Molded zeolite body

Abstract

The purpose of the present invention is to provide at least one of a zeolite-containing molded body and a potassium adsorption method using the molded body, said molded body being capable of suppressing aluminum elution and removing potassium from a dialysis waste liquid compared to conventional dialysis waste liquid treatment using zeolite.

Description

Technical Field

[0001] The present invention relates to a zeolite shaped body. Background Art

[0002] Artificial dialysis is a treatment that uses a dialysate to artificially remove metabolic waste from the blood. Metabolic waste, mainly potassium, is removed from the blood by bringing the blood into contact with the dialysate through a semipermeable membrane. The amount of dialysate used in each artificial dialysis is also large, and its frequency is also high. Therefore, after artificial dialysis, the dialysate is discharged and processed in large quantities as drainage (dialysis drainage). In recent years, from the perspective of improving QOL, home dialysis, where dialysis patients perform artificial dialysis in their homes, has been focused on, but the processing of dialysis drainage has hindered its popularization.

[0003] However, zeolite is also known as a potassium adsorbing material that is easily available compared to ion exchange resins, etc. Therefore, treatment of dialysis effluent using zeolite has been studied for the purpose of treatment and regeneration of dialysis effluent.

[0004] For example, Patent Document 1 reports that SiO 2 / Al 2 O 3 Different FAU-type zeolites treat the dialysis effluent, remove potassium from the dialysis effluent and regenerate it.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: U.S. Patent Application Publication No. 2015 / 0297815 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] However, there is a problem that, in the treatment of the dialysis effluent using the zeolite of Patent Document 1, aluminum is eluted while potassium is removed and mixed into the dialysis effluent.

[0010] An object of the present invention is to provide at least one of a molded body containing zeolite and a potassium adsorption method using the molded body, wherein the zeolite can suppress the dissolution of aluminum and remove potassium from the dialysis effluent as compared with conventional dialysis effluent treatment using zeolite.

[0011] Technical solutions for solving technical problems

[0012] Regarding zeolite for removing potassium from dialysis effluent, the present inventors focused on the structure of zeolite and the form of zeolite when used for the treatment of dialysis effluent. As a result, they found that a molded body containing zeolite having a specific structure and having a controlled pore state is less likely to cause aluminum to dissolve and exhibits excellent potassium adsorption characteristics.

[0013] That is, the present invention is as described in the claims, and the gist of the present invention is as follows.

[0014] [1] A molded body comprising: a zeolite having an oxygen 8-membered ring structure, and at least one of a silica binder and a zirconia binder, wherein the ratio of the cumulative pore volume with a pore diameter of 10 nm to 100 nm to the cumulative pore volume with a pore diameter of 5 nm to 300 nm is 25% by volume to 70% by volume, and the following (1) or (2) is satisfied.

[0015] (1) The average aspect ratio is 1.55 or less, and the particle size D50 is 200 μm or more and 600 μm or less.

[0016] (2) The average aspect ratio exceeds 1.55.

[0017] [2] The molded body according to [1], comprising: a zeolite having an oxygen octahedral ring structure, and at least one of a silica binder and a zirconia binder, wherein the ratio of the cumulative pore volume with a pore diameter of 10 nm to 100 nm to the cumulative pore volume with a pore diameter of 5 nm to 300 nm is 25% by volume to 70% by volume, and the average aspect ratio exceeds 1.55.

[0018] [3] The molded body according to [1], comprising: a zeolite having an oxygen octahedral ring structure, and at least one of a silica binder and a zirconia binder, wherein the ratio of the cumulative pore volume with a pore diameter of 10 nm to 100 nm to the cumulative pore volume with a pore diameter of 5 nm to 300 nm is 25% by volume to 70% by volume, the average aspect ratio is 1.55 or less, and the particle size D50 is 200 μm to 600 μm.

[0019] [4] The molded article according to any one of [1] to [3], wherein the cumulative pore area of ​​pores having a pore diameter of 5 nm or more and 300 nm or less is 10.0 m 2 / g or more and 35.0m 2 / g or less.

[0020] [5] The molded product according to any one of [1] to [4], wherein the cumulative pore volume of pores with a pore diameter of 5 nm to 300 nm is 0.35 mL / g to 0.70 mL / g.

[0021] [6] The molded body according to any one of [1] to [5], wherein the pore diameter accounting for 50% by volume of the cumulative pore volume of pore diameters of 5 nm to 300 nm is 75 nm to 160 nm.

[0022] [7] The molded body according to any one of [1] to [6], wherein the ratio of the cumulative pore volume with a pore diameter of 5 nm to 10 nm to the cumulative pore volume with a pore diameter of 5 nm to 300 nm is 0.1% by volume to 5.0% by volume.

[0023] [8] A molded body according to any one of [1] to [7], wherein the zeolite is a zeolite having a skeleton structure of one or more selected from the group consisting of a FER structure, a HEU structure, a YFI structure, a MAZ structure, a CHA structure, a MER structure and a MOR structure.

[0024] [9] The molded article according to any one of [1] to [8], wherein the molar ratio of silicon dioxide to aluminum oxide (SiO 2 / Al 2 O 3 ratio) is greater than 3 and less than 100.

[0025]

[10] A potassium adsorption method comprising the step of bringing the molded body according to any one of [1] to [9] into contact with a solution containing potassium ions.

[0026]

[11] A column comprising the molded body according to any one of [1] to [9].

[0027]

[12] A potassium adsorption system comprising the column described in

[11] .

[0028] Effects of the Invention

[0029] According to the present invention, at least one of a molded body containing zeolite and a potassium adsorption method using the molded body can be provided, wherein the molded body can suppress the elution of aluminum and remove potassium from the dialysate as compared with the conventional dialysate treatment using zeolite. DETAILED DESCRIPTION

[0030] Hereinafter, an example of an embodiment is shown for explanation of the present invention. It should be noted that the terms in the present embodiment are as follows. In addition, each structure and parameter disclosed in this specification can be set to any combination, and the upper and lower limits of the values ​​disclosed in this specification are also included in the present invention based on the range of any combination. Hereinafter, the main terms in the present invention are shown.

[0031] "Aluminosilicate" is a composite oxide having a network-like repeating structure containing aluminum (Al) and silicon (Si) via oxygen (O). Since aluminum and silicon have different charges, in order to compensate for the charges, for example, H + 、Na + Such a counter cation. Among aluminosilicates, a substance having a crystallinity XRD peak in its powder X-ray diffraction (hereinafter, also referred to as "XRD") pattern is called "crystalline aluminosilicate", and a substance having no crystallinity XRD peak is called "amorphous aluminosilicate".

[0032] "Zeolite" refers to a compound having an ordered structure formed by skeleton atoms (hereinafter also referred to as "T atoms") via oxygen (O), and the T atoms include at least one of metal atoms and / or semi-metal atoms. As metal atoms, one or more selected from the group consisting of aluminum (Al), titanium (Ti), iron (Fe), zinc (Zn), gallium (Ga) and tin (Sn) can be exemplified, preferably at least one of aluminum and iron, and more preferably aluminum. As semi-metal atoms, at least one selected from the group consisting of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb) and tellurium (Te) can be exemplified, preferably silicon.

