar ratio=10

[0194] MFI zeolite was added to the raw material composition as seed crystals. The amount of seed crystals added was determined based on the Al content of the raw material composition. ２ O ３ and SiO ２ The content of the seed crystals was 0.6% by mass relative to the total mass of the raw material composition. The seed crystal-added raw material composition was sealed in a stainless steel autoclave and crystallized for 4 days while stirring at 120°C, yielding a slurry-like mixed liquid. The slurry-like mixed liquid was subjected to solid-liquid separation using a centrifugal settler, and the solid particles were washed with a sufficient amount of pure water and dried at 110°C to obtain a dry powder. The obtained dry powder was dispersed in 1 mol / L hydrochloric acid at room temperature, filtered, washed with a sufficient amount of pure water, and filtered again. The obtained solid particles were dried overnight at 100°C and calcined in an air atmosphere at 550°C for 1 hour. The calcined solid particles were contacted with steam containing 30% by volume of water vapor and 70% by volume of air at 600°C for 2 hours. The steam-treated solid particles were dispersed in 1 mol / L hydrochloric acid at room temperature, filtered, washed with a sufficient amount of pure water, and filtered to obtain MFI zeolite. The obtained MFI zeolite had a Si / Al ２ O ３ The molar ratio was 46.

[0195] To 100 parts by weight of the obtained MFI zeolite, 25 parts by weight of silica (manufactured by Nissan Chemical Industries, Ltd., (trade name) Snowtex 50-T, average particle size 22 nm), 5 parts by weight of cellulose, and 28 parts by weight of pure water were added and kneaded to obtain a raw material mixture. The obtained raw material mixture was formed into a cylindrical molded body having a diameter of 1.5 mm and a length of 1.0 to 7.0 mm (average length 3.5 mm). This was dried overnight at 100°C and then calcined in an air atmosphere at 550°C for 1 hour, thereby obtaining a molded body of MFI zeolite of Preparation Example 7B. The density of the molded MFI zeolite of Preparation Example 7B was 0.96 g / cm ３ It was.

[0196] Preparation Example 8B (Preparation of Cylindrical Zeolite Molded Body) 24 parts by weight of silica (Nissan Chemical Industries, Ltd., (trade name) Snowtex 50-T, average particle size 22 nm), 5 parts by weight of cellulose, and 35 parts by weight of pure water were added to 100 parts by weight of MFI zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA (Si / Al molar ratio 24)) and kneaded to obtain a raw material mixture. The obtained raw material mixture was formed into a cylindrical molded body having a diameter of 5.0 mm and a length of 5.0 to 10.0 mm (average length 7.5 mm). This was dried overnight at 100°C and then calcined in an air atmosphere at 550°C for 1 hour. The calcined molded body was contacted with steam containing 50% by volume of water vapor and 50% by volume of air at 600°C for 4 hours to obtain the MFI zeolite molded body of Preparation Example 8B. The density of the MFI zeolite shaped body of Preparation Example 8B was 0.95 g / cm ３ It was.

[0197] Preparation Example 9B (Preparation of Cylindrical Zeolite Molded Body) 24 parts by weight of silica (Nissan Chemical Industries, Ltd., (trade name) Snowtex 50-T, average particle size 22 nm), 5 parts by weight of cellulose, and 35 parts by weight of pure water were added to 100 parts by weight of MFI zeolite (manufactured by Tosoh Corporation, (trade name) HSZ-822HOA (Si / Al molar ratio 24)) and kneaded to obtain a raw material mixture. The obtained raw material mixture was formed into a cylindrical molded body having a diameter of 1.0 mm and a length of 1.0 to 2.0 mm (average length 1.5 mm). This was dried overnight at 100°C and then calcined in air at 550°C for 1 hour. The calcined molded body was contacted with steam containing 50% by volume of water vapor and 50% by volume of air at 600°C for 4 hours to obtain the MFI zeolite molded body of Preparation Example 9B. The density of the MFI zeolite shaped body of Preparation Example 9B was 0.97 g / cm ３ It was.

[0198] Example 1B A plurality of MFI zeolite shaped bodies obtained in Preparation Example 1B were packed into the packing section of a large packing container. The packing section of the large packing container was cylindrical with a length L of 2.0 m in the supply direction of the aqueous zinc solution and a diameter of 10 cm. The packed plurality of MFI zeolite shaped bodies weighed 10.1 kg, and the porosity of the packing section calculated from the above formula (I) was 33%.

[0199] 1.34 kg of zinc nitrate hexahydrate was dissolved in 49.5 L of pure water to prepare a 90 mmol / L zinc nitrate aqueous solution. A chemical-resistant polyolefin hose connected to a circulation pump was connected to a large filling container to form a circulation flow path. The zinc nitrate aqueous solution at 25°C was circulated for 24 hours at a linear flow rate of 26 cm / min so that the zinc aqueous solution was supplied vertically from the bottom to the filling section.

