Method for producing oriented zeolite

Abstract

To provide a production method of an oriented zeolite body which is highly general-use and which can produce an oriented zeolite without using a strong magnetic field.SOLUTION: A production method of an oriented zeolite body comprises: a magnetization step of immersing a raw material zeolite in an aqueous solution including a magnetic ion element to perform ion exchange, thereby producing a magnetized zeolite having the magnetic ion element introduced into a crystal structure of the raw material zeolite; and an orienting step of dispersing a powder of the magnetized zeolite in a solvent to form dispersed liquid and, while applying a magnetic field to the dispersed liquid, depositing and assembling the magnetized zeolite and removing the solvent, thereby producing the oriented zeolite body in which a micropore the magnetized zeolite has is regularly arranged.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing an oriented zeolite body and an oriented zeolite body. [Background technology]

[0002] Zeolites are crystalline aluminosilicates with numerous molecular-sized micropores. Zeolites are used as adsorbents, catalysts, and ion exchangers. In recent years, the use of zeolites has been explored in fields such as separation membranes, chemical sensors, and optoelectronics.

[0003] Regarding zeolites, techniques for regularly arranging (orienting) the micropores of zeolites are being investigated. As methods for orienting zeolite, a method of performing hydrothermal synthesis treatment with a specific raw material composition and reaction temperature, a method of using organic molecules as a structure-directing agent, and a method of using a magnetic field have been proposed. As a method of using a magnetic field, Non-Patent Documents 1 and 2 describe a method of controlling the orientation of zeolite using a strong magnetic field. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Chika Matsunaga, Tetsuo Uchikoshi, Tohru S. Suzuki, Yoshio Sakka, Motohide Matsuda, Orientation control of mordenite zeolite in strong magnetic field Microporous and Mesoporous Materials 151 (2012) 188‐194 [Non-patent document 2] Chika Matsunaga, Tetsuo Uchikoshi, Tohru S. Suzuki, Yoshio Sakka, Motohide Matsuda, Fabrication of the c-axis oriented zeolite L compacts using strong magnetic field Materials Letters 93 (2013) 408‐410 Summary of the Invention [Problem to be solved by the invention]

[0005] In the conventional method of orienting zeolite using a magnetic field, a strong magnetic field of 12 T was used to orient the zeolite. However, applying a strong magnetic field to zeolite requires large-scale equipment, making the conventional method of orienting zeolite using a magnetic field less versatile and difficult to use as a method for industrially producing oriented zeolite.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a versatile method for producing oriented zeolite that can produce oriented zeolite without using a strong magnetic field. Another object of the present invention is to provide an oriented zeolite that can be produced by a highly versatile method without using a strong magnetic field. [Means for solving the problem]

[0007] [1] a magnetization step of immersing a raw zeolite in an aqueous solution containing a magnetic ion element to perform ion exchange, thereby producing a magnetized zeolite in which the magnetic ion element is introduced into the crystal structure of the raw zeolite; A method for producing an oriented zeolite body, comprising: an orientation step of dispersing the magnetized zeolite powder in a solvent to form a dispersion; applying a magnetic field to the dispersion while depositing and aggregating the magnetized zeolite and removing the solvent, thereby producing an oriented zeolite body in which the micropores of the magnetized zeolite are regularly arranged.

[0008] [2] The method for producing an oriented zeolite body according to the above [1], wherein the magnetic ion element is one or more magnetic elements selected from the group consisting of transition metal elements and rare earth metal elements. [3] The method for producing an oriented zeolite body according to the above [1], wherein the magnetic ion element is one or more elements selected from the group consisting of Ho, Dy, Tb, and Er. [4] The method for producing an oriented zeolite according to any one of [1] to [3], wherein the magnetic zeolite is selected from the group consisting of A-type zeolite having an ion exchange rate of 5% to 90%, L-type zeolite having an ion exchange rate of 5% to 40%, X-type zeolite having an ion exchange rate of 5% to 80%, and Y-type zeolite having an ion exchange rate of 5% to 70%. [5] The method for producing an oriented zeolite body according to any one of the above [1] to [4], wherein a magnetic field of 0.5 to 4 T is applied to the dispersion in the orientation step.

[0009] [6] A method for producing a zeolite oriented body according to any one of [1] to [5] above, comprising an ion exchange step of exchanging the cationic element with the magnetic ionic element contained in the magnetized zeolite constituting the zeolite oriented body by bringing an aqueous solution containing the cationic element into contact with the zeolite oriented body. [7] A method for producing a zeolite oriented body described in [6] above, wherein the zeolite oriented body is composed of magnetized L-type zeolite, and the L-type zeolite constituting the zeolite oriented body after the ion exchange process has a magnetic ion residual rate of 4% or less. [8] The method for producing an oriented zeolite according to the above [7], wherein the L-type zeolite is c-axis oriented.

[0010] [9] An oriented zeolite having a degree of orientation of 0.05 to 0.6 according to the Lotgering method, in which magnetic ions are introduced into the crystal structure of zeolite constituting the oriented zeolite.

[10] The oriented zeolite according to the above [9], wherein the magnetic ion element is one or more magnetic elements selected from the group consisting of transition metal elements and rare earth metal elements.

[11] The oriented zeolite according to the above

[10] , wherein the magnetic ion element is one or more elements selected from the group consisting of Ho, Dy, Tb, and Er.

[12] The oriented zeolite according to any one of the above [9] to

[11] , wherein the zeolite constituting the oriented zeolite is L-type zeolite.

[13] The oriented zeolite according to the above

[12] , wherein the oriented zeolite is c-axis oriented. [Effects of the Invention]

[0011] The method for producing zeolite of the present invention includes a magnetization step of immersing raw zeolite in an aqueous solution containing a magnetic ion element to perform ion exchange to produce a magnetized zeolite having the magnetic ion element introduced into the crystalline structure of the raw zeolite, and an orientation step of dispersing a powder of the magnetized zeolite in a solvent to form a dispersion, depositing and aggregating the magnetized zeolite while applying a magnetic field to the dispersion, and removing the solvent to produce an oriented zeolite having micropores regularly arranged in the magnetized zeolite. Because the powder of magnetized zeolite in the dispersion has the magnetic ion element introduced into its crystalline structure, the micropores are regularly arranged even when a low magnetic field is applied to the dispersion. Therefore, the method for producing an oriented zeolite of the present invention can produce an oriented zeolite without using a strong magnetic field. Therefore, the method for producing an oriented zeolite of the present invention is highly versatile and suitable as a method for industrially producing oriented zeolite.

[0012] The oriented zeolite of the present invention has an orientation degree of 0.05 to 0.6 by the Lotgering method, and the zeolite micropores are regularly arranged, so that it can be preferably used in fields such as separation membranes, chemical sensors, and optoelectronics. Moreover, the oriented zeolite of the present invention can be produced using the highly versatile method for producing an oriented zeolite of the present invention. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a diagram illustrating an example of the orientation step in the manufacturing method of this embodiment. [Figure 2] FIG. 2 is a diagram illustrating another example of the orientation step in the manufacturing method of this embodiment. [Figure 3] Fig. 3(a) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 1 and raw zeolite 1. Fig. 3(b) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 2 and raw zeolite 2. Fig. 3(c) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 3 and raw zeolite 3. Fig. 3(d) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 4 and raw zeolite 4. [Figure 4] Fig. 4(a) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 5 and raw zeolite 4. Fig. 4(b) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 6 and raw zeolite 4. [Figure 5] Fig. 5(a) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 7 and raw zeolite 4. Fig. 5(b) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 8 and raw zeolite 4. Fig. 5(c) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 9 and raw zeolite 4. [Figure 6]Fig. 6(a) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 10 and raw zeolite 4. Fig. 6(b) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 11 and raw zeolite 4. Fig. 6(c) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 12 and raw zeolite 4. [Figure 7] Fig. 7(a) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Reference Production Example 1 and raw zeolite 4. Fig. 7(b) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Reference Production Example 2 and raw zeolite 4. [Figure 8] Fig. 8(a) is a photograph of the oriented zeolite body of Production Example 13 taken obliquely from above. Fig. 8(b) is a photograph of the oriented zeolite body of Production Example 13 taken from above. [Figure 9] Figure 9 is a chart showing X-ray diffraction results for the zeolite powder used as the raw material (raw material powder), the powdered magnetized zeolite powder (magnetized powder) of Production Example 4, the oriented zeolite of Production Example 13, and the oriented zeolite after the ion exchange process. [Figure 10] Figure 10 is a chart showing the X-ray diffraction results for the zeolite powder (raw material powder) used as the raw material, the oriented zeolite body of Production Example 14, the oriented zeolite body of Production Example 23, and the zeolite molded body of Reference Production Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0014] In order to solve the above problems, the present inventors have conducted extensive research as described below. In other words, the magnetism of zeolite is extremely weak. Therefore, in order to orient zeolite using a magnetic field, a strong magnetic field must be used. Therefore, the inventors thought that in order to be able to orient zeolite using a weak magnetic field, it would be sufficient to increase the magnetic field sensitivity of zeolite before applying a magnetic field.