[0033] “Zeolite-like substances” refer to compounds having an ordered structure of T atoms formed via oxygen, and the T atoms include at least atoms other than metals and semimetals (hereinafter referred to as “non-metal atoms”). Examples of non-metal atoms include phosphorus (P). Examples of zeolite-like substances include complex phosphorus compounds containing phosphorus (P) as T atoms, such as aluminophosphate (AlPO) and silicoaluminophosphate (SAPO).

[0034] The "ordered structure (hereinafter also referred to as "zeolite structure")" in zeolite and zeolite-like substances refers to a framework structure determined by the structure code (hereinafter also referred to as "structure code") specified by the Structure Commission of the International Zeolite Association. For example, the FER structure is a framework structure determined as the structure code "FER". Regarding the FER structure, the zeolite structure can be identified by comparing it with the XRD pattern (hereinafter also referred to as "reference pattern") recorded in the Zeolite Framework Types of the IZA's Structure Committee's homepage http: / / www.iza-struture.org / databases / . With respect to the zeolite structure, the framework structure, crystal structure or crystalline phase are used synonymously.

[0035] In the present embodiment, "FER-type zeolite" or the like "zeolite of type 2 to 3" means a zeolite having a zeolite structure of the structure code, and preferably means a crystalline aluminosilicate having a zeolite structure of the structure code.

[0036] The "oxygen eight-membered ring structure" refers to a ring structure containing eight T atoms, and is also called a small pore.

[0037] "Zeolite molded body" refers to a composition in which powdered zeolite maintains a certain shape, and is not only a composition containing only zeolite, but may also contain at least one of a binder and a molding aid in addition to zeolite. It should be noted that in the present invention, "molded body" and "zeolite molded body" can be used interchangeably.

[0038] Hereinafter, the molded product according to the present embodiment will be described.

[0039] The present embodiment is a molded body comprising a zeolite having an oxygen 8-membered ring structure and at least one of a silica binder and a zirconia binder, wherein the volume ratio of pores having a size of 10 to 100 nm is 25% by volume or more and 70% by volume or less, and the following (1) or (2) is satisfied.

[0040] (1) The average aspect ratio is 1.55 or less, and the particle size D50 is 200 μm or more and 600 μm or less.

[0041] (2) The average aspect ratio exceeds 1.55.

[0042] The molded body of the present embodiment is a molded body having zeolite as a main component, a so-called zeolite molded body, and particularly comprises a zeolite having an oxygen eight-membered ring structure (hereinafter also referred to as "eight-membered ring zeolite"), and at least one of a silica binder and a zirconium oxide binder (hereinafter also referred to as "inorganic binder").

[0043] The zeolite contained in the molded body of the present embodiment has an oxygen eight-membered ring structure. By having an oxygen eight-membered ring structure, potassium can easily enter the pores inside the molded body of the present embodiment during the treatment of dialysis drainage, and the potassium adsorbed on the zeolite is not easy to be separated from the zeolite. The eight-membered ring zeolite can be selected from ABW structure, ACO structure, AEI structure, AEN structure, AFN structure, AFT structure, AFX structure, ANA structure, APC structure, APD structure, ATN structure, ATT structure, ATV structure, AWO structure, AWW structure, BCT structure, BIK structure, BRE structure, CAS structure, CDO structure, CHA structure, DDR structure, DFT structure, EAB structure, EDI structure, EPI structure, ERI structure, ESV structure, FER structure, GIS structure, GME structure, GOO structure, HEU structure, IHW structure, IT structure. A zeolite with one or more framework structures selected from the group consisting of E structure, ITW structure, JBW structure, KFI structure, LEV structure, LTA structure, LTL structure, MAZ structure, MER structure, MON structure, MOR structure, MTF structure, NSI structure, OFF structure, OWE structure, PAU structure, PHI structure, RHO structure, RTE structure, RTH structure, RWR structure, SAS structure, SAT structure, SAV structure, SIV structure, SZR structure, THO structure, TSC structure, UEI structure, UFI structure, VNI structure, YFI structure, YUG structure and ZON structure. The selectivity for potassium is improved by the configuration of the oxygen atoms contained in the oxygen eight-membered ring structure, so the eight-membered ring zeolite is preferably a zeolite having one or more skeleton structures selected from the group consisting of FER structure, HEU structure, YFI structure, MAZ structure, CHA structure and MOR structure, more preferably a zeolite having one or more skeleton structures selected from the group consisting of FER structure, HEU structure, YFI structure, MAZ structure, CHA structure and MOR structure, further preferably a zeolite having one or more skeleton structures selected from the group consisting of FER structure, HEU structure, YFI structure and MOR structure, further preferably a zeolite having FER structure, HEU structure, YFI structure or MOR structure. As particularly preferred eight-membered ring zeolites, zeolites having FER structure, MER structure or MOR structure can be cited, and zeolites having FER structure (FER type zeolite) can further be cited.

[0044] The molar ratio of silicon dioxide to aluminum oxide (SiO 2 / Al 2 O 3 The ratio is 3 or more, 7 or more, 10 or more, 13 or more, or 15 or more, and preferably 100 or less, 80 or less, 50 or less, or 35 or less. 2 / Al2 O 3 Compared with dialysis, the potassium adsorption performance from the dialysis effluent is likely to be higher. 2 / Al 2 O 3 The upper limit and lower limit of the ratio may be any combination of the above, and may be, for example, 3 or more and 100 or less, 7 or more and 80 or less, or 15 or more and 35 or less.

[0045] From the viewpoint of easily improving the potassium adsorption performance from the dialysis effluent, the cation type of the eight-membered ring zeolite is preferably at least one of cation type: Na (sodium) and cation type: H (proton), and more preferably cation type: Na.

[0046] The primary particle size of the eight-membered ring zeolite is preferably 0.1 μm or more and 15 μm or less.

[0047] The particle size D50 of the eight-membered ring zeolite is preferably 1 μm or more and 100 μm or less.

[0048] The molded body of the present embodiment includes an inorganic binder, preferably a silica binder. By including a silica binder as an inorganic binder, aluminum dissolution when dialysis drainage and the like come into contact with a solution is easily reduced. In addition, by condensing the eight-membered ring zeolite with the silica contained in the silica binder, the strength of the molded body is easily improved. On the other hand, the molded body of the present embodiment may include a zirconia binder as an inorganic binder. By condensing the zeolite with the zirconium oxide contained in the zirconia binder, the strength of the molded body is easily improved.

[0049] The silica binder is a compound mainly containing silicon (Si) and oxygen (O), preferably containing silicon dioxide (SiO 2 ) compound, more preferably silicon dioxide.

[0050] The zirconia binder is a compound mainly containing zirconium (Zr) and oxygen (O), preferably containing zirconium oxide (ZrO 2 ) compound, more preferably zirconium oxide.

[0051] The inorganic binder contained in the molded body of the present embodiment may contain either a silica binder or a zirconia binder alone, or may contain both.