[0200] After the zinc nitrate aqueous solution was completely removed, 50.0 L of pure water was circulated at the same linear flow velocity for 0.5 hours, and then the cleaning solution was completely removed. This operation was repeated four times, and cleaning was performed for a total of two hours. After cleaning, a number of MFI zeolite shaped bodies located at the center of the packed section (the center in the direction of supply of the zinc aqueous solution) were sampled. A cleaning confirmation test was performed on some of the sampled MFI zeolite shaped bodies, and it was confirmed that the pH of the water after the cleaning confirmation test was 4.3. The cleaning confirmation test was performed by placing the sampled MFI zeolite shaped bodies (MFI zeolite shaped bodies immediately after cessation of contact with the cleaning solution) in a beaker separate from the beaker used for the cleaning confirmation test, allowing them to stand in the air for five minutes, and then transferring them to a container (100 mL beaker) for the cleaning confirmation test. Specifically, 10.0 g of the MFI zeolite shaped body and 20.0 g of pure water were placed in a 100 mL beaker and allowed to stand at 25°C for 60 minutes, and the pH of the water was measured after 60 minutes, thereby carrying out a cleaning confirmation test. The remaining collected MFI zeolite shaped body was heated to 110°C at a heating rate of 10°C / min and dried overnight. It was then calcined at 550°C for 3 hours, yielding a zinc-containing MFI zeolite shaped body of Example 1B.

[0201] The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0202] Example 2B A plurality of MFI zeolite shaped bodies obtained in Preparation Example 1B were packed into the packing section of a large packing vessel. The packing section of the large packing vessel was cylindrical with a length L of 4.0 m in the supply direction of the aqueous zinc solution and a diameter of 10 cm. The packed MFI zeolite shaped bodies weighed 20.9 kg, and the porosity of the packing section calculated from the above formula (I) was 30.7%.

[0203] 20.5 kg of zinc nitrate hexahydrate was dissolved in 90.8 L of pure water to prepare a 700 mmol / L zinc nitrate aqueous solution. A chemical-resistant polyolefin hose connected to a circulation pump was connected to a large filling container to form a circulation flow path. The zinc nitrate aqueous solution at 25°C was circulated for 8 hours at a linear flow velocity of 21 cm / min so that the zinc nitrate aqueous solution was supplied vertically from the bottom to the filling section.

[0204] After the zinc nitrate aqueous solution was completely removed, 110.0 L of pure water was circulated at the same linear flow velocity for 1.0 hour, and then the cleaning solution was completely removed. This operation was repeated five times, and cleaning was carried out for a total of five hours. After cleaning, a number of MFI zeolite shaped bodies located at the center of the packed section (the center in the direction of supply of the zinc aqueous solution) were sampled. A cleaning confirmation test was carried out on some of the sampled MFI zeolite shaped bodies, and it was confirmed that the pH of the water after the cleaning confirmation test was 5.0. The cleaning confirmation test was carried out in the same manner as in Example 1B. The remaining sampled MFI zeolite shaped bodies were heated to 110°C at a heating rate of 10°C / min and dried overnight. Subsequently, calcination was carried out at 550°C for 2 hours, yielding a zinc-containing MFI zeolite shaped body of Example 2B.

[0205] The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0206] Example 3B A plurality of MFI zeolite shaped bodies obtained in Preparation Example 2B were packed into the packing section of a large packing container. The packing section of the large packing container was cylindrical with a length L of 0.5 m in the supply direction of the aqueous zinc solution and a diameter of 10 cm. The packed MFI zeolite shaped bodies weighed 2.4 kg, and the porosity of the packing section calculated from the above formula (I) was 35%.

[0207] 3.5 kg of zinc acetate dihydrate was dissolved in 8.8 L of pure water to prepare a 1700 mmol / L zinc acetate aqueous solution. A chemical-resistant polyolefin hose connected to a circulation pump was connected to a large filling container to form a circulation flow path. The zinc acetate aqueous solution was circulated at 24°C for 12 hours at a linear flow velocity of 23 cm / min so that the zinc acetate aqueous solution was supplied vertically from the bottom to the filling section.