[0015] The present inventors have conducted extensive research focusing on the magnetic properties and ion exchange properties of zeolites, and have found that a magnetized zeolite with high magnetic field sensitivity can be obtained by ion-exchanging some or all of the cationic elements contained in zeolite with magnetic ionic elements. Furthermore, the inventors have confirmed that oriented zeolite can be produced using a low magnetic field that can be applied using highly versatile equipment and methods by dispersing the magnetized zeolite powder obtained after ion exchange in a solvent to form a dispersion, and then applying a magnetic field to the dispersion while depositing and aggregating the magnetized zeolite and removing the solvent, thereby completing the present invention.

[0016] The method for producing an oriented zeolite body and the oriented zeolite body of the present invention will be described in detail below. [Oriented zeolite] The oriented zeolite of this embodiment is manufactured using the manufacturing method for the oriented zeolite of this embodiment. The oriented zeolite of this embodiment is a molded body in which the micropores of powdered magnetized zeolite are regularly arranged and aggregated. The oriented zeolite of this embodiment has an orientation degree of 0.05 to 0.6 according to the Lotgering method, and is a zeolite in which magnetic ion elements have been introduced into the crystal structure and the micropores are regularly arranged. In the orientation degree according to the Lotgering method, an orientation degree of 1 indicates complete orientation, and an orientation degree of 0 indicates no orientation.

[0017] The oriented zeolite of this embodiment has an orientation degree of 0.05 to 0.6, preferably 0.05 to 0.5, and more preferably 0.1 to 0.5, as determined by the Lotgering method. The orientation degree of the oriented zeolite can be determined appropriately depending on the application. When the orientation degree of the oriented zeolite is 0.05 or more, the effect of the ordered arrangement of micropores due to the orientation can be sufficiently obtained. The orientation degree of the oriented zeolite is preferably 0.1 or more, and more preferably 0.2 or more, since the effect of the ordered arrangement of micropores becomes significant. Furthermore, oriented zeolite having an orientation degree of 0.5 or less can be produced with a high yield by the production method of this embodiment.

[0018] The type of zeolite constituting the oriented zeolite of the present embodiment can be appropriately selected depending on the application of the oriented zeolite, and is not particularly limited. For example, the type of zeolite constituting the oriented zeolite of this embodiment may be any of A-type (LTA), X-type (FAU), Y-type (FAU), and L-type (LTL). When the zeolite constituting the oriented zeolite is L-type, which has a large anisotropy of crystal structure, the effects due to the orientation of the zeolite, such as molecular sieving ability and adsorption ability, are easily exhibited, which is preferable.

[0019] The magnetized zeolite constituting the oriented zeolite of this embodiment is a crystalline aluminosilicate, and contains Al, Si, O (oxygen), a cationic element, and a magnetic ionic element. The ratio of the number of silicon atoms to the number of aluminum atoms (Si:Al) contained in the magnetized zeolite constituting the oriented zeolite of this embodiment, and the types and contents of the cation elements and magnetic ion elements can be appropriately determined depending on the application and are not particularly limited.

[0020] The ratio of the number of silicon atoms to the number of aluminum atoms (Si:Al) can be set to, for example, 1:1 to 5:1. Examples of cationic elements include Cs, Rb, K, Ba, Sr, Na, Ca, and Mg. The cationic element is preferably K or Na, since this allows the magnetization step and ion exchange step in the manufacturing method of this embodiment, which will be described later, to be carried out efficiently. The cationic element contained in the zeolite constituting the oriented zeolite body may be one type only, or two or more types.

[0021] The magnetic ionic element introduced into the crystal structure of the magnetic zeolite constituting the oriented zeolite of this embodiment is one or more magnetic elements selected from the transition metal element group and the rare earth metal element group. Examples of magnetic elements selected from the transition metal element group include Fe and Co. Examples of magnetic elements selected from the rare earth metal element group include Ho and Dy. The magnetic ionic element is preferably an element that becomes an ion with a large magnetic moment. This is because a highly oriented zeolite is more likely to be obtained in the orientation step described below, which is performed to produce the oriented zeolite of this embodiment. The magnetic ionic element introduced into the crystal structure of the zeolite may be only one type, or two or more types. In this embodiment, if the magnetic ionic element introduced into the crystal structure of the magnetic zeolite constituting the oriented zeolite is also a cation element contained in the raw zeolite, it is considered to be a magnetic ionic element rather than a cation.

[0022] Specific examples of the ions of the magnetic ion element introduced into the crystal structure of the magnetized zeolite constituting the oriented zeolite of this embodiment include Fe 3+ (Magnetic moment 5.92(μ B )),Fe 2+ (Magnetic moment 6.70(μ B )),Co 2+ (Magnetic moment 6.63(μ B )),Ni 2+ (Magnetic moment 5.59(μ B )),Gd 3+ (Magnetic moment 7.98(μ B )),Ho 3+(Magnetic moment 10.60(μ B )),Dy 3+ (Magnetic moment 10.63(μ B )), Mn 2+ (Magnetic moment 5.92(μ B )),Tb 3+ (Magnetic moment 9.72(μ B )),Er 3+ (Magnetic moment 9.59(μ B )),Tm 3+ (Magnetic moment 7.57(μ B )),Ti 3+ , V 4+ (Magnetic moment 1.55(μ B )),V 3+ (Magnetic moment 1.63(μ B )),Cr 2+ , V 2+ (Magnetic moment 0.77(μ B )),Cu 2+ (Magnetic moment 3.55(μ B )),Ce 3+ (Magnetic moment 2.54(μ B )),Pr 3+ (Magnetic moment 3.58(μ B )),Nd 3+ (Magnetic moment 3.62(μ B )),Pm 3+ (Magnetic moment 2.68(μ B )),Sm 3+ (Magnetic moment 0.85(μ B )),Yb 3+ (Magnetic moment 4.53(μ B Among these magnetic ion elements, the magnetic ion element introduced into the crystal structure of the magnetized zeolite constituting the oriented zeolite has a large magnetic moment, and therefore is preferably one or more elements selected from Ho, Dy, Tb, and Er. Furthermore, of these, Ho is more preferred from the viewpoint of easy availability of the raw material.

[0023] The ratio of the number of cation elements to the number of magnetic ion elements in the magnetized zeolite constituting the oriented zeolite of this embodiment can be appropriately selected depending on the application of the oriented zeolite. When the magnetic ion elements introduced into the magnetized zeolite constituting the oriented zeolite of this embodiment also serve as cation elements, the magnetized zeolite constituting the oriented zeolite of this embodiment does not need to contain cation elements.

[0024] The ion exchange rate of the magnetic zeolite constituting the oriented zeolite of this embodiment varies depending on the type of zeolite. The higher the ion exchange rate of the magnetic zeolite, the greater the amount of magnetic ion elements introduced into the crystal structure, and the higher the magnetic field sensitivity, which is preferable because the oriented zeolite can be produced in a lower magnetic field. In this specification, the term "ion exchange rate" refers to a value calculated by the following formula. Ion exchange rate (%) = {b / (a+b)} x 100 (In the formula, a is the product of the valence and number of cations, and b is the product of the valence and number of magnetic ions.)

[0025] The ion exchange rate of the magnetic zeolite is 5% to 90% in the case of A-type zeolite, and to obtain an oriented zeolite using a weaker magnetic field, the ion exchange rate is preferably 10% to 90%, and more preferably 20% to 90%. When the ion exchange rate is 20% or more, the effect of including a magnetic ion element is easily obtained. The ion exchange rate of the magnetic zeolite is 5% to 40% in the case of L-type zeolite, and to obtain an oriented zeolite using a weaker magnetic field, the ion exchange rate is preferably 10% to 40%, and more preferably 20% to 40%. When the ion exchange rate is 20% or more, the effect of including a magnetic ion element is easily obtained.