[0052] The primary particle size of the inorganic binder is preferably 10 nm (0.010 μm) or more and 150 nm (0.150 μm) or less. From the viewpoint of promoting coagulation with zeolite, the primary particle size of the inorganic binder is more preferably 10 nm (0.010 μm) or more and 20 nm (0.020 μm) or less. On the other hand, from the viewpoint of preventing dissolution into the dialysis effluent, the primary particle size of the inorganic binder is more preferably 70 nm (0.070 μm) or more and 120 nm (0.120 μm) or less.

[0053] The particle size D50 of the silica binder is preferably 15 μm or more and 40 μm or less. The particle size D50 of the zirconium oxide binder is preferably 0.05 μm or more and 40 μm or less.

[0054] The particle size of the 8-membered ring zeolite and the particle size D50 of the inorganic binder are particle sizes corresponding to D50 (median diameter) of volume particle size distribution obtained by laser diffraction scattering method using a conventional particle size distribution measuring device (eg, device name: MT-3100II, manufactured by Microtrac BEL).

[0055] The molded body of this embodiment can easily improve the potassium adsorption characteristics while maintaining the strength of the molded body. Therefore, the mass of the inorganic binder is preferably 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more relative to 100 parts by mass (anhydrous conversion mass) of the eight-membered ring zeolite, and is preferably 40 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less. For example, if the inorganic binder is 10 parts by mass or more and 40 parts by mass or less, 15 parts by mass or more and 30 parts by mass or less, or 20 parts by mass or more and 25 parts by mass or less relative to 100 parts by mass (anhydrous conversion mass) of the eight-membered ring zeolite, the aluminum elution amount is more likely to decrease.

[0056] The anhydrous mass of the 8-membered ring zeolite and the inorganic binder is the mass after heat treatment at 600°C for 1 hour in air. The anhydrous mass of the molding aid is the mass after heat treatment at 80°C for 1 hour in air.

[0057] Preferably, the molded body of the present embodiment comprises: a zeolite having an oxygen 8-membered ring structure, and at least one of a silica binder and a zirconia binder, wherein the ratio of the cumulative pore volume of pore diameters of 10 nm to 100 nm to the cumulative pore volume of pore diameters of 5 nm to 300 nm is 25% by volume to 70% by volume, and the average aspect ratio exceeds 1.55. By satisfying such an average aspect ratio, a molded body showing high potassium adsorption performance is obtained regardless of the particle diameter D50.

[0058] From the viewpoint of increasing the contact area with the dialysate by increasing the external surface area of ​​the molded body, the average aspect ratio is preferably greater than 1.55, more preferably greater than 1.55 and less than 2.70, further preferably greater than 1.60 and less than 2.60, and even more preferably greater than 1.80 and less than 2.55.

[0059] In the present embodiment, the "aspect ratio" of the molded body is a value represented by the ratio of the major diameter of the molded body to the minor diameter, and the "average aspect ratio" is the average value of the aspect ratio. Regarding the major diameter and minor diameter of the molded body, in the scanning electron microscope (hereinafter also referred to as "SEM") observation, the long side of the side of the rectangle circumscribed with the molded body image is set as the major diameter [μm], and the short side of the side is set as the minor diameter [μm], and the above molded body image is obtained when the independently observed molded body is projected onto the same plane. Therefore, the "aspect ratio" is greater than 1.00. SEM observation is performed using a conventional scanning electron microscope (for example, device name: JSM-IT200, manufactured by JEOL Ltd.) under the following conditions.

[0060] Accelerating voltage: 6kV

[0061] Magnification: 30±10 times

[0062] The average aspect ratio of the molded article of the present embodiment can be calculated by arithmetic averaging the aspect ratios of 50±5 molded articles observed by the above method.

[0063] The average minor diameter of the molded body of the present embodiment is preferably 150 μm or more and 700 μm or less, more preferably 200 μm or more and 650 μm or less, and further preferably 400 μm or more and 650 μm or less. The "average minor diameter" of the molded body refers to the average value of the minor diameter of the molded body, and the minor diameters of 50±5 molded bodies observed in the same manner as above can be calculated by arithmetic average through SEM observation.

[0064] The molded body of this embodiment may include: a zeolite having an oxygen octahedral ring structure, and at least any one of a silica binder and a zirconium oxide binder, wherein the ratio of the cumulative pore volume with a pore diameter of greater than 10 nm and less than 100 nm to the cumulative pore volume with a pore diameter of greater than 5 nm and less than 300 nm is greater than 25 volume % and less than 70 volume %, the average aspect ratio is less than 1.55, and the particle size D50 is greater than 200 μm and less than 600 μm.

[0065] When the average aspect ratio is 1.55 or less, the value of the particle size D50 contributes more to the potassium adsorption performance. By having such an average aspect ratio and particle size D50, the potassium adsorption performance tends to be higher. From the viewpoint of easily increasing the packing density of the molded body, the average aspect ratio is preferably greater than 1.00 and less than 1.55, and more preferably greater than 1.30 and less than 1.50.

[0066] When the average aspect ratio of the molded body of the present embodiment is less than 1.55, its particle size D50 is greater than 200μm and less than 600μm. If the particle size D50 of the molded body is less than 200μm, the flow rate of the dialysis drainage and the like slows down. On the other hand, if the particle size D50 exceeds 600μm, the molded body itself becomes too large. As a result, it is difficult for the dialysis drainage to penetrate into the interior of the molded body, and the efficiency of removing potassium from the dialysis drainage becomes too low. The particle size D50 of the molded body of the present embodiment is greater than 250μm, greater than 300μm, or greater than 350μm, and is preferably less than 550μm, less than 500μm, or less than 450μm. The upper and lower limits of the particle size D50 may be any combination of the above. For example, if it is 250 μm to 550 μm, 300 μm to 500 μm, or 350 μm to 450 μm, the potassium adsorption characteristics will not be reduced and the aluminum elution amount can be easily suppressed.

[0067] The particle size D50 of the molded product is a particle size corresponding to the D50 (median particle size) of the volume particle size distribution obtained by a laser diffraction scattering method using a conventional particle size distribution measuring device (for example, device name: MT-3100II, manufactured by Microtrac BEL). Specific measuring conditions include the following measuring conditions.

[0068] Pretreatment: Dry at 110°C for 1 hour in air atmosphere

[0069] Measuring range: 0.7 to 1000 μm

[0070] Permeability: Permeable

[0071] Shape: Non-spherical

[0072] Refractive index: 1.66

[0073] Atmosphere: Air (dry)

[0074] Solvent refractive index: 1

[0075] The ratio of the cumulative pore volume of the pore diameter of 10 nm or more and 100 nm or less of the molded body of the present embodiment to the cumulative pore volume of the pore diameter of 5 nm or more and 300 nm or less (hereinafter, also referred to as the "total pore volume") (hereinafter, also referred to as the "10-100 nm pore volume ratio") is 25% by volume or more and 70% by volume or less. When the pore volume ratio of 10-100 nm of the molded body is less than 25% by volume, the adsorption capacity of potassium is easily reduced. In addition, if it exceeds 70% by volume, other ions are easily adsorbed, and the selectivity of potassium is easily reduced. The pore volume ratio of 10-100 nm of the molded body of the present embodiment is preferably 30% by volume or more, 33% by volume or more, 43% by volume or more, or 53% by volume or more, and is preferably 69% by volume or less, 67% by volume or less, or 65% by volume or less. The upper and lower limits of the pore volume ratio of 10 to 100 nm can be any combination of the above, for example, it can be greater than 25 volume % and less than 70 volume %, greater than 30 volume % and less than 70 volume %, greater than 33 volume % and less than 69 volume %, greater than 43 volume % and less than 67 volume %, or greater than 53 volume % and less than 65 volume %.