[0208] After the zinc acetate aqueous solution was completely removed, 11.3 L of pure water was circulated for 0.5 hours at the same linear flow velocity, and then the operation of completely removing the cleaning solution was repeated once, followed by 0.5-hour cleaning. After cleaning, a plurality of zeolite shaped bodies located at the center of the packed section (the center in the direction of supply of the zinc aqueous solution) were sampled. A cleaning confirmation test was performed on some of the sampled MFI zeolite shaped bodies, and it was confirmed that the pH of the water after the cleaning confirmation test was 3.5. The cleaning confirmation test was performed in the same manner as in Example 1B. The remaining sampled MFI zeolite shaped bodies were heated to 110°C at a heating rate of 10°C / min and dried overnight. Thereafter, calcination was performed at 480°C for 12 hours to obtain the zinc-containing MFI zeolite shaped body of Example 3B.

[0209] The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0210] Example 4B A plurality of MFI zeolite shaped bodies obtained in Preparation Example 3B were packed into the packing section of a large packing container. The packing section of the large packing container was cylindrical with a length L of 2.0 m in the supply direction of the aqueous zinc solution and a diameter of 10 cm. The packed MFI zeolite shaped bodies weighed 9.8 kg, and the porosity of the packing section calculated from the above formula (I) was 33.6%.

[0211] 1.7 kg of zinc acetate dihydrate was dissolved in 38.9 L of pure water to prepare a 200 mmol / L zinc acetate aqueous solution. A chemical-resistant polyolefin hose connected to a circulation pump was connected to a large filling container to form a circulation flow path. The zinc acetate aqueous solution at 29°C was circulated for 4 hours at a linear flow velocity of 33 cm / min so that the zinc aqueous solution was supplied vertically from the bottom to the filling section.

[0212] After the zinc acetate aqueous solution was completely removed, 40.0 L of pure water was circulated at the same linear flow velocity for 6 hours, and then the cleaning solution was completely removed. This operation was repeated four times, for a total of 24 hours of cleaning. After cleaning, multiple MFI zeolite shaped bodies located at the center of the packed section (the center in the direction of supply of the zinc aqueous solution) were sampled. A cleaning confirmation test was performed on some of the sampled MFI zeolite shaped bodies, and it was confirmed that the pH of the water after the cleaning confirmation test was 7.2. The cleaning confirmation test was performed in the same manner as in Example 1B. The remaining sampled MFI zeolite shaped bodies were heated to 170°C at a heating rate of 10°C / min and dried overnight. Thereafter, the samples were calcined at 500°C for 7 hours, and then contacted with steam containing 50% by volume of water vapor and 50% by volume of air at 600°C for 4 hours, thereby obtaining the zinc-containing MFI zeolite shaped body of Example 4B.

[0213] The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0214] Example 5B A plurality of MFI zeolite shaped bodies obtained in Preparation Example 4B were packed into the packing section of a large packing container. The packing section of the large packing container was cylindrical with a length L of 2.0 m in the supply direction of the aqueous zinc solution and a diameter of 10 cm. The packed MFI zeolite shaped bodies weighed 9.9 kg, and the porosity of the packing section calculated from the above formula (I) was 33.7%.

[0215] 0.23 kg of zinc chloride was dissolved in 55.4 L of pure water to prepare a 30 mmol / L aqueous zinc chloride solution. A chemical-resistant polyolefin hose connected to a circulation pump was connected to a large filling container to form a circulation flow path. The aqueous zinc chloride solution at 25°C was circulated for 48 hours at a linear flow rate of 28 cm / min so that the aqueous zinc chloride solution was supplied vertically from the bottom to the filling section.

[0216] After the entire zinc chloride aqueous solution was removed, 55.4 L of pure water was circulated at the same linear flow velocity for 1.0 hour, and then the cleaning solution was completely removed. This operation was repeated four times, and cleaning was carried out for a total of four hours. After cleaning, multiple MFI zeolite shaped bodies located at the center of the packed section (the center in the direction of supply of the zinc aqueous solution) were collected. A cleaning confirmation test was performed on some of the collected MFI zeolite shaped bodies, and it was confirmed that the pH of the water after the cleaning confirmation test was 4.7. The cleaning confirmation test was carried out in the same manner as in Example 1B. The remaining collected MFI zeolite shaped bodies were heated to 110°C at a heating rate of 10°C / min and dried overnight. Thereafter, the shaped bodies were calcined at 450°C for 12 hours, and then contacted with steam containing 50% by volume of water vapor and 50% by volume of air at 500°C for 12 hours, thereby obtaining the zinc-containing MFI zeolite shaped body of Example 5B.

[0217] The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0218] Example 6B A plurality of MFI zeolite shaped bodies obtained in Preparation Example 5B were packed into the packing section of a large packing container. The packing section of the large packing container was cylindrical with a length L of 2.0 m in the supply direction of the aqueous zinc solution and a diameter of 10 cm. The packed MFI zeolite shaped bodies weighed 10.2 kg, and the porosity of the packing section calculated from the above formula (I) was 31.6%.