[0026] The ion exchange rate of the magnetic zeolite is 5% to 80% in the case of X-type zeolite, and to obtain an oriented zeolite using a weaker magnetic field, the ion exchange rate is preferably 10% to 80%, and more preferably 20% to 80%. When the ion exchange rate is 20% or more, the effect of including a magnetic ion element is easily obtained. The ion exchange rate of the magnetic zeolite is 5% to 70% in the case of Y-type zeolite, and to obtain an oriented zeolite using a weaker magnetic field, the ion exchange rate is preferably 10% to 70%, and more preferably 20% to 70%. When the ion exchange rate is 20% or more, the effect of including a magnetic ion element is easily obtained.

[0027] The crystal orientation of the oriented zeolite body of this embodiment is not particularly limited, and may be, for example, a c-axis orientation or an ab-plane orientation. For example, when the oriented zeolite of the present embodiment is L-type zeolite, the L-type zeolite may be c-axis oriented or ab-plane oriented. When the zeolite constituting the oriented zeolite of this embodiment is, for example, L-type zeolite, in order to easily produce a c-axis oriented body in which the crystal orientation is c-axis oriented, it is preferable that the magnetic ion element introduced into the crystal structure of the magnetized zeolite is one or more selected from Ce, Pr, Nd, Tb, Dy, and Ho. When the zeolite constituting the oriented zeolite of this embodiment is, for example, L-type zeolite, in order to easily produce an ab-plane oriented body having an ab-plane crystal orientation, it is preferable that the magnetic ion element introduced into the crystal structure of the magnetized zeolite is one or more selected from Pm, Sm, Er, Tm, and Yb.

[0028] The oriented zeolite of this embodiment has an orientation degree of 0.05 to 0.6 by the Lotgering method, and is a zeolite having magnetic ion elements introduced into its crystal structure, with micropores arranged in an orderly fashion. Therefore, the oriented zeolite of this embodiment can be suitably used in fields such as separation membranes, chemical sensors, and optoelectronics. Furthermore, the oriented zeolite of this embodiment can be manufactured using the highly versatile manufacturing method for the oriented zeolite of this embodiment, which will be described later.

[0029] [Method of manufacturing oriented zeolite] The method for producing an oriented zeolite body of this embodiment includes a magnetization step and an orientation step. In the method for producing an oriented zeolite body of this embodiment, an ion exchange step is carried out as needed after the orientation step. (Magnetization process) First, raw zeolite is immersed in an aqueous solution containing magnetic ion elements to perform ion exchange. As a result, the cation elements contained in the raw zeolite are exchanged with magnetic ion elements, and magnetic zeolite is produced in which the magnetic ion elements are introduced into the crystal structure of the raw zeolite.

[0030] The raw material zeolite used in the magnetization step is a crystalline aluminosilicate, and contains Al, Si, O (oxygen), and cationic elements. The type and content of the cationic elements contained in the raw material zeolite are determined appropriately depending on the type of zeolite.

[0031] Examples of cationic elements contained in the raw material zeolite include Cs, Rb, K, Ba, Sr, Na, Ca, and Mg. The raw material zeolite may contain only one type of cationic element, or two or more types of cationic elements. The cationic elements contained in the raw material zeolite may be the same as or different from the cationic elements contained in the target oriented zeolite. When the cationic elements contained in the raw material zeolite are the same as the cationic elements contained in the target oriented zeolite, the oriented zeolite may be easily produced without performing an ion exchange step to change the type of cationic element in the production process of the oriented zeolite.

[0032] The type of raw material zeolite used in the magnetization step may be any type, such as A-type, X-type, Y-type, or L-type, and is particularly preferably L-type, which has a large anisotropy of crystal structure. The type can be appropriately determined depending on the type of oriented zeolite that is the target product. As the raw material zeolite, commercially available zeolite may be used.

[0033] As the raw material zeolite, powdered zeolite can be used. As the raw material zeolite, powdered zeolite may be formed into any shape such as a plate or pellet, as necessary, and used. As a method for molding powdered zeolite, a known method such as uniaxial pressing can be used.

[0034] Examples of the aqueous solution containing the magnetic ion element used in the magnetization step include an aqueous solution of a nitrate containing the above-mentioned magnetic ion element, an aqueous solution of a chloride, etc. For example, when the magnetic ion element is Ho, a holmium nitrate aqueous solution or the like can be preferably used as the aqueous solution containing the magnetic ion element. The concentration of the magnetic ion element in the aqueous solution containing the magnetic ion element can be, for example, 0.01 mol / L to 1 mol / L, and can be appropriately determined depending on the type of raw material zeolite, the composition of the target magnetized zeolite, etc.

[0035] The crystal orientation of the oriented zeolite body produced in this embodiment can be controlled by the type of magnetic ion element used in the magnetization step. Therefore, it is preferable to select the magnetic ion element used in the magnetization step depending on the crystal orientation of the oriented zeolite body to be produced. Specifically, for example, when producing a c-axis oriented zeolite L, it is preferable to select one or more magnetic ion elements selected from Ce, Pr, Nd, Tb, Dy, and Ho. Furthermore, for example, when producing an ab-plane oriented zeolite L, it is preferable to select one or more magnetic ion elements selected from Pm, Sm, Er, Tm, and Yb.

[0036] In the magnetization step, the method for immersing the raw zeolite in the aqueous solution containing the magnetic ion element can be any known method, and is not particularly limited depending on the type of raw zeolite. In the magnetization step, the conditions such as temperature and time for immersing the raw zeolite in the aqueous solution containing the magnetic ion element can be appropriately determined depending on the type of raw zeolite, the composition of the target magnetized zeolite, etc.

[0037] In the magnetization step, only a portion of the cation elements contained in the raw zeolite may be exchanged with magnetic ion elements, or all of the cation elements may be exchanged with magnetic ion elements. When all of the cation elements contained in the raw zeolite are exchanged with magnetic ion elements, the produced magnetized zeolite does not contain any cation elements.

[0038] The ion exchange rate of the magnetized zeolite produced in the magnetization step varies depending on the type of magnetized zeolite (raw material zeolite). The higher the ion exchange rate of the magnetized zeolite, the greater the amount of magnetic ion elements introduced into the crystal structure, and the higher the magnetic field sensitivity. Therefore, the higher the ion exchange rate of the magnetized zeolite, the lower the magnetic field that can be used in the orientation step described below, making it preferable.

[0039] The ion exchange rate of the magnetic zeolite is 5% to 90% when it is type A zeolite, and to obtain an oriented zeolite, the ion exchange rate is preferably 10% to 90%, more preferably 20% to 90%. An ion exchange rate of 20% or more results in a magnetic zeolite with sufficient magnetic field sensitivity. Therefore, an ion exchange rate of 20% or more significantly reduces the strength of the magnetic field applied to the magnetic zeolite in the orientation step described below, and also facilitates the production of an oriented zeolite with a high degree of orientation. Furthermore, an ion exchange rate of 90% or less can be used to obtain an oriented zeolite with a low residual amount of magnetic ionic elements by performing the ion exchange step described below as necessary.

[0040] The ion exchange rate of the magnetic zeolite is 5% to 40% when it is L-type zeolite. To obtain an oriented zeolite, the ion exchange rate is preferably 10% to 40%, more preferably 20% to 40%. An ion exchange rate of 20% or more results in a magnetic zeolite with sufficient magnetic field sensitivity. Therefore, an ion exchange rate of 20% or more significantly reduces the strength of the magnetic field applied to the magnetic zeolite in the orientation step described below, and also makes it easier to obtain an oriented zeolite with a high degree of orientation. Furthermore, an ion exchange rate of 40% or less can be used to obtain an oriented zeolite with a low residual amount of magnetic ion elements, with a magnetic ion residual rate of 4% or less, by performing the ion exchange step described below as necessary.

[0041] The ion exchange rate of the magnetic zeolite is 5% to 80% when it is X-type zeolite, and to obtain an oriented zeolite, the ion exchange rate is preferably 10% to 80%, more preferably 20% to 80%. An ion exchange rate of 20% or more results in a magnetic zeolite with sufficient magnetic field sensitivity. Therefore, an ion exchange rate of 20% or more significantly reduces the strength of the magnetic field applied to the magnetic zeolite in the orientation step described below, and also facilitates the production of an oriented zeolite with a high degree of orientation. Furthermore, an ion exchange rate of 80% or less can be used to obtain an oriented zeolite with a low residual amount of magnetic ion elements by optionally performing the ion exchange step described below.