[0076] The cumulative pore area (hereinafter also referred to as “total pore area”) of the pore diameter of the molded article of the present embodiment of 5 nm or more and 300 nm or less is preferably 10.0 m 2 / g or more, 20.0m 2 / g or above or 25.0m 2 / g or more, and preferably 35.0 m 2 / g or below or 32.0m 2 The upper and lower limits of the total pore area can be any combination of the above, for example, 10.0 m 2 / g or more and 35.0m 2 / g or less, 20.0m 2 / g or more and 35.0m 2 / g or less, or 25.0m 2 / g or more and 32.0m 2 / g or less.

[0077] The total pore volume of the molded body of the present embodiment is preferably 0.35 mL / g or more, 0.36 mL / g or more, or 0.38 mL / g or more, and preferably 0.70 mL / g or less, 0.60 mL / g or less, 0.50 mL / g or less, 0.48 mL / g or less, or 0.45 mL / g or less. The upper limit and lower limit of the total pore volume may be any combination of the above, for example, 0.35 mL / g or more and 0.70 mL / g or less, 0.35 mL / g or more and 0.60 mL / g or less, 0.35 mL / g or more and 0.50 mL / g or less, 0.36 mL / g or more and 0.60 mL / g or less, 0.36 mL / g or more and 0.50 mL / g or less, 0.36 mL / g or more and 0.48 mL / g or less, or 0.38 mL / g or more and 0.45 mL / g or less.

[0078] The combination of the total pore area and the total pore volume, as well as the upper and lower limits of each, may be any combination of the above. For example, the total pore area may be 10.0 m 2 / g or more and 35.0m 2 / g or less, 20.0m 2 / g or more and 32.0m 2 / g or less, or 25.0m 2 / g or more and 32.0m 2 In addition, the upper limit and lower limit of the total pore volume may be any combination of the above, for example, 0.35 mL / g to 0.50 mL / g, 0.36 mL / g to 0.48 mL / g, or 0.38 mL / g to 0.45 mL / g.

[0079] By setting the total pore area or total pore volume as described above, the dialysate can easily penetrate into the molded body, and as a result, the potassium adsorption performance can be easily improved.

[0080] The pore diameter (hereinafter also referred to as "pore diameter D50") at which the cumulative pore volume of the molded body of the present embodiment is 50% relative to the total pore volume is preferably 75 nm or more and 160 nm or less. The pore diameter D50 is more preferably 76 nm or more, 80 nm or more, or 100 nm or more, and more preferably 155 nm or less, 120 nm or less, 118 nm or less, 116 nm or less, or 114 nm or less. The upper limit and lower limit of the pore diameter D50 may be any combination of the above, and the pore diameter D50 may be, for example, 76 nm or more and 160 nm or less, 80 nm or more and 160 nm or less, 100 nm or more and 155 nm or less, 75 nm or more and 155 nm or less, 75 nm or more and 120 nm or less, 76 nm or more and 118 nm or less, 80 nm or more and 116 nm or less, or 100 nm or more and 114 nm or less.

[0081] By setting the pore diameter D50 to be within the above range, the potassium adsorption performance is likely to be further improved.

[0082] The ratio of the cumulative pore volume of the pore diameter of the molded body of this embodiment of the present invention of 5 nm or more and 10 nm or less to the total pore volume (hereinafter, also referred to as "5-10 nm pore volume ratio") is preferably 0.1 volume % or more and 5.0 volume % or less. The 5-10 nm pore volume ratio is selected to be 1.5 volume % or more, 2.2 volume % or more, or 3.1 volume % or more, and preferably 4.9 volume % or less, 4.1 volume % or less, or 3.7 volume % or less. By making the 5-10 nm pore volume ratio the above ratio, the adsorption of potassium tends to become faster. The upper limit and lower limit of the 5-10 nm pore volume ratio can be any combination of the above, for example, 1.5 volume % or more and 4.9 volume % or less, 2.2 volume % or more and 4.1 volume % or less, or 3.1 volume % or more and 3.7 volume % or less.

[0083] The pore area, pore volume and pore diameter of the molded body can be measured by mercury porosimetry in accordance with JIS Z 1655. Specific measurement conditions include the following.

[0084] Sample mass: 0.10g

[0085] Mercury inlet pressure: 601.6psia~36098.1psia(4.1MPa~248.9MPa)

[0086] Measuring pore diameter: 5nm~300nm

[0087] Use cuvette: Press into 1.1cc glass cuvette

[0088] Mercury surface tension: 480 dyn

[0089] Mercury contact angle: 130°

[0090] Pretreatment conditions: Degassing treatment at 110°C for 1 hour or more (1 hour or more and 3 hours or less) in air atmosphere

[0091] A conventional mercury porosimeter (for example, device name: AutoPore 9510, manufactured by Micromeritics) can be used for the measurement.

[0092] The bulk density of the molded article of this embodiment is preferably 0.1 g / cm 3 Above and 0.65g / cm 3 If the bulk density is 0.1 g / cm 3 On the other hand, if the bulk density is 0.65 g / cm 3 The bulk density of the molded article of this embodiment is preferably 0.1 g / cm 3 Above, 0.2g / cm 3 Above or 0.3g / cm 3 More than 0.65 g / cm 3 Below, 0.60g / cm 3 Below or 0.58g / cm 3 The upper and lower limits of the bulk density can be any combination of the above, for example, 0.1 g / cm 3 Above and 0.65g / cm 3 Below, 0.2g / cm 3 Above and 0.60g / cm 3 Below, or 0.3g / cm 3 Above 0.58g / cm 3 the following.

[0093] The molded body of the present embodiment can be made into a desired shape suitable for the purpose. As the shape of the molded body of the present embodiment, one or more selected from the group consisting of cylindrical, granular, beaded, roughly spherical and annular shapes can be cited, and at least one of cylindrical and beaded shapes can be further cited. In addition, it can be any shape corresponding to the purpose.

[0094] The molded article of this embodiment is suitable for removing potassium from the dialysate. For example, the molded article of this embodiment is used in the following potassium adsorption evaluation of simulated dialysate (hereinafter also referred to as "simulated adsorption evaluation") using potassium (K + ) The removal rate is preferably 20% or more, 30% or more, or 40% or more, and is preferably 100% or less, 99% or less, or 98% or less,

[0095] The simulated adsorption evaluation can be performed as follows. That is, a solution containing KCl, NaCl, MgCl 2 and CaCl 2 An aqueous solution containing the following composition was used as a simulated dialysate.