[0219] 0.80 kg of zinc chloride was dissolved in 49.0 L of pure water to prepare a 120 mmol / L aqueous zinc chloride solution. A chemical-resistant polyolefin hose connected to a circulation pump was connected to a large filling container to form a circulation flow path. The aqueous zinc chloride solution at 26°C was circulated for 10 hours at a linear flow rate of 18 cm / min so that the zinc aqueous solution was supplied from the bottom to the filling section in the vertical direction.

[0220] After the zinc chloride aqueous solution was completely removed, 49.0 L of pure water was circulated at the same linear flow velocity for 1.0 hour, and then the cleaning solution was completely removed. This operation was repeated twice, for a total of 2 hours of cleaning. After cleaning, multiple MFI zeolite shaped bodies located at the center of the packed section (the center in the direction of supply of the zinc aqueous solution) were collected on a porcelain dish. A cleaning confirmation test was performed on some of the collected MFI zeolite shaped bodies, and it was confirmed that the pH of the water after the cleaning confirmation test was 2.7. The cleaning confirmation test was performed in the same manner as in Example 1B. The remaining collected MFI zeolite shaped bodies were heated to 110°C at a heating rate of 10°C / min and dried overnight. Subsequently, they were calcined at 550°C for 1 hour, yielding a zinc-containing MFI zeolite shaped body of Example 6B.