[0042] The ion exchange rate of the magnetic zeolite is 5% to 70% when it is Y-type zeolite, and to obtain an oriented zeolite, the ion exchange rate is preferably 10% to 70%, more preferably 20% to 70%. An ion exchange rate of 20% or more results in a magnetic zeolite with sufficient magnetic field sensitivity. Therefore, an ion exchange rate of 20% or more significantly reduces the strength of the magnetic field applied to the magnetic zeolite in the orientation step described below, and also facilitates the production of an oriented zeolite with a high degree of orientation. Furthermore, an ion exchange rate of 70% or less can be used to obtain an oriented zeolite with a low residual amount of magnetic ion elements by performing the ion exchange step described below as necessary.

[0043] (Orientation process) Next, in this embodiment, the magnetized zeolite powder produced in the magnetization step is dispersed in a solvent to form a dispersion, and while a magnetic field is applied to the dispersion, the magnetized zeolite is deposited and aggregated, and the solvent is then removed. This results in the formation of an oriented zeolite body, which is a compact in which the micropores of the magnetized zeolite powder are regularly arranged and aggregated.

[0044] The magnetized zeolite is used in powder form. When powdered zeolite is used as the raw zeolite, powdered magnetized zeolite can be obtained by carrying out the magnetization step. Therefore, the magnetized zeolite produced in the magnetization step can be used as is in the orientation step. When powdered zeolite molded into any shape such as a plate or pellet is used as the raw material zeolite, the magnetized zeolite produced in the magnetization step is pulverized into powder by a known method and then used in the orientation step.

[0045] The magnetic zeolite powder can be dispersed in a solvent to form a dispersion liquid by any known method, and the solvent can be, for example, water.

[0046] As a method for applying a magnetic field to the dispersion, known methods such as a method using a commercially available neodymium magnet, a method using a commercially available samarium-cobalt magnet, or a method using an electromagnet can be used, and can be appropriately selected depending on the magnetic field sensitivity of the magnetized zeolite.

[0047] In the orientation step, the magnetic field applied to the dispersion is preferably 0.5 to 4 T, more preferably 0.9 to 1.5 T. When the magnetic field applied to the dispersion is 0.5 T or more, oriented zeolite with an orientation degree of 0.05 or more is easily obtained, which is preferable. When the magnetic field applied to the dispersion is 0.9 T or more, oriented zeolite with an orientation degree of 0.2 or more is easily obtained, which is preferable. When the magnetic field applied to the dispersion is 4 T or less, a magnetic field can be applied to the dispersion using a highly versatile method and device without using a superconducting magnet, which is preferable. When the magnetic field applied to the dispersion is 1.5 T or less, more versatile methods and devices such as commercially available neodymium magnets and samarium-cobalt magnets can be used.

[0048] In the orientation step, it is preferable to use a slip casting method. Specifically, the slip casting method can be performed using the following method. First, a dispersion liquid is prepared by dispersing magnetized zeolite powder in a solvent. Next, a frame-shaped mold is prepared and placed on a substrate. The mold may have any shape as long as it is frame-shaped, such as a circular or polygonal shape in plan view. Next, the dispersion liquid is poured into the mold, and a magnetic field in a predetermined direction is applied to the dispersion liquid to orient the magnetized zeolite in the dispersion liquid. The magnetized zeolite is then deposited and aggregated within the mold, and the solvent in the dispersion liquid is removed. The resulting deposit is then dried, and the mold is removed. Through these steps, an oriented zeolite body having a shape corresponding to the shape of the mold is obtained.

[0049] The oriented zeolite body may have any shape, such as a spherical shape, a cylindrical shape, or a columnar shape.

[0050] Fig. 1 is a diagram illustrating an example of the orientation step in the production method of this embodiment, in which an example is taken of the use of L-type zeolite. As shown in FIG. 1, for example, while applying a magnetic field B1 in a direction perpendicular to the substrate S to the dispersion, Dy is formed in the crystalline structure of the zeolite. 3+ , Ho 3+ , Tb 3+ , Nd 3+ , Pr 3+ or Ce 3+ The magnetized zeolite MZ1 into which the magnetic flux is introduced is condensed and deposited, and the solvent is removed. This results in the formation of an oriented zeolite A1, which is a compact in which the c-axes of the magnetized zeolite MZ1 are aligned along the direction of application of the magnetic field B1 and the micropores MP1 of the powdered magnetized zeolite MZ1 are regularly aligned in a direction perpendicular to the substrate S. This oriented zeolite A1 is a c-axis-oriented compact in which the c-axes of the magnetized zeolite MZ1 are aligned perpendicular to the substrate surface.

[0051] Also, for example, while applying a magnetic field B1, Er is formed in the crystalline structure of the zeolite. 3+ , Yb 3 or Tm 3+The magnetized zeolite MZ2 into which the magnetic particles have been introduced is condensed and deposited, and the solvent is removed. This results in the formation of an oriented zeolite A2, which is a compact in which the ab planes of the magnetized zeolite MZ2 are aligned along the direction of application of the magnetic field B1 and the micropores MP2 of the powdered magnetized zeolite MZ2 are regularly aligned in the in-plane direction of the substrate S. This oriented zeolite A2 is an ab-plane oriented compact in which the ab planes of the magnetized zeolite MZ1 are aligned perpendicular to the substrate surface.

[0052] On the other hand, for example, while applying a magnetic field B1, Gd 3+ or EU 3 The magnetized zeolite MZ3 containing the introduced β-hydroxybenzoates is condensed and deposited, and the solvent is removed. In this case, neither the c-axis nor the ab-plane of the magnetized zeolite MZ3 is aligned along the direction of the applied magnetic field B1, and an oriented zeolite A3 is formed, which is a compact in which the micropores MP3 of the powdered magnetized zeolite MZ3 are aggregated in a non-oriented state.

[0053] FIG. 2 is a diagram illustrating another example of the orientation step in the manufacturing method of this embodiment. As shown in FIG. 2, for example, while applying a magnetic field B2 in a direction parallel to the substrate S to the dispersion, Dy is formed in the crystalline structure of the zeolite. 3+ , Ho 3+ , Tb 3+ , Nd 3+ , Pr 3+ or Ce 3+ The magnetized zeolite MZ1 into which the magnetic flux is introduced is condensed and deposited, and the solvent is removed. This results in the formation of an oriented zeolite A4, which is a compact in which the c-axes of the magnetized zeolite MZ1 are aligned along the direction of application of the magnetic field B2 and the micropores MP1 of the powdered magnetized zeolite MZ1 are regularly aligned along the direction of application of the magnetic field to the substrate S. This oriented zeolite A4 is an ab-plane oriented compact in which the ab planes of the magnetized zeolite MZ1 are aligned perpendicular to the substrate surface.

[0054] Also, for example, while applying a magnetic field B2, Er is formed in the crystalline structure of the zeolite. 3+ , Yb 3 or Tm3+ The magnetized zeolite MZ2 into which the magnetic flux is introduced is condensed and deposited, and the solvent is removed. This results in the formation of an oriented zeolite A5, a compact in which the ab planes of the magnetized zeolite MZ2 are aligned along the direction of application of the magnetic field B2 and the micropores MP2 of the powdered magnetized zeolite MZ2 are regularly aligned in a direction perpendicular to the substrate S. This oriented zeolite A5 is a c-axis oriented compact in which the c-axes of the magnetized zeolite MZ2 are aligned perpendicular to the substrate surface.

[0055] On the other hand, for example, while applying a magnetic field B2, Gd 3+ or EU 3 The magnetized zeolite MZ3 containing the introduced zeolite MZ3 is then condensed and deposited, and the solvent is removed. In this case, neither the c-axis nor the ab-plane of the magnetized zeolite MZ3 is aligned along the direction of the applied magnetic field B2, and the micropores MP3 of the powdered magnetized zeolite MZ3 are aggregated in a non-oriented state, forming an oriented zeolite A6.

[0056] In the above-mentioned orientation process, Tm 3+ , Pm 3+ or Sm 3+ When using magnetic zeolite with Er introduced, the electronic state of these metal ions becomes Er. 3+ Since these are similar to the magnetic zeolite MZ2 and magnetic zeolite MZ5, it is presumed that they will exhibit the same orientation behavior as the magnetic zeolite MZ2 or magnetic zeolite MZ5. In addition, Lu exists in the crystal structure of zeolite. 3+ When using a magnetic zeolite with Gd 3+ Since these are similar to the magnetized zeolite MZ3 and MZ6, it is presumed that they will exhibit the same orientation behavior as the magnetized zeolite MZ3 or MZ6.