[0096] K: 1.0mEq / L

[0097] Na: 132.0 mEq / L

[0098] Mg: 0.5 mEq / L

[0099] Ca: 3.5 mEq / L

[0100] Next, 2.5 mL of the molded body of the present embodiment is filled into a glass column with an inner diameter of 8.4 mmφ, and the simulated dialysate is circulated in the glass column at a liquid delivery rate of 100 mL / min. A total of 500 mL of the simulated dialysate discharged from the glass column is recovered for every 100 mL from the start of discharge, and each is diluted 10 times with pure water to prepare a measurement solution. After the concentrations of potassium, calcium, and magnesium in the obtained measurement solution are measured by ICP emission spectrometry using a conventional ICP-AES device (e.g., OPTIMA3000DV, manufactured by PERKIN-ELMER), the potassium removal rate can be calculated by the following formulas (1) and (2).

[0101] Potassium removal rate [%] = (A1 + A2 + A3 + A4 + A5) / 5 × 100 (1)

[0102] (1) In the formula, A1 to A5 are the potassium removal rates [%] of the respective test solutions.

[0103] Potassium removal rate of each test solution [%] = (C0-Cn) / C0×100 (2)

[0104] (2) where C0 is the potassium concentration of the simulated dialysate [1.0 mEq / L], and Cn is the potassium concentration in each assay solution [mEq / L].

[0105] Before the simulated adsorption evaluation, the molded body of the present embodiment may be pretreated by mixing with 1 L of a sodium chloride aqueous solution having a NaCl concentration of 10 mass % and then washing with 1.5 L of pure water.

[0106] In the simulated adsorption evaluation, the magnesium removal rate and calcium removal rate are preferably lower than the potassium removal rate. For example, magnesium (Mg 2 + ) removal rate is 15% or less, 10% or less, or 6% or less. On the other hand, calcium (Ca 2+) The removal rate can also be 15% or less, 10% or less, or 6% or less.

[0107] The lower limits of the magnesium removal rate and the calcium removal rate can be exemplified by 0% or more, 0.5% or more, or 1.0% or more, respectively.

[0108] The calcium removal rate or the magnesium removal rate can be obtained by replacing potassium with calcium or magnesium in the above formula (1) and formula (2).

[0109] The molded body of this embodiment has little aluminum elution when in contact with a solution such as dialysis effluent. For example, the aluminum elution amount of the molded body of this embodiment in the following aluminum elution evaluation can be 0.01 mass ppm or more and 0.50 mass ppm or less, 0.01 mass ppm or more and 0.20 mass ppm or less, or 0.01 mass ppm or more and 0.15 mass ppm or less.

[0110] Regarding the evaluation of aluminum dissolution, 1 mL of the molded body of the present embodiment was mixed in 10 mL of pure water and then shaken for 6 hours at 37°C and 1.0±0.5 Hz. After shaking, the supernatant was filtered using a membrane filter to prepare a test solution. The aluminum content of the test solution was measured by ICP emission spectrometry using ICP-AES (product name: OPTIMA3000DV, manufactured by PERKIN-ELMER) as the aluminum dissolution amount.

[0111] Before the evaluation of aluminum dissolution, the measurement sample may be pretreated by mixing it with 1 L of a sodium chloride aqueous solution having a NaCl concentration of 10 mass % and then washing it with 1.5 L of pure water.

[0112] The amount of aluminum elution in the aluminum elution evaluation is preferably small, and may be, for example, 0 mass ppm or more or 0.01 mass ppm or more.

[0113] The molded article of this embodiment is suitable for removing potassium from dialysis effluent, but can also be used in a potassium adsorption method having a step of contacting with a solution containing potassium ions.

[0114] Furthermore, the molded article of the present embodiment can be used as an adsorbent for selectively removing potassium from a solution containing at least two of alkali metal ions and alkaline earth metal ions. The molded article of the present embodiment can be used as a potassium adsorbent, an adsorbent for removing potassium from a solution containing at least one of sodium and magnesium and potassium, and an adsorbent for removing potassium from at least one of biological fluids, blood products, blood, and dialysate.

[0115] The molded article of the present embodiment is packed in a column, and the column including the molded article of the present embodiment can be used in a potassium adsorption method, and further can be used as a potassium adsorption system including the column.

[0116] Next, a method for producing the molded product according to the present embodiment will be described.

[0117] The method for producing the molded body of the present embodiment may be any method as long as the molded body contains an eight-membered ring zeolite and an inorganic binder source and has the above-mentioned structure.

[0118] As a preferred production method, for example, there can be mentioned a production method comprising a mixing step of mixing an eight-membered ring zeolite and an inorganic binder source to obtain a mixture, and a molding step of molding the mixture to obtain a molded body.

[0119] In the mixing step, the eight-membered ring zeolite and the inorganic binder source may be mixed uniformly by any method. Examples of the mixing method include mixing using one or more selected from the group consisting of a ribbon mixer, a kneader, a Nauta mixer, and a Mix-Muller.

[0120] The primary particle size and particle size D50 of the eight-membered ring zeolite and inorganic binder source used in the mixing step and the primary particle size and particle size D50 of the eight-membered ring zeolite and inorganic binder contained in the molded body of the present embodiment are not particularly limited as long as the above-mentioned molded body can be obtained.

[0121] In the mixing step, the eight-membered ring zeolite and the inorganic binder are preferably mixed so that the mass of the inorganic binder is 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, and is 40 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less, relative to 100 parts by mass (anhydrous equivalent mass) of the eight-membered ring zeolite.

[0122] Examples of the inorganic binder source include compounds containing silicon (Si) and oxygen (O) by firing, preferably silicon dioxide (SiO 2 ), more preferably a compound that becomes silicon dioxide, or a compound containing zirconium (Zr) and oxygen (O), preferably a compound containing zirconium oxide (ZrO 2), more preferably a compound that becomes zirconium oxide and functions as an inorganic binder, preferably one or more selected from the group consisting of silica sol, colloidal silica, wet silica, dry silica, dry zirconium oxide, wet zirconium oxide, zirconium oxide sol, zirconium hydroxide, zirconium carbonate, ammonium zirconium carbonate, zirconium oxynitrate, zirconium oxychloride, zirconium oxysulfate, zirconium acetate and zirconium oxyacetate, more preferably one or more selected from the group consisting of colloidal silica, zirconium acetate, zirconium oxyacetate, wet zirconium oxide, zirconium oxide sol and zirconium hydroxide, and further preferably at least one of colloidal silica and zirconium oxide sol. As a specific colloidal silica, at least one of sodium ion stabilized colloidal silica and ammonium ion stabilized colloidal silica can be exemplified. In addition, the properties of the inorganic binder source can be exemplified by a solid, slurry, colloidal solution or aqueous solution containing the above-mentioned compound.

[0123] In the mixing process, a molding aid may be mixed as needed. A molding aid is a substance that improves moldability. By using a molding aid, it is easy to control the pore structure of the molded body. The molding aid can be exemplified by one or more selected from the group consisting of cellulose, alcohol, lignin, starch, and guar gum. For easy operation, the molding aid is preferably at least one of cellulose and alcohol. Cellulose can be exemplified by one or more selected from the group consisting of crystalline cellulose, hydroxypropyl methylcellulose, and sodium carboxymethyl cellulose (CMC). Alcohol can be exemplified by at least one of polyvinyl alcohol and ethylene glycol.