[0221] The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0222] Example 7B A zinc-containing MFI zeolite shaped body of Example 7B was obtained in the same manner as in Example 1B, except that the circulation time of the zinc nitrate aqueous solution in Example 1B was changed to 3 hours. In this example, the pH of the water after the cleaning confirmation test was 4.4. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0223] Example 8B A zinc-containing MFI zeolite shaped body of Example 8B was obtained in the same manner as in Example 1B, except that the circulation time of the zinc nitrate aqueous solution in Example 1B was changed to 150 hours. In this example, the pH of the water after the cleaning confirmation test was 3.5. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0224] Example 9B A zinc-containing MFI zeolite shaped body of Example 9B was obtained in the same manner as in Example 1B, except that a 90 mmol / L zinc nitrate aqueous solution prepared by dissolving 2.14 kg of zinc nitrate hexahydrate in 79.2 L of pure water was circulated instead of the zinc nitrate aqueous solution used in Example 1B. In this example, the pH of the water after the cleaning confirmation test was 3.8. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0225] Example 10B A zinc-containing MFI zeolite shaped body of Example 10B was obtained in the same manner as in Example 1B, except that a 90 mmol / L zinc nitrate aqueous solution prepared by dissolving 0.67 kg of zinc nitrate hexahydrate in 24.8 L of pure water was circulated instead of the zinc nitrate aqueous solution used in Example 1B. In this example, the pH of the water after the cleaning confirmation test was 4.6. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0226] Example 11B A zinc-containing MFI zeolite shaped body of Example 11B was obtained in the same manner as in Example 1B, except that the washing treatment in Example 1B was changed to a washing treatment in which 50.0 L of pure water was circulated for 5 hours at a linear flow velocity of 26 cm / min and then all of the washing liquid was removed, and this operation was repeated six times (total washing time: 30 hours). In this example, the pH of the water after the washing confirmation test was 7.2. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0227] Example 12B A zinc-containing MFI zeolite shaped body of Example 12B was obtained in the same manner as in Example 1B, except that the washing treatment in Example 1B was changed to a washing treatment in which 50.0 L of pure water was circulated at a linear flow velocity of 26 cm / min for 0.2 hours and then all of the washing liquid was removed, this operation being carried out a total of 10 times (total of 2 hours of washing). In this example, the pH of the water after the washing confirmation test was 5.3. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0228] Example 13B A zinc-containing MFI zeolite shaped body of Example 13B was obtained in the same manner as in Example 1B, except that the washing treatment in Example 1B was changed to a washing treatment in which 100.0 L of pure water was circulated at a linear flow velocity of 26 cm / min for 0.5 hours and then all of the washing liquid was removed, and this operation was repeated four times (total of 2 hours of washing). In this example, the pH of the water after the washing confirmation test was 5.2. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0229] Example 14B A zinc-containing MFI zeolite shaped body of Example 14B was obtained in the same manner as in Example 1B, except that the washing treatment in Example 1B was changed to a washing treatment in which 20.0 L of pure water was circulated at a linear flow velocity of 26 cm / min for 0.5 hours and then all of the washing liquid was removed, and this operation was repeated four times (total of 2 hours of washing). In this example, the pH of the water after the washing confirmation test was 3.6. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0230] Example 15B A zinc-containing MFI zeolite shaped body of Example 15B was obtained in the same manner as in Example 1B, except that the linear flow velocity of the zinc nitrate aqueous solution used in Example 1B was changed to 40 cm / min. In this example, the pH of the water after the cleaning confirmation test was 4.3. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0231] Example 16B A zinc-containing MFI zeolite shaped body of Example 16B was obtained in the same manner as in Example 1B, except that the linear flow velocity of the zinc nitrate aqueous solution used in Example 1B was changed to 10 cm / min. In this example, the pH of the water after the cleaning confirmation test was 4.2. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0232] Example 17B A zinc-containing MFI zeolite shaped body of Example 17B was obtained in the same manner as in Example 1B, except that the linear flow velocity of the cleaning liquid (pure water) used in Example 1B was changed to 40 cm / min. In this example, the pH of the water after the cleaning confirmation test was 4.3. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0233] Example 18B A zinc-containing MFI zeolite shaped body of Example 18B was obtained in the same manner as in Example 1B, except that the linear flow velocity of the cleaning liquid (pure water) used in Example 1B was changed to 10 cm / min. In this example, the pH of the water after the cleaning confirmation test was 4.2. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0234] Example 19B A zinc-containing MFI zeolite shaped body of Example 19B was obtained in the same manner as in Example 1B, except that the MFI zeolite shaped body of Preparation Example 6B was used instead of the MFI zeolite shaped body of Preparation Example 1B used in Example 1B. In this example, the porosity of the packed portion calculated from the above formula (I) was 33%. In addition, in this example, the pH of the water after the cleaning confirmation test was 4.2. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0235] Example 20B A zinc-containing MFI zeolite shaped body of Example 20B was obtained in the same manner as in Example 1B, except that the MFI zeolite shaped body of Preparation Example 7B was used instead of the MFI zeolite shaped body of Preparation Example 1B used in Example 1B. In this example, the porosity of the packed portion calculated from the above formula (I) was 33%. In addition, in this example, the pH of the water after the cleaning confirmation test was 4.2. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0236] Example 21B A zinc-containing MFI zeolite shaped body of Example 21B was obtained in the same manner as in Example 1B, except that the MFI zeolite shaped body of Preparation Example 8B was used instead of the MFI zeolite shaped body of Preparation Example 1B used in Example 1B, and the amount of MFI zeolite shaped body packed in the packed section was 9.5 kg. In this example, the porosity of the packed section calculated from the above formula (I) was 36.3%. In this example, the pH of the water after the cleaning confirmation test was 4.4. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0237] Example 22B A zinc-containing MFI zeolite shaped body of Example 22B was obtained in the same manner as in Example 1B, except that the MFI zeolite shaped body of Preparation Example 9B was used instead of the MFI zeolite shaped body of Preparation Example 1B used in Example 1B, and that the amount of MFI zeolite shaped body packed in the packed section was 11 kg. In this example, the porosity of the packed section calculated from the above formula (I) was 27.8%. In this example, the pH of the water after the cleaning confirmation test was 4.2. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0238] Example 23B A zinc-containing MFI zeolite shaped body of Example 23B was obtained in the same manner as in Example 1B, except that 50.0 L of 1 mass percent aqueous ammonia was used as the cleaning liquid in the first two cycles of four cycles (0.5 hours x 4) in which a cleaning liquid (pure water) was circulated. In this example, the pH of the water after the cleaning confirmation test was 8.0. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0239] Example 24B A zinc-containing MFI zeolite shaped body of Example 24B was obtained in the same manner as in Example 1B, except that the washing treatment in Example 1B was changed to a washing treatment in which 50.0 L of pure water was circulated at a linear flow velocity of 26 cm / min for 0.25 hours and then all of the washing liquid was removed, and this operation was repeated four times (total washing time: 1 hour). In this example, the pH of the water after the washing confirmation test was 3.0. The production conditions for this example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this example are shown in Tables 7 and 8 below.

[0240] Comparative Example 1B A plurality of MFI zeolite shaped bodies obtained in Preparation Example 1B were packed into the packing section of a large packing container. The packing section of the large packing container was cylindrical with a length L of 2.0 m in the supply direction of the aqueous zinc solution and a diameter of 10 cm. The packed MFI zeolite shaped bodies weighed 10.2 kg, and the porosity of the packing section calculated from the above formula (I) was 32.4%.

[0241] 7.4 kg of zinc nitrate hexahydrate was dissolved in 47.3 L of pure water to prepare a 500 mmol / L zinc nitrate aqueous solution. A chemical-resistant polyolefin hose connected to a circulation pump was connected to a large filling container to form a circulation flow path. The zinc nitrate aqueous solution at 25°C was circulated for 2 hours at a linear flow rate of 24 cm / min so that the zinc aqueous solution was supplied vertically from the bottom to the filling section.