[0057] In this way, by adjusting the type of metal ions introduced into the crystal structure of the magnetic zeolite and the direction of the applied magnetic field in the above-mentioned orientation process, it is possible to obtain oriented zeolite bodies containing various magnetic ion elements and with different orientations of the magnetic zeolite.

[0058] (Ion exchange process) Next, in this embodiment, the oriented zeolite produced in the orientation step is brought into contact with an aqueous solution containing cationic elements, as needed, to exchange the cationic elements with the magnetic ionic elements contained in the magnetized zeolite that constitutes the oriented zeolite.

[0059] Examples of the aqueous solution containing a cationic element used in the ion exchange step include an aqueous solution of a chloride containing the above-mentioned element that becomes a cation. For example, when the cationic element is K, an aqueous solution of potassium chloride can be preferably used. The cationic element in the aqueous solution containing a cationic element may be the same as or different from the cationic element contained in the raw zeolite. The concentration of the cationic element in the aqueous solution containing the cationic element can be, for example, 0.01 to 1 mol / L, and can be appropriately determined depending on the type of zeolite that constitutes the oriented zeolite body, the composition of the zeolite that constitutes the oriented zeolite body after the ion exchange process, etc.

[0060] In the ion exchange process, the method of contacting the oriented zeolite body with an aqueous solution containing cationic elements can be, for example, a method of immersing the oriented zeolite body in an aqueous solution containing cationic elements, and is not particularly limited by the type of zeolite that constitutes the oriented zeolite body. In the ion exchange process, the conditions such as temperature and time for contacting the aqueous solution containing cationic elements with the zeolite oriented body can be appropriately determined depending on the type of zeolite that constitutes the zeolite oriented body and the composition of the desired zeolite oriented body after the ion exchange process.

[0061] The residual rate of magnetic ions in the zeolite constituting the oriented zeolite obtained in the ion exchange step differs depending on the type of zeolite constituting the oriented zeolite. The residual magnetic ion rate of the zeolite constituting the oriented zeolite after the ion exchange process can be 4% or less, preferably 1% or less, for example, in the case of L-type zeolite. When the residual magnetic ion rate is 4% or less, the number of magnetic ion elements is sufficiently small, so that the oriented zeolite can be used for the same purposes as an oriented zeolite that does not contain magnetic ion elements. Furthermore, a zeolite constituting the oriented zeolite after the ion exchange process with a residual magnetic ion rate of 4% or less can be easily produced by carrying out the ion exchange process of this embodiment.

[0062] In the ion exchange process, the conditions such as temperature and time for contacting the aqueous solution containing cationic elements with the oriented zeolite can be appropriately determined depending on the composition of the magnetic zeolite that constitutes the oriented zeolite, the type of zeolite that constitutes the oriented zeolite, etc. In this embodiment, by adjusting the conditions of the ion exchange process, the amount of magnetic ion elements remaining in the zeolite oriented body after the ion exchange process may be below the detection limit (i.e., no magnetic ion elements are contained).

[0063] The ion exchange process of this embodiment has only a slight effect on the orientation of the zeolite oriented body (degree of orientation as determined by the Lotgering method), and it can be considered that the ion exchange process has no effect on the orientation of the zeolite oriented body.

[0064] In the method for producing an oriented zeolite body of this embodiment, a powder of magnetized zeolite produced by a magnetization step is dispersed in a solvent to form a dispersion, and a magnetic field is applied to the dispersion to deposit and aggregate the magnetized zeolite, and the solvent is then removed. Because the magnetized zeolite has magnetic ion elements introduced into its crystalline structure, the micropores are regularly arranged even when a weak magnetic field is applied to the dispersion. Therefore, according to the method for producing an oriented zeolite body of this embodiment, an oriented zeolite body can be produced without using a strong magnetic field.

[0065] Furthermore, in the method for producing the oriented zeolite of this embodiment, if necessary, an ion exchange step is performed to exchange cation elements with magnetic ion elements contained in the magnetized zeolite constituting the oriented zeolite, thereby obtaining an oriented zeolite that does not contain magnetic ion elements or has a small amount of residual magnetic ion elements. Therefore, it is possible to obtain an oriented zeolite that is suitable for applications where it is preferable that the oriented zeolite does not contain magnetic ion elements or has a small amount of residual magnetic ion elements. [Example]

[0066] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. [Manufacturing Example 1] (Magnetization process) Holmium nitrate n-hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in pure water to prepare a 0.1 mol / L holmium nitrate aqueous solution as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 1 was prepared. (Raw Zeolite 1) A-type zeolite, trade name: Synthetic Zeolite A-4 Powder, manufactured by Wako Pure Chemical Industries, Ltd., ratio of the number of silicon atoms to the number of aluminum atoms (Si / Al=1.0)

[0067] The magnetic properties (magnetization and magnetic field) of raw material zeolite 1 were measured at room temperature using a vibrating sample magnetometer (VSM) (product name: TM-VSM15148S, manufactured by Tamagawa Seisakusho Co., Ltd.) under the following conditions: frequency 82.5 Hz, amplitude 3 mm P-P, maximum magnetic field 2 T, lock-in amplifier sensitivity 100 μV, and time constant 30 msec. The results are shown in Figure 3(a).

[0068] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L holmium nitrate aqueous solution and stirred at 160 rpm using a shaker (manufactured by Taitec Co., Ltd.) at room temperature (25°C) for 24 hours to form a crystalline structure of zeolite with Ho. 3+ The magnetic zeolite was prepared by incorporating The reaction solution in which the magnetized zeolite was produced was filtered using a membrane filter with a mesh size of 0.2 μm, and washed three times with pure water to obtain powdery magnetized zeolite.

[0069] The magnetic properties (magnetization and magnetic field) of the magnetized zeolite of Production Example 1 obtained in this manner were measured in the same manner as for raw material zeolite 1. The results are shown in Figure 3(a). FIG. 3(a) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 1 and Raw Zeolite 1.

[0070] [Manufacturing Examples 2-3] The magnetization step was carried out in the same manner as in Production Example 1, except that powdered raw zeolites 2 and 3 shown below were used instead of raw zeolite 1, to obtain powdered magnetized zeolites of Production Examples 2 and 3.

[0071] (Raw Zeolite 2) Commercially available X-type zeolite, trade name: NaX, ratio of silicon atoms to aluminum atoms (Si / Al=1.3) (Raw Zeolite 3) Y-type zeolite, product name: HSZ-320NAA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=2.7)

[0072] [Manufacturing Example 4] Holmium nitrate n-hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in pure water to prepare a 0.1 mol / L holmium nitrate aqueous solution as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 4 was prepared. (Raw Zeolite 4) L-type zeolite, product name: HSZ-500KOA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=3.0)

[0073] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L holmium nitrate aqueous solution and stirred at 160 rpm using a shaker (manufactured by Taitec Co., Ltd.) at room temperature (25°C) for 24 hours to form a crystalline structure of zeolite with Ho. 3+ The magnetic zeolite was prepared by incorporating

[0074] The magnetic properties (magnetization and magnetic field) of raw material zeolites 2 to 4 and the magnetized zeolites of Production Examples 2 to 4 were measured in the same manner as for raw material zeolite 1. The results are shown in Figures 3(b) to 3(d).

[0075] Fig. 3(b) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 2 and raw zeolite 2. Fig. 3(c) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 3 and raw zeolite 3. Fig. 3(d) is a graph showing the relationship between the magnetic field and magnetization for the magnetized zeolite of Production Example 4 and raw zeolite 4.

[0076] As shown in Figures 3(a) to 3(d), it was confirmed that the magnetization of raw material zeolites 1 to 4 hardly changed when the magnetic field was changed, and that they had weak magnetism. On the other hand, as shown in Figures 3(a) to 3(d), the magnetized zeolites of Production Examples 1 to 4 all showed increased magnetization as the magnetic field was increased. This confirmed that, regardless of the type of raw material zeolite, magnetized zeolites with high magnetic field sensitivity can be obtained by performing the magnetization step.