[0124] The amount of the molding aid is preferably 1 part by mass or more or 2 parts by mass or more, and is preferably 5 parts by mass or less or 4 parts by mass or less, based on 100 parts by mass (anhydrous equivalent) of zeolite.

[0125] In the molding step, the mixture obtained by the mixing step is molded into any shape. The molding method is any as long as it can form the desired shape. If it is a cylindrical molded body, molding using an extrusion method can be exemplified, and if it is a beaded molded body, molding using at least one of a tumbling granulation method and a stirring granulation method can be exemplified.

[0126] In the case of manufacturing a molded body having an average aspect ratio of more than 1.55, from the viewpoint of being easy to control the short diameter and the long diameter of the molded body, the molding process is preferably a molding method capable of molding into a cylindrical shape, and more preferably molding by extrusion. As for a specific method of molding by extrusion, a method of molding the mixture obtained by the above mixing process into a cylindrical shape having a diameter of more than 0.1 mm and less than 10.0 mm can be cited using a conventional extruder (for example, product name: MG-55-1, manufactured by Dalton). As the diameter of the mixture extruded decreases, the average aspect ratio tends to increase.

[0127] When manufacturing a molded body having an average aspect ratio of 1.55 or less, from the viewpoint of easily reducing the average aspect ratio, the molding step is preferably a molding method capable of molding into a substantially spherical or spherical shape, and more preferably a molding method using at least one of a tumbling granulation method and a stirring granulation method. As the stirring granulation method, there can be mentioned a method of forming a bead-shaped molded body from the mixture obtained by the above mixing step using a conventional stirring granulation device (for example, product name: FM mixer (FM5), manufactured by Nippon Coke Industries Co., Ltd.).

[0128] The method for manufacturing the molded body of the present embodiment may include a firing step of heat-treating the molded body as required. The firing step can improve the strength of the molded body. The firing conditions may be any conditions as long as at least a portion of the inorganic binder source is melted and fused with the eight-membered ring zeolite, and examples include firing at 500° C. to 900° C. for 2 hours to 4 hours. The firing atmosphere may be an oxidizing atmosphere, such as an air atmosphere.

[0129] Example

[0130] Hereinafter, the present invention will be described in further detail in Examples, but the present invention is not limited to these Examples.

[0131] <Simulated adsorption evaluation>

[0132] The potassium adsorption performance of the measurement sample was evaluated using simulated dialysate.

[0133] That is, as a potassium solution, a solution containing KCl, NaCl, MgCl 2 and CaCl 2 The simulated dialysate was prepared by an aqueous solution containing the following composition.

[0134] K: 1.0mEq / L

[0135] Na: 132.0 mEq / L

[0136] Mg: 0.5 mEq / L

[0137] Ca: 3.5 mEq / L

[0138] A glass column having an inner diameter of 8.4 mmφ was filled with 2.5 mL of the measurement sample, and a simulated dialysate was flowed through the glass column at a liquid feeding rate of 100 mL / min.

[0139] The simulated dialysate discharged from the glass column was collected in a total of 500 mL per 100 mL from the start of discharge, and each was diluted 10 times with pure water to prepare a measurement solution.

[0140] The potassium, calcium and magnesium concentrations of the obtained test solution were measured by ICP emission spectrometry using an ICP-AES device (product name: OPTIMA3000DV, manufactured by PERKIN-ELMER), and the potassium removal rate, calcium removal rate and magnesium removal rate were calculated from the above formulas (1) and (2), respectively.

[0141] Prior to the simulated adsorption evaluation, the measurement sample was mixed with 1 L of a sodium chloride aqueous solution having a NaCl concentration of 10 mass %, and then washed with 1.5 L of pure water to perform pretreatment.

[0142] <Aluminum Dissolution Evaluation>

[0143] The aluminum dissolution evaluation of the samples was measured by the following method.

[0144] That is, 1 mL of the test sample was mixed in 10 mL of pure water and then shaken for 6 hours at 37°C and 1.0±0.5 Hz. After shaking, the supernatant was filtered using a membrane filter to prepare a test solution. The aluminum content of the test solution was measured by ICP emission spectrometry using ICP-AES (product name: OPTIMA3000DV, manufactured by PERKIN-ELMER) as the aluminum elution amount.

[0145] Prior to the evaluation of aluminum dissolution, the measurement sample was mixed with 1 L of a sodium chloride aqueous solution having a NaCl concentration of 10 mass %, and then washed with 1.5 L of pure water to perform pretreatment.

[0146] <Measurement of pore diameter and pore volume>

[0147] The pore volume and pore diameter of the measurement sample were measured using a mercury intrusion instrument (device name: AutoPore 9510, manufactured by Micromeritics) by mercury intrusion porosimetry in accordance with JIS Z 1655. The porosity and pore diameter were measured under the following conditions.

[0148] Sample weight: 0.10g

[0149] Mercury inlet pressure: 601.6psia~36,098.1psia(4.1MPa~248.9MPa)

[0150] Measuring pore diameter: 5nm~300nm

[0151] Use cuvette: Press into 1.1cc glass cuvette

[0152] Mercury surface tension: 480 dyn

[0153] Mercury contact angle: 130°

[0154] Pretreatment conditions: Degassing treatment at 110°C for more than 1 hour in air atmosphere

[0155] <Measurement of Particle Size Distribution>

[0156] The particle size distribution of the sample was measured by laser diffraction scattering method. The measurement was performed using a conventional particle size distribution measuring device (device name: MT-3100II, manufactured by Microtrac BEL). The measurement conditions were as follows.

[0157] Pretreatment: Dry at 110°C for 1 hour in air atmosphere

[0158] Measuring range: 0.7 to 1000 μm

[0159] Permeability: Permeable

[0160] Shape: Non-spherical

[0161] Refractive index: 1.66

[0162] Atmosphere: Air (dry)

[0163] Solvent refractive index: 1

[0164] Example 1

[0165] FER type zeolite (product name: HSZ (registered trademark)-720KOA, manufactured by Tosoh Corporation, SiO 2 / Al 2 O 3 ratio: 18, particle size D50: 8.7 μm) 100 parts by mass (anhydrous equivalent mass: 300.0 g), sodium ion stabilized colloidal silica (product name: ST-30, manufactured by Nissan Chemical Co., Ltd., SiO 220 parts by mass (anhydrous equivalent mass: 60.0 g) of cellulose (product name: SUNROSE F-20LC, manufactured by Nippon Paper Industries) and 4 parts by mass (anhydrous equivalent mass: 12.0 g) of sodium carboxymethyl cellulose (product name: SUNROSE F-20LC, manufactured by Nippon Paper Industries) were stirred and mixed for 5 minutes using a stirring granulator (product name: FM mixer (FM5, manufactured by Nippon Coke Industries). 105.4 g of pure water was added to the mixture, and the mixture was further stirred for 5 minutes. Then, after drying overnight at 100° C. in an air atmosphere, the mixture was shaken using a Ro-Tap shaker (product name: IIDA SHAVE The pellets were classified by SHAKER (manufactured by Iida Seisakusho Co., Ltd.) at an impact rate of 165 rpm, a rotation speed of 290 rpm, and a treatment time of 5 minutes, and then passed through a sieve with a mesh size of 300 μm, and the molded bodies deposited on the sieve with a mesh size of 180 μm were recovered. The recovered molded bodies were calcined at 600°C for 2 hours in an air atmosphere to obtain bead-shaped molded bodies containing FER type zeolite (eight-membered ring zeolite) and silica (silica binder).