[0242] After the zinc nitrate aqueous solution was completely removed, 50.0 L of pure water was circulated at the same linear flow velocity for 0.5 hours, and then the cleaning solution was completely removed. This operation was repeated six times, for a total of three hours of cleaning. After cleaning, several MFI zeolite shaped bodies located at the center of the packed section (the center in the direction of supply of the zinc aqueous solution) were collected on a porcelain dish. A cleaning confirmation test was performed on some of the collected MFI zeolite shaped bodies, and it was confirmed that the pH of the water after the cleaning confirmation test was 5.3. The cleaning confirmation test was performed in the same manner as in Example 1B. The remaining collected MFI zeolite shaped bodies were heated to 110°C at a heating rate of 10°C / min and dried overnight. Subsequently, they were calcined at 550°C for two hours, yielding a zinc-containing MFI zeolite shaped body of Comparative Example 1B.

[0243] The production conditions for this comparative example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this comparative example are shown in Tables 7 and 8 below.

[0244] Comparative Example 2B A zinc-containing MFI zeolite shaped body of Comparative Example 2B was obtained in the same manner as in Example 1B, except that the washing treatment in Example 1B was changed to a washing treatment in which 50.0 L of pure water was circulated at a linear flow velocity of 26 cm / min for 0.25 hours and then all of the washing liquid was removed, which was performed twice (total washing time: 0.5 hours), and the calcination conditions for the MFI zeolite shaped body were changed to 510°C for 4 hours. In this comparative example, the pH of the water after the washing confirmation test was 2.1. The production conditions for this comparative example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this comparative example are shown in Tables 7 and 8 below.

[0245] Comparative Example 3B A zinc-containing MFI zeolite shaped body of Comparative Example 3B was obtained in the same manner as in Example 1B, except that the washing treatment in Example 1B was changed to a washing treatment in which 50.0 L of pure water was circulated at a linear flow velocity of 26 cm / min for 0.25 hours and then all of the washing liquid was removed, and this was repeated three times (total washing time: 0.75 hours), and the calcination conditions for the MFI zeolite shaped body were changed to 510°C for 4 hours. In this comparative example, the pH of the water after the washing confirmation test was 2.4. The production conditions for this comparative example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this comparative example are shown in Tables 7 and 8 below.

[0246] Comparative Example 4B A plurality of MFI zeolite shaped bodies obtained in Preparation Example 3B were packed into the packing section of a large packing container. The packing section of the large packing container was cylindrical with a length L of 1.0 m in the supply direction of the aqueous zinc solution and a diameter of 10 cm. The packed MFI zeolite shaped bodies weighed 4.9 kg, and the porosity of the packing section calculated from the above formula (I) was 34.3%.

[0247] 17.4 kg of zinc acetate dihydrate was dissolved in 23.6 L of pure water to prepare a 3000 mmol / L zinc acetate aqueous solution. A chemical-resistant polyolefin hose connected to a circulation pump was connected to a large filling container to form a circulation flow path. The zinc acetate aqueous solution at 28°C was circulated for 16 hours at a linear flow velocity of 27 cm / min so that the zinc aqueous solution was supplied vertically from the bottom to the filling section.

[0248] After the zinc acetate aqueous solution was completely removed, 26.5 L of pure water was circulated at the same linear flow velocity for 6 hours, and then the cleaning solution was completely removed. This operation was repeated four times, for a total of 24 hours of cleaning. After cleaning, a zeolite shaped body located at the center of the packed section (the center in the direction of supply of the zinc aqueous solution) was collected. A cleaning confirmation test was performed on some of the collected MFI zeolite shaped bodies, and it was confirmed that the pH of the water after the cleaning confirmation test was 6.1. The cleaning confirmation test was performed in the same manner as in Example 1B. The remaining collected MFI zeolite shaped body was heated to 100°C at a heating rate of 10°C / min and dried overnight. Thereafter, it was calcined at 510°C for 4 hours, and then contacted with steam containing 50% by volume of water vapor and 50% by volume of air at 600°C for 4 hours, thereby obtaining a zinc-containing MFI zeolite shaped body of Comparative Example 4B.

[0249] The production conditions for this comparative example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this comparative example are shown in Tables 7 and 8 below.

[0250] Comparative Example 5B A plurality of MFI zeolite shaped bodies obtained in Preparation Example 4B were packed into the packing section of a large packing container. The packing section of the large packing container was cylindrical with a length L of 2.0 m in the supply direction of the aqueous zinc solution and a diameter of 10 cm. The packed MFI zeolite shaped bodies weighed 10 kg, and the porosity of the packing section calculated from the above formula (I) was 33%.