[0077] [Manufacturing Example 5] Dysprosium nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in pure water to prepare a 0.1 mol / L dysprosium nitrate aqueous solution as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 4 was prepared. (Raw Zeolite 4) L-type zeolite, product name: HSZ-500KOA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=3.0)

[0078] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L dysprosium nitrate aqueous solution and stirred at 160 rpm for 24 hours at room temperature (25°C) using a shaker (manufactured by Taitec Co., Ltd.). 3+ The magnetic zeolite was prepared by incorporating

[0079] [Manufacturing Example 6] Terbium (III) chloride hexahydrate (manufactured by Kanto Chemical Co., Inc.) was dissolved in pure water to prepare a 0.1 mol / L aqueous solution of terbium chloride as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 4 was prepared. (Raw Zeolite 4) L-type zeolite, product name: HSZ-500KOA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=3.0)

[0080] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L terbium chloride aqueous solution and stirred at 160 rpm for 24 hours at room temperature (25°C) using a shaker (manufactured by Taitec Co., Ltd.). This stirred mixture allowed the formation of Tb in the zeolite crystal structure. 3+ The magnetic zeolite was prepared by incorporating

[0081] [Manufacturing Example 7] Neodymium (III) nitrate hexahydrate (manufactured by Nacalai Tesque, Inc.) was dissolved in pure water to prepare a 0.1 mol / L aqueous solution of neodymium nitrate as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 4 was prepared. (Raw Zeolite 4) L-type zeolite, product name: HSZ-500KOA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=3.0)

[0082] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L neodymium nitrate aqueous solution and stirred at room temperature (25°C) for 24 hours at a rotation speed of 160 rpm using a shaker (manufactured by Taitec Co., Ltd.). 3+ The magnetic zeolite was prepared by incorporating

[0083] [Manufacturing Example 8] Praseodymium (III) nitrate hexahydrate (manufactured by Kanto Chemical Co., Inc.) was dissolved in pure water to prepare a 0.1 mol / L aqueous solution of praseodymium nitrate as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 4 was prepared. (Raw Zeolite 4) L-type zeolite, product name: HSZ-500KOA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=3.0)

[0084] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L praseodymium nitrate aqueous solution and stirred at room temperature (25°C) for 24 hours at a rotation speed of 160 rpm using a shaker (manufactured by Taitec Co., Ltd.). 3+ The magnetic zeolite was prepared by incorporating

[0085] [Manufacturing Example 9] Cerium (III) nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in pure water to prepare a 0.1 mol / L aqueous solution of cerium nitrate as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 4 was prepared. (Raw Zeolite 4) L-type zeolite, product name: HSZ-500KOA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=3.0)

[0086] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L cerium nitrate aqueous solution, and the mixture was stirred at room temperature (25°C) for 24 hours at a rotation speed of 160 rpm using a shaker (manufactured by Taitec Co., Ltd.). 3+ The magnetic zeolite was prepared by incorporating

[0087] [Manufacturing Example 10] Erbium (III) chloride hexahydrate (manufactured by Sigma-Aldrich Japan LLC) was dissolved in pure water to prepare a 0.1 mol / L aqueous solution of erbium chloride as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 4 was prepared. (Raw Zeolite 4) L-type zeolite, product name: HSZ-500KOA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=3.0)

[0088] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L erbium chloride aqueous solution, and the mixture was stirred at room temperature (25°C) for 24 hours at a rotation speed of 160 rpm using a shaker (manufactured by Taitec Co., Ltd.). 3+ The magnetic zeolite was prepared by incorporating

[0089] [Manufacturing Example 11] Ytterbium (III) nitrate n-hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in pure water to prepare a 0.1 mol / L ytterbium nitrate aqueous solution as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 4 was prepared. (Raw Zeolite 4) L-type zeolite, product name: HSZ-500KOA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=3.0)

[0090] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L ytterbium nitrate aqueous solution and stirred at room temperature (25°C) for 24 hours at a rotation speed of 160 rpm using a shaker (manufactured by Taitec Co., Ltd.). This resulted in the formation of Yb 3+ The magnetic zeolite was prepared by incorporating

[0091] [Manufacturing Example 12] Thulium (III) chloride hexahydrate (manufactured by Mitsuwa Chemical Co., Ltd.) was dissolved in pure water to prepare a 0.1 mol / L thulium chloride aqueous solution as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 4 was prepared. (Raw Zeolite 4) L-type zeolite, product name: HSZ-500KOA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=3.0)

[0092] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L thulium chloride aqueous solution, and the mixture was stirred at room temperature (25°C) for 24 hours at a rotation speed of 160 rpm using a shaker (manufactured by Taitec Co., Ltd.). 3+ The magnetic zeolite was prepared by incorporating

[0093] [Reference production example 1] Gadolinium nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in pure water to prepare a 0.1 mol / L gadolinium nitrate aqueous solution as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 4 was prepared. (Raw Zeolite 4) L-type zeolite, product name: HSZ-500KOA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=3.0)

[0094] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L gadolinium nitrate aqueous solution and stirred at 160 rpm for 24 hours at room temperature (25°C) using a shaker (manufactured by Taitec Co., Ltd.). 3+ The magnetic zeolite was prepared by incorporating

[0095] [Reference production example 2] Europium (III) chloride hexahydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in pure water to prepare a 0.1 mol / L europium chloride aqueous solution as an aqueous solution containing a magnetic ion element. Furthermore, as the raw material zeolite, the following powdery raw material zeolite 4 was prepared. (Raw Zeolite 4) L-type zeolite, product name: HSZ-500KOA, manufactured by Tosoh Corporation, ratio of silicon atoms to aluminum atoms (Si / Al=3.0)

[0096] Two grams of raw zeolite 1 was immersed in 40 mL of the above 0.1 mol / L europium chloride aqueous solution and stirred at 160 rpm for 24 hours at room temperature (25°C) using a shaker (manufactured by Taitec Co., Ltd.). 3+ The magnetic zeolite was prepared by incorporating

[0097] The magnetic properties (magnetization and magnetic field) of raw material zeolite 4 and the magnetized zeolites of Production Examples 5 to 12 and Reference Production Examples 1 and 2 were measured in the same manner as for raw material zeolite 1. The results are shown in Figures 4(a) to 7(b).

[0098] 4(a) to 4(b) and 5(a) to 5(c) are graphs showing the relationship between the magnetic field and magnetization for the magnetized zeolites and raw zeolite 4 of Production Examples 5 to 9, respectively. FIGS. 6(a) to 6(b) are graphs showing the relationship between the magnetic field and magnetization for the magnetized zeolites and raw zeolite 4 of Production Examples 10 to 12, respectively. FIGS. 7(a) to 7(b) are graphs showing the relationship between the magnetic field and magnetization for the magnetized zeolites and raw zeolite 4 of Reference Production Examples 1 and 2, respectively.

[0099] As shown in Figures 4(a) to 7(b), the magnetized zeolites of Production Examples 5 to 12 and Reference Production Examples 1 and 2 all show increased magnetization as the magnetic field strength increases. This confirms that, regardless of the type of magnetic metal ion introduced, performing the magnetization step can produce magnetized zeolites with high magnetic field sensitivity. In addition, among Production Examples 5 to 9, Dy 3+ or Tb 3+ The magnetic zeolite (Production Examples 5 and 6) into which Nd 3+ , Pr 3+ or Ce 3+ It was found that the degree of magnetization relative to the height of the magnetic field was greater than that of the magnetized zeolites (Production Examples 7 to 9) into which Er was introduced. 3+ The magnetic zeolite (Production Example 10) into which Yb 3+ or Tm 3+ It was found that the degree of magnetization relative to the height of the magnetic field was greater than that of the magnetized zeolite into which .beta. was introduced (Production Examples 11 and 12).

[0100] In addition, among Reference Manufacturing Examples 1 and 2, Gd 3+ The magnetic zeolite (Reference Production Example 1) into which Eu 3+ It was found that the degree of magnetization relative to the height of the magnetic field was greater than that of the magnetized zeolite into which .alpha. was introduced (Reference Production Example 2).

[0101] [Manufacturing Example 13] (Orientation process) 5 g of ultrapure water, 1 g of the powdered magnetized zeolite of Production Example 4, and 0.004 g of polyethyleneimine (PEI, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and dispersed for 5 minutes using an ultrasonic homogenizer (manufactured by Sonics & Materials) to obtain a dispersion. The obtained dispersion was allowed to stand at room temperature (25°C) for 3 days, and then the supernatant was collected to separate it from the large particle size precipitate.