[0166] 500.0 g of a 10 mass % NaCl aqueous solution was passed through the bead-like molded body to perform ion exchange to obtain a cationic type: Na, thereby obtaining a molded body of this example.

[0167] Example 2

[0168] A molded body of this example was obtained by the same method as in Example 1 except that the molded body that passed through the sieve with an opening of 425 μm and accumulated on the sieve with an opening of 300 μm was recovered.

[0169] Example 3

[0170] The molded product of this example was obtained by the same method as in Example 1, except that the mixture was mixed for 60 minutes using a mixer (HIVIS MIX: manufactured by PRIMIX) and then molded into a 0.5 mm cylindrical shape using an extruder (product name: MG-55-1, manufactured by Dalton). After drying, the mixture was crushed using a granulator (product name: FXB-3, manufactured by Fuji Paudal) at a hammer speed of 15 Hz, and the molded product that passed through a sieve with a mesh size of 425 μm and accumulated on a sieve with a mesh size of 300 μm was recovered.

[0171] Example 4

[0172] Ammonium ion stabilized colloidal silica (product name: ST-N-30G, manufactured by Nissan Chemical Co., Ltd., SiO 2 A molded body of this example was obtained by the same method as in Example 1 except that the sodium ion-stabilized colloidal silica was replaced with 2-nitro-2-nitro-2-ol (converted Si concentration: 30 mass %, primary particle size: 12.5 nm±2.5 nm).

[0173] Example 5

[0174] Ammonium ion stabilized colloidal silica (product name: ST-N-30G, manufactured by Nissan Chemical Co., Ltd., SiO 2 The molded body of this example was obtained by the same method as in Example 1, except that the sodium ion-stabilized colloidal silica was replaced with the silica gel (converted Si concentration: 30 mass %, primary particle size: 12.5 nm±2.5 nm) and the molded body that passed through a sieve with a mesh of 425 μm and accumulated on a sieve with a mesh of 300 μm was recovered.

[0175] Example 6

[0176] As zeolite, FER type zeolite (product name: HSZ (registered trademark))-720NHA, manufactured by Tosoh Corporation, was used. 2 / Al 2 O 3 The zeolite was treated with an acid to obtain an H-type zeolite with a ratio of 18 and a particle size D50 of 10.9 μm, and ammonium ion-stabilized colloidal silica (product name: ST-N-30G, manufactured by Nissan Chemical Co., Ltd., SiO 2 A molded body of this example was obtained by the same method as in Example 1 except that the sodium ion-stabilized colloidal silica was replaced with 2-nitro-2-nitro-2-ol (converted Si concentration: 30 mass %, primary particle size: 12.5 nm±2.5 nm).

[0177] Example 7

[0178] A molded body of this example was obtained by the same method as in Example 6 except that the molded body that passed through the sieve with an opening of 425 μm and accumulated on the sieve with an opening of 300 μm was recovered.

[0179] Example 8

[0180] FER type zeolite (product name: HSZ (registered trademark)-720KOA, manufactured by Tosoh Corporation) was mixed with a mixer (HIVIS MIX: manufactured by PRIMIX). SiO 2 / Al 2 O 3 ratio: 18, particle size D50: 8.7 μm) 100 parts by mass (anhydrous equivalent mass: 300.0 g), zirconium oxide binder (product name: NanoUse ZR, manufactured by Nissan Chemical Co., Ltd., ZrO 220 parts by mass (anhydrous equivalent mass: 60.0 g) of cellulose (Zr concentration: 40% by mass, primary particle size: 90 nm) and 4 parts by mass (anhydrous equivalent mass: 12.0 g) of sodium carboxymethyl cellulose (product name: SUNROSE F-20LC, manufactured by Nippon Paper Industries) were mixed for 60 minutes. 252.5 g of pure water was added to the mixture, and after further stirring for 5 minutes, it was molded into a cylindrical shape with a diameter of 0.3 mm using an extruder (product name: MG-55-1, manufactured by Dalton), dried at 100° C. overnight in an air atmosphere, and pulverized at a hammer speed of 15 Hz using a granulator (product name: FXB-3, manufactured by Fuji Paudal) to obtain a molded body. The obtained molded body was classified using a Ro-Tap shaker (product name: IIDA SHAVE SHAKER, manufactured by Iida Manufacturing Co., Ltd.) under the conditions of impact number 165 rpm, rotation speed 290 rpm, and treatment time 5 minutes, and passed through a sieve with a mesh size of 710 μm, and the molded body accumulated on the sieve with a mesh size of 180 μm was recovered. The recovered molded body was calcined at 600°C for 2 hours in an air atmosphere to obtain a cylindrical molded body containing FER type zeolite (eight-membered ring zeolite) and zirconium oxide (zirconia binder).

[0181] 500.0 g of a 10 mass % NaCl aqueous solution was passed through the cylindrical molded body to perform ion exchange, thereby obtaining a cation type: Na, which was used as a molded body of this example.

[0182] Example 9

[0183] Sodium ion stabilized colloidal silica (product name: SH-3, manufactured by Fuso Chemical Industries, Ltd., SiO 2 The molded body of this example is obtained by the same method as in Example 8, except that 20 parts by mass (anhydrous converted mass: 60.0 g) of zirconia binder (converted Si concentration: 34.4% by mass, primary particle size: 35.6 nm) are added to the mixture in place of the zirconium oxide binder, 174.0 g of pure water is added to the mixture, and the recovered molded body is calcined at 800°C for 2 hours in an air atmosphere.

[0184] Example 10

[0185] Sodium ion stabilized colloidal silica (product name: SH-3, manufactured by Fuso Chemical Co., Ltd., SiO 2 The molded body of this embodiment is obtained by the same method as in Example 9, except that 10 parts by mass (anhydrous converted mass: 30.0 g) of 10 parts by mass of 1,000 nanometers (converted Si concentration: 34.4% by mass, primary particle size: 35.6 nm) are mixed, 230.1 g of pure water is added to the mixture, and it is molded into a cylindrical shape with a diameter of 0.5 mm using an extruder.

[0186] Embodiment 11

[0187] Sodium ion stabilized colloidal silica (product name: SH-3, manufactured by Fuso Chemical Co., Ltd., SiO 2 The molded body of this example was obtained by the same method as in Example 9, except that 15 parts by mass of granular materials (converted Si concentration: 34.4% by mass, primary particle size: 35.6 nm) (anhydrous converted mass: 45.0 g) were mixed and 63.6 g of pure water was added to the mixture.