[0251] 6.4 kg of zinc chloride was dissolved in 47.0 L of pure water to prepare a 1000 mmol / L aqueous zinc chloride solution. A chemical-resistant polyolefin hose connected to a circulation pump was connected to a large filling container to form a circulation flow path. The aqueous zinc chloride solution at 22°C was circulated for 5 hours at a linear flow velocity of 29 cm / min so that the aqueous zinc chloride solution was supplied vertically from the bottom to the filling section.

[0252] After the zinc chloride aqueous solution was completely removed, 47.0 L of pure water was circulated at the same linear flow velocity for 1 hour, and then the cleaning solution was completely removed. This operation was repeated twice, for a total of 2 hours of cleaning. After cleaning, a zeolite shaped body located at the center of the packed section (the center in the direction of supply of the zinc aqueous solution) was collected. A cleaning confirmation test was performed on some of the collected MFI zeolite shaped bodies, and it was confirmed that the pH of the water after the cleaning confirmation test was 2.2. The cleaning confirmation test was performed in the same manner as in Example 1B. The remaining collected MFI zeolite shaped body was heated to 110°C at a heating rate of 10°C / min and dried overnight. Thereafter, it was calcined at 520°C for 3 hours, and then contacted with steam containing 50% by volume of water vapor and 50% by volume of air at 600°C for 4 hours, thereby obtaining a zinc-containing MFI zeolite shaped body of Comparative Example 5B.

[0253] The production conditions for this comparative example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this comparative example are shown in Tables 7 and 8 below.

[0254] Comparative Example 6B A zinc-containing MFI zeolite shaped body of Comparative Example 6B was obtained in the same manner as in Example 1B, except that the circulation time of the zinc nitrate aqueous solution in Example 1B was changed to 0.5 hours. In this comparative example, the pH of the water after the cleaning confirmation test was 4.8. The production conditions for this comparative example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this comparative example are shown in Tables 7 and 8 below.

[0255] Comparative Example 7B A zinc-containing MFI zeolite shaped body of Comparative Example 7B was obtained in the same manner as in Example 1B, except that the circulation time of the zinc nitrate aqueous solution in Example 1B was changed to 1 hour. In this comparative example, the pH of the water after the cleaning confirmation test was 4.6. The production conditions for this comparative example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this comparative example are shown in Tables 7 and 8 below.

[0256] Comparative Example 8B A zinc-containing MFI zeolite shaped body of Comparative Example 8B was obtained in the same manner as in Example 1B, except that the circulation time of the zinc nitrate aqueous solution in Example 1B was changed to 2 hours. In this comparative example, the pH of the water after the cleaning confirmation test was 4.4. The production conditions for this comparative example are shown in Table 6 below, and the properties of the zinc-containing MFI zeolite shaped body of this comparative example are shown in Tables 7 and 8 below.

[0257]

[0258]

[0259]

[0260] As shown in Tables 6 to 8, the zinc-containing MFI zeolite shaped bodies of the present invention that satisfy the above-mentioned properties (i) to (iii) could be produced by the production methods of Examples 1B to 24B. From these results, it was understood that the zinc-containing MFI zeolite shaped bodies of the present invention can be produced by the production method including the above-mentioned filling step (1), zinc-incorporating step (2), and washing step (3).

[0261] The novel zinc-containing MFI zeolite shaped article of the present invention enables a stable production method that is excellent in productivity and balance for each of the processes, for example, when producing aromatic hydrocarbon compounds from aliphatic hydrocarbons, or further when producing light hydrocarbon compounds and aromatic hydrocarbon compounds simultaneously, and is therefore extremely useful industrially as a catalyst for producing aromatic hydrocarbon compounds, or further as a catalyst for the simultaneous production of light hydrocarbon compounds and aromatic hydrocarbon compounds.

[0262] F: Filling part L: Length of filling part D: Diameter of filling part H ｉｎ :Inlet H ｏｕｔ: Outlet P: Flow path P1: Flow path connected to the outlet of the filling part P2: Flow path connected to the inlet of the filling part Pp: Pump

Claims

1. A zinc-containing MFI zeolite shaped body, comprising an inorganic binder and MFI zeolite, and satisfying the following characteristics (i) to (iii): (i) the inorganic binder content is 5 to 50 mass %; (ii) when a reduction treatment test is conducted under test conditions of a test temperature of 600°C, a test atmosphere of 50 mL / min of hydrogen and 50 mL / min of nitrogen, and a test time of 16 hours, the ratio of the zinc content reduced by the reduction treatment test to the zinc content before the reduction treatment test is 30% or less; and (iii) the ratio of zinc content (mass %) / acid amount (mmol / g), expressed as the ratio of the zinc content to the acid amount, is 1 to 15.