[0102] Furthermore, 8 mol% yttria-stabilized zirconia powder (YSZ, product name: TZ-8Y, manufactured by Tosoh Corporation) was filled into a mold and uniaxially pressed at a pressure of 100 MPa. The YSZ compact was then heat-treated at 1250°C for 10 hours to obtain a YSZ substrate. This resulted in a YSZ substrate with a diameter of 8.5 mm and a thickness of 1.9 mm.

[0103] Next, the supernatant of the dispersion containing the magnetized zeolite was slip-cast in a magnetic field to produce an oriented zeolite body. More specifically, a mold was placed on a YSZ substrate, and the supernatant of the dispersion containing the magnetized zeolite was poured into the mold. A magnetic field was then applied to the dispersion poured into the mold, orienting the magnetized zeolite in the dispersion. The oriented magnetized zeolite was then deposited in the mold, and the water in the dispersion was removed. A magnetic field of 0.9 T was applied to the dispersion in a direction perpendicular to the YSZ substrate using a neodymium magnet. The resulting deposit was then dried, and the mold was removed to produce the oriented zeolite body of Production Example 13 on the cylindrical YSZ substrate. Fig. 8(a) is a photograph taken obliquely from above of the oriented zeolite body on the cylindrical YSZ substrate of Production Example 13. Fig. 8(b) is a photograph taken from above of the oriented zeolite body on the cylindrical YSZ substrate of Production Example 13.

[0104] (Ion exchange process) Potassium chloride (Kishida Chemical Co., Ltd.) was dissolved in pure water to prepare a 0.2 mol / L potassium chloride aqueous solution as an aqueous solution containing cationic elements. The oriented zeolite on the cylindrical YSZ substrate of Production Example 5 was immersed in 5 mL of a 0.2 mol / L potassium chloride aqueous solution and allowed to stand at room temperature (25°C) for 24 hours. 3+ and K. + and exchanged it. Then, Ho 3+ and K. +The oriented zeolite body of Production Example 13, which had been exchanged with ions, was washed three times with pure water to obtain an oriented zeolite body after the ion exchange step.

[0105] Next, X-ray diffraction measurements were performed on the powdered raw zeolite 4, the powdered magnetized zeolite of Production Example 4, the oriented zeolite of Production Example 13, and the oriented zeolite after the ion exchange process using an X-ray diffraction (XRD) device (product name: Ultima IV, manufactured by Rigaku Corporation). The X-ray diffraction measurements were performed using CuKα radiation as the X-ray source under the measurement conditions of a tube voltage of 40 kV and a tube current of 40 mA. The scan speed for the powdered raw zeolite 4 (raw powder) and the powdered magnetized zeolite of Production Example 4 (magnetized powder) was 10 degrees / min. The scan speed for the oriented zeolite of Production Example 13 and the oriented zeolite after the ion exchange process was 8 degrees / min. The results are shown in Figure 9.

[0106] 9 is a chart showing X-ray diffraction results for powdered raw zeolite 4 (raw material powder), powdered magnetized zeolite of Production Example 4 (magnetized powder), the oriented zeolite of Production Example 13, and the oriented zeolite after the ion exchange step. The "○" in FIG. 9 indicates a diffraction peak confirmed in the X-ray diffraction measurement of the YSZ substrate.

[0107] From the chart of the powdered magnetized zeolite (magnetized powder) of Production Example 4 and the chart of the oriented zeolite of Production Example 13 shown in Figure 9, it was confirmed that orientation was possible by applying a magnetic field of 0.9 T using a neodymium magnet. Furthermore, from the chart of the oriented zeolite of Production Example 13 and the chart of the oriented zeolite after the ion exchange step, it was confirmed that the effect of the ion exchange step on the degree of orientation was slight.

[0108] Using the results of X-ray diffraction measurements of powdered raw zeolite 4 (raw material powder) shown in FIG. 9, the magnetized zeolite of Production Example 4 (magnetized powder), the oriented zeolite of Production Example 13, and the oriented zeolite after the ion exchange process, the degree of orientation (f) was calculated by the Lotgering method according to the following formula. In the formula, ρ is the integrated intensity ratio of the oriented zeolite of Production Example 13 or the oriented zeolite after the ion exchange process. In the case of the oriented zeolite of Production Example 13, ρ0 is the integrated intensity ratio of the magnetized zeolite powder (magnetized zeolite of Production Example 4) used in Production Example 13. In the case of the oriented zeolite after the ion exchange process, ρ0 is the integrated intensity ratio of the powdered raw zeolite 4. When f = 1, it means complete orientation, and when f = 0, it means non-orientation. f=(ρ-ρ0) / (1-ρ0) ρ and ρ0 are calculated using the following formulas. For evaluation of c-axis orientation ρ=ΣI(00l) / ΣI(hkl) ρ0=ΣI0(00l) / ΣI0(hkl) For evaluation of ab plane orientation ρ=ΣI(hk0) / ΣI(hkl) ρ0=ΣI0(hk0) / ΣI0(hkl)

[0109] The degree of orientation of the oriented zeolite of Production Example 13 calculated by the Lotgering method using the above formula was 0.21. This confirmed that magnetized zeolite could be oriented by applying a magnetic field of 0.9 T using a neodymium magnet. Furthermore, the degree of orientation of the oriented zeolite after the ion exchange process, calculated by the Lotgering method using the above formula, was 0.18, which was slightly different from the degree of orientation of the oriented zeolite of Production Example 13. This confirmed that the effect of the ion exchange process on the degree of orientation was slight.

[0110] Next, the powdered raw material zeolite 4, the oriented zeolite of Production Example 5, and the oriented zeolite after the ion exchange process were analyzed using a wavelength-dispersive X-ray fluorescence (XRF) analyzer (product name: ZSX Primus II, manufactured by Rigaku Corporation) to identify their compositions. The wavelength-dispersive X-ray fluorescence (XRF) analysis was performed in a vacuum under the conditions of a tube voltage of 50 kV, a tube current of 50 mA, and a target element of Rh. The results are shown below. (Powdered raw zeolite 4) K9Al9Si 27 O 72 (Oriented zeolite of Production Example 13) K 6.6 Ho 0.8 Al9Si 27 O 72 (Oriented zeolite after ion exchange process) K 8.7 Ho 0.1 Al9Si 27 O 72

[0111] From the above results, it was confirmed that raw material zeolite 4 contains Al, Si, O (oxygen), and K as a cationic element. Furthermore, from the above results, it is clear that the magnetization step reduces the amount of K contained in raw material zeolite 4. + Ho 3+ and Ho is formed in the zeolite crystal structure. 3+ It was confirmed that a magnetized zeolite into which Ho was introduced (i.e., the composition of the oriented zeolite of Production Example 13) was produced. Furthermore, from the above results, it was confirmed that the ion exchange step increased the amount of Ho contained in the magnetized zeolite constituting the oriented zeolite of Production Example 13. 3+ and K. + It was confirmed that the two were exchanged.

[0112] [Manufacturing Example 14] The procedure of Production Example 13 was repeated except that 5 g of ultrapure water, 1 g of the powdered magnetic zeolite of Production Example 4, and 0.020 g of polyethyleneimine (PEI, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed.3+ We fabricated an oriented zeolite material incorporating

[0113] [Manufacturing Examples 15-19] Dy was prepared in the same manner as in Production Example 13, except that 5 g of ethanol, 1 g of powdered magnetic zeolite of Production Examples 5 to 9, and 0.010 g of polyethyleneimine (PEI, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. 3+ , Tb 3+ , Nd 3+ , Pr 3+ or Ce 3+ We fabricated an oriented zeolite material incorporating

[0114] [Manufacturing Example 20] The procedure of Production Example 13 was repeated except that 5 g of ethanol, 1 g of the powdered magnetic zeolite of Production Example 10, and 0.015 g of polyethyleneimine (PEI, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. 3+ We fabricated an oriented zeolite material incorporating

[0115] [Manufacturing Example 21] Tm was prepared in the same manner as in Production Example 13, except that 5 g of ethanol, 1 g of the powdered magnetic zeolite of Production Example 12, and 0.010 g of polyethyleneimine (PEI, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. 3+ We fabricated an oriented zeolite material incorporating

[0116] [Manufacturing Example 22] Yb was prepared in the same manner as in Production Example 13, except that 5 g of ethanol, 1 g of the powdered magnetized zeolite of Production Example 11, and 0.010 g of polyethyleneimine (PEI, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. 3+ We fabricated an oriented zeolite material incorporating

[0117] [Reference production example 3] Gd was prepared in the same manner as in Production Example 13, except that 5 g of ultrapure water, 1 g of the powdered magnetized zeolite of Reference Production Example 1, and 0.004 g of polyethyleneimine (PEI, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. 3+ A zeolite molded body into which was introduced was prepared.

