JP2017006837A - Adsorption element and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adsorption element excellent in filtration capacity and cleaning ability, in which an adsorbent is not departed from a support medium in use.SOLUTION: In an adsorption element 10 having a support medium 1, and an adsorbent 3 supported by the support medium 1, the adsorbent 3 comprises an adsorption body 3a and a finishing layer, the adsorption body 3a is positioned inside the adsorbent 3 and formed of adsorption fine powder and fine fibrous cellulose, the finishing layer encloses the adsorption body 3a, and the finishing layer is formed of the fine fibrous cellulose.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an adsorption element and a method for producing the same.

  Patent Document 1 discloses a conventional adsorption element. The adsorbing element has a support such as a non-woven sheet filled in the cartridge, and an adsorbent supported by the support. The adsorbent contains adsorbed fine powder such as ion exchange resin and fine fibrous cellulose, and can adsorb adsorbate such as foreign matter.

  Patent Document 1 also discloses a method for manufacturing this adsorption element. This manufacturing method includes a preparation process, a coarse material forming process, and a completion process. In the preparation step, an adsorbent dispersion system is prepared in which the dispersion medium is water and the dispersoids are adsorbed fine powder and fine fibrous cellulose. In the coarse material forming step, the adsorbent dispersion is brought into contact with the support to obtain the coarse material. In the