2. The zinc-containing MFI zeolite shaped body according to claim 1, characterized in that it satisfies the following properties (iv) to (V): (iv) The zinc content is 0.2 to 3.0 mass %, and (V) The acid amount is 0.05 to 0.85 mmol / g.

3. The zinc-containing MFI zeolite shaped body according to claim 1 or 2, characterized in that, in the relationship between pore diameter and cumulative pore volume as determined by mercury intrusion porosimetry, the cumulative pore volume of pores having a pore diameter in the range of 0.011 to 0.090 μm is 0.040 to 0.800 cc / g.

4. The zinc-containing MFI zeolite formed body according to claim 3, characterized in that, in the relationship between pore diameter and cumulative pore volume as determined by mercury intrusion porosimetry, the cumulative pore volume of pores having a pore diameter in the range of 0.090 to 200 μm is 0.100 to 0.800 cc / g.

5. The zinc-containing MFI zeolite shaped body according to claim 1 or 2, characterized in that it has a cylindrical, cylindrical, spherical, spheroidal, or polygonal prism shape.

6. A catalyst for producing aromatic hydrocarbon compounds, comprising the zinc-containing MFI zeolite shaped article according to claim 1 or 2.

7. A method for producing aromatic hydrocarbon compounds, which comprises contacting the catalyst for producing aromatic hydrocarbon compounds according to claim 6 with an aliphatic hydrocarbon having 30 or less carbon atoms at 400 to 800°C.

8. The method for producing aromatic hydrocarbon compounds according to claim 7, characterized in that the aliphatic hydrocarbons having 30 or less carbon atoms include aliphatic hydrocarbons derived from plants and / or chemical recycling.

9. A method for producing a zeolite shaped body, comprising: a packing step (1) of packing a plurality of MFI zeolite shaped bodies into a packing section having a length L in the supply direction of the aqueous zinc solution; a zinc-containing step (2) of supplying an aqueous zinc solution having a zinc concentration of 10 to 2000 mM to the packing section and bringing the plurality of MFI zeolite shaped bodies into contact with the aqueous zinc solution; and a washing step (3) of supplying a washing liquid to the packing section and bringing the plurality of MFI zeolite shaped bodies that have been contacted with the aqueous zinc solution into contact with the washing liquid, wherein in the zinc-containing step (2), the plurality of MFI zeolite shaped bodies are brought into contact with the aqueous zinc solution until a contact time T1 between the plurality of MFI zeolite shaped bodies and the aqueous zinc solution satisfies the following formula (A): In the washing step (3), the plurality of MFI zeolite shaped bodies are brought into contact with the washing solution such that when the MFI zeolite shaped bodies that have been contacted with the washing solution are tested for 60 minutes in contact with 2 parts by mass of water per 1 part by mass of the MFI zeolite shaped bodies, the pH of the water used in the test is 2.5 or higher. T1≧L×1.5 (A) In the above formula (A), T1 is the contact time [hr] of the plurality of MFI zeolite shaped bodies with the aqueous zinc solution, and L is the length [m] of the packed section in the supply direction of the aqueous zinc solution.

10. The method for producing a zinc-containing MFI zeolite shaped body according to claim 9, wherein the MFI zeolite shaped body has an inorganic binder content of 5 to 50 mass %.

11. A method for producing a zinc-containing MFI zeolite shaped body according to claim 9 or 10, characterized in that the MFI zeolite shaped body is obtained by a production method including the steps of drying a mixture containing at least MFI zeolite, an inorganic binder, and water, and separating aluminum from the framework structure of the MFI zeolite contained in the dried mixture.

12. The method for producing a zinc-containing MFI zeolite shaped body according to claim 9 or 10, characterized in that the MFI zeolite shaped body has a cylindrical, cylindrical, spherical, spheroidal, or polygonal prism shape.

13. A method for producing a zinc-containing MFI-type zeolite molded body as described in claim 9 or 10, wherein the filling section has a cylindrical shape with a length L in the supply direction of 0.5 m or more and a cross section perpendicular to the supply direction that is a circle with a diameter of 10 cm or more.

14. A method for producing a zinc-containing MFI-type zeolite molded body as described in claim 9 or 10, characterized in that the zinc aqueous solution circulates through a circulation flow path formed by the filling section and a flow path connected to the filling section.

15. A method for producing a zinc-containing MFI-type zeolite molded body as described in claim 9 or 10, characterized in that the zinc aqueous solution is supplied to the filling section from below to above in the vertical direction.

16. The method for producing a zinc-containing MFI zeolite shaped body according to claim 9 or 10, further comprising: a drying step (4) of drying the plurality of MFI zeolite shaped bodies that have been brought into contact with the cleaning liquid; and a dealumination step (6) of removing aluminum from the framework structure of MFI zeolite contained in the plurality of dried MFI zeolite shaped bodies.

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