[0118] [Reference production example 4] Eu was prepared in the same manner as in Production Example 13, except that 5 g of ultrapure water, 1 g of the powdered magnetic zeolite of Reference Production Example 2, and 0.004 g of polyethyleneimine (PEI, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. 3+ A zeolite molded body into which was introduced was prepared.

[0119] The f values ​​were calculated by the Lotgering method using the above formula for the oriented zeolite bodies obtained in Production Examples 14 to 22 and Reference Production Examples 3 and 4. The results are shown in Table 1.

[0120] [Table 1]

[0121] From the results in Table 1, it was confirmed that the degree of orientation (f) of the oriented zeolite of Production Examples 14 to 19 measured by the Lotgering method was 0.12 to 0.44, and that the magnetized zeolite could be oriented by applying a magnetic field of 0.9 T using a neodymium magnet. 3+ , Dy 3+ or Tb 3+ When the magnetic zeolite into which was introduced was used, the degree of orientation measured by the Lotgering method was 0.33 to 0.44, and it was confirmed that the degree of orientation of the magnetic zeolite was greater.

[0122] Furthermore, the degrees of orientation (f) of the oriented zeolite bodies of Production Examples 20 to 22 measured by the Lotgering method were 0.11 to 0.13, and it was confirmed that magnetized zeolite could be oriented by applying a magnetic field of 0.9 T using a neodymium magnet.

[0123] On the other hand, in Reference Production Examples 3 and 4, the degree of orientation measured by the Lotgering method was 0.03 to 0.04, and it was confirmed that the degree of orientation of the magnetized zeolite was extremely small and the magnetized zeolite was hardly oriented.

[0124] As a reference for the degree of orientation, the oriented zeolite obtained in Production Examples 14 to 19 was calculated using the Lotgering factor orthogonal (F ortho The calculation formula and the calculation results are shown in Table 1. In the formula, ρ ortho is the diffraction intensity ratio of the oriented body, ρ 0ortho is the diffraction intensity ratio of the non-oriented body.

[0125] F ortho =(ρ ortho -ρ 0ortho ) / (1-ρ 0ortho ) ρ ortho =ΣI(00l) / ΣI((h00)+(0k0)+(00l)) ρ 0ortho =ΣI0(00l) / ΣI0((h00)+(0k0)+(00l))

[0126] As shown in Table 1, the F of the oriented zeolite of Production Examples 14 to 19 calculated from the above formula ortho The values ​​were 0.28 to 0.91. From this, it was found that in this example, when calculated by the method described in JP 2020-158323 A, the degree of orientation of the magnetic zeolite was a larger value. In particular, in Examples 14 to 16, Ho 3+ , Dy 3+ or Tb 3+ When magnetic zeolite containing F was used, ortho The values ​​were 0.86 to 0.92, and it was found that the degree of orientation of the magnetized zeolite was greater than that of the oriented zeolite described in JP 2020-158323 A.

[0127] [Manufacturing Example 23] Next, the zeolite oriented body of Production Example 23 was produced on a cylindrical YSZ substrate in the same manner as Production Example 14, except that a magnetic field of 0.9 T was applied to the dispersion liquid in a direction parallel to the YSZ substrate using a neodymium magnet.

[0128] [Reference production example 5] As a reference example, a zeolite shaped body of Reference Production Example 5 was produced on a cylindrical YSZ substrate in the same manner as in Production Example 14, except that no magnetic field was applied.

[0129] Next, the oriented zeolite body of Production Example 23 and the shaped zeolite body of Reference Production Example 5 were subjected to X-ray diffraction measurement using an X-ray diffraction (XRD) device (product name: Ultima IV, manufactured by Rigaku Corporation) under the same measurement conditions as above.

[0130] Fig. 10 is a chart showing the X-ray diffraction results for the magnetized zeolite (magnetized powder) of Production Example 4, the oriented zeolite of Production Example 14, the oriented zeolite of Production Example 23, and the zeolite molded body of Reference Production Example 5. The "○" in Fig. 10 indicates a diffraction peak confirmed in the X-ray diffraction measurement of the YSZ substrate.

[0131] The degree of orientation of the zeolite molded body of Reference Production Example 5 by the Lotgering method calculated from the above formula was 0.02, the degree of orientation of the oriented zeolite of Production Example 14 by the Lotgering method was 0.44, and the degree of orientation of the oriented zeolite of Production Example 23 by the Lotgering method was 0.40. From these results, it can be seen that (1) by applying a magnetic field of 0.9 T perpendicular to the substrate, Ho 3+ The magnetic zeolite containing the introduced Ho was c-axially oriented. (2) By applying a 0.9 T magnetic field horizontally to the substrate, the Ho 3+ It was confirmed that the magnetic zeolite into which β was introduced was oriented in the ab plane.

[0132] Furthermore, from this result, (3) when a magnetic field of 0.9 T is applied perpendicular to the substrate, Dy 3+ , Tb 3+ , Nd 3+ , Pr3+ or Ce 3+ The magnetic zeolite into which Dy was introduced exhibited c-axis orientation. (4) When a magnetic field of 0.9 T was applied horizontally to the substrate, Dy 3+ , Tb 3+ , Nd 3+ , Pr 3+ or Ce 3+ It is presumed that the magnetic zeolite into which is introduced is oriented in the ab plane.

[0133] Similarly, (5) when a magnetic field of 0.9 T is applied perpendicular to the substrate, Er 3+ , Yb 3+ or Tm 3+ The magnetized zeolite into which Er is introduced is oriented in the ab plane. (6) When a magnetic field of 0.9 T is applied horizontally to the substrate, Er 3+ , Yb 3+ or Tm 3+ It is presumed that the magnetic zeolite into which is introduced will have a c-axis orientation. [Explanation of symbols]

[0134] A1 Oriented Zeolite A2 Oriented Zeolite A3 Oriented Zeolite A4 Oriented Zeolite A5 Oriented Zeolite A6 Oriented Zeolite MZ1 magnetic zeolite MZ2 magnetic zeolite MP1 Micropore MP2 Micropore MP3 Micro Hole S board B1 magnetic field B2 magnetic field

Claims

1. a magnetization step of immersing a raw material zeolite in an aqueous solution containing a magnetic ion element to perform ion exchange, thereby producing a magnetized zeolite in which the magnetic ion element is introduced into the crystal structure of the raw material zeolite; an orientation step in which a powder of the magnetized zeolite is dispersed in a solvent to form a dispersion, and the magnetized zeolite is deposited and aggregated while applying a magnetic field to the dispersion, and the solvent is removed, thereby producing an oriented zeolite body in which micropores of the magnetized zeolite are regularly arranged; A method for producing a zeolite oriented body, comprising an ion exchange process in which an aqueous solution containing a cationic element is brought into contact with the zeolite oriented body, thereby exchanging the cationic element with the magnetic ionic element contained in the magnetized zeolite that constitutes the zeolite oriented body.

2. 2. The method for producing an oriented zeolite body according to claim 1, wherein the magnetic ion element is one or more magnetic elements selected from the group consisting of transition metal elements and rare earth metal elements.

3. 2. The method for producing an oriented zeolite body according to claim 1, wherein the magnetic ion element is one or more elements selected from the group consisting of Ho, Dy, Tb, and Er.

4. The method for producing an oriented zeolite according to any one of claims 1 to 3, wherein the magnetic zeolite is selected from the group consisting of A-type zeolite having an ion exchange rate of 5% to 90%, L-type zeolite having an ion exchange rate of 5% to 40%, X-type zeolite having an ion exchange rate of 5% to 80%, and Y-type zeolite having an ion exchange rate of 5% to 70%.

5. The method for producing an oriented zeolite body according to any one of claims 1 to 4, wherein a magnetic field of 0.5 to 4 T is applied to the dispersion in the orientation step.

6. 2. The method for producing a zeolite oriented body according to claim 1, wherein the zeolite oriented body is composed of magnetized L-type zeolite, and the L-type zeolite constituting the zeolite oriented body after the ion exchange process has a magnetic ion residual rate of 4% or less.

7. The method for producing an oriented zeolite according to claim 6, wherein the L-type zeolite is c-axis oriented.

Images