[0188] Comparative Example 1

[0189] As zeolite, FAU type zeolite (product name: HSZ (registered trademark)-320NAA: manufactured by Tosoh Corporation, SiO 2 / Al 2 O 3 A molded body of this comparative example was obtained by the same method as in Example 1 except for the above-mentioned differences.

[0190] Comparative Example 2

[0191] A molded body of this comparative example was obtained by the same method as in Example 1 except that the molded body that passed through the sieve with an opening of 1.2 mm and accumulated on the sieve with an opening of 1.0 mm was recovered.

[0192] Comparative Example 3

[0193] A commercially available FER zeolite molded body (product name: HSZ (registered trademark)-720KOD1C, 1.5 mmφ cylindrical particles, binder: clay, SiO 2 / Al 2 O 3 The obtained product was ground into powder and passed through a sieve with a mesh size of 425 μm to obtain a cylindrical granular molded body deposited on a sieve with a mesh size of 300 μm.

[0194] 500.0 g of a 10 mass % NaCl aqueous solution was passed through the cylindrical pellet molded body to perform ion exchange, thereby obtaining a cation-type: Na molded body of this comparative example.

[0195] Comparative Example 4

[0196] MOR type zeolite (product name: HSZ (registered trademark)-620 HOA, manufactured by Tosoh Corporation) was mixed with a mixer (HIVIS MIX: manufactured by PRIMIX). SiO 2 / Al 2 O 3ratio: 18, particle size D50: 10.1 μm) 100 parts by mass, sodium ion stabilized colloidal silica (product name: SH-3, manufactured by Fuso Chemical Industries, Ltd., SiO 2 20 parts by mass (anhydrous equivalent mass: 60.0 g) of cellulose (product name: SUNROSE F-20LC, manufactured by Nippon Paper Industries) and 4 parts by mass (anhydrous equivalent mass: 12.0 g) of sodium carboxymethyl cellulose (product name: SUNROSE F-20LC, manufactured by Nippon Paper Industries) were mixed for 60 minutes. 95.1 g of pure water was added to the mixture, and after further stirring for 5 minutes, it was molded into a 1.0 mm cylindrical shape using an extruder (product name: MG-55-1, manufactured by Dalton), dried at 100° C. overnight in an air atmosphere, and pulverized at a hammer speed of 15 Hz using a granulator (product name: FXB-3, manufactured by Fuji Paudal) to obtain a molded body. The obtained molded body was classified using a Ro-Tap shaker (product name: IIDA SHAVE SHAKER, manufactured by Iida Manufacturing Co., Ltd.) under the conditions of impact number 165 rpm, rotation speed 290 rpm, and treatment time 5 minutes, and passed through a sieve with a mesh size of 1.2 mm, and the molded body accumulated on the sieve with a mesh size of 1.0 mm was recovered. The recovered molded body was calcined at 600° C. for 2 hours in an air atmosphere to obtain a cylindrical molded body containing MOR type zeolite (eight-membered ring zeolite) and silica (silica binder).

[0197] 500.0 g of a 10 mass % NaCl aqueous solution was passed through the cylindrical molded body to perform ion exchange, thereby obtaining a cation type: Na, which was used as a molded body of this example.

[0198] The evaluation results of Examples and Comparative Examples are shown in the following table.

[0199] [Table 1]

[0200]

[0201] [Table 2]

[0202]

[0203] Industrial Applicability

[0204] The molded article of the present invention has a pore size distribution and a particle size useful for adsorption and removal of potassium ions, and can therefore be usefully used for adsorbing potassium contained in a solution, preferably for adsorbing potassium from a discharge containing potassium ions generated by artificial dialysis.

[0205] The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2022-176351 filed on November 2, 2022, and the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2023-132534 filed on August 16, 2023 are cited here and introduced as a disclosure of the specification of the present invention.

Claims

1. A molded body, characterized in that Include: Zeolite having an oxygen eight-membered ring structure, and at least one of a silica binder and a zirconia binder, The ratio of the cumulative pore volume of the pores with a pore diameter of 10 nm to 100 nm to the cumulative pore volume of the pore diameter of 5 nm to 300 nm of the molded body is 25% by volume to 70% by volume, and the molded body satisfies the following (1) or (2): (1) The average aspect ratio is 1.55 or less, and the particle size D50 is 200 μm or more and 600 μm or less (2) The average aspect ratio exceeds 1.

55.

2. The molded article according to claim 1, wherein The molded body comprises: Zeolite having an oxygen eight-membered ring structure, and at least one of a silica binder and a zirconia binder, The ratio of the cumulative pore volume of pores with a pore diameter of 10 nm to 100 nm to the cumulative pore volume of pores with a pore diameter of 5 nm to 300 nm in the molded body is 25% to 70% by volume, and the average aspect ratio exceeds 1.

55.

3. The molded article according to claim 1, wherein The molded body comprises: Zeolite having an oxygen eight-membered ring structure, and at least one of a silica binder and a zirconia binder, The ratio of the cumulative pore volume of the pore diameter of the molded body being greater than 10 nm and less than 100 nm to the cumulative pore volume of the pore diameter being greater than 5 nm and less than 300 nm is greater than 25% by volume and less than 70% by volume, the average aspect ratio is less than 1.55, and the particle size D50 is greater than 200 μm and less than 600 μm.

4. The molded body according to any one of claims 1 to 3, wherein The cumulative pore area of ​​the molded body having a pore diameter of 5 nm or more and 300 nm or less is 10.0 m 2 / g or more and 35.0m 2 / g or less.

5. The molded body according to any one of claims 1 to 4, wherein The cumulative pore volume of the molded body having pore diameters of 5 nm to 300 nm is 0.35 mL / g to 0.70 mL / g.

6. The molded body according to any one of claims 1 to 5, wherein The molded body has a pore size of 75 nm to 160 nm, at which 50% by volume of the cumulative pore volume relative to the cumulative pore volume of pores having a pore size of 5 nm to 300 nm is present.

7. The molded body according to any one of claims 1 to 6, wherein The ratio of the cumulative pore volume of the molded body having pore diameters of 5 nm to 10 nm to the cumulative pore volume of the molded body having pore diameters of 5 nm to 300 nm is 0.1% by volume to 5.0% by volume.

8. The molded body according to any one of claims 1 to 7, wherein The zeolite is a zeolite having one or more framework structures selected from the group consisting of a FER structure, a HEU structure, a YFI structure, a MAZ structure, a CHA structure, and a MOR structure.

9. The molded body according to any one of claims 1 to 8, wherein The zeolite has a molar ratio of silicon dioxide to aluminum oxide (SiO 2 / Al 2 O 3 ratio) of 3 or more and 100 or less.

10. A potassium adsorption method, characterized in that: It has the following processes: The molded body according to any one of claims 1 to 9 is brought into contact with a solution containing potassium ions.

11. A column, characterized in that A shaped body comprising the shaped body according to any one of claims 1 to 9.

12. A potassium adsorption system, characterized in that: A column according to claim 11 is provided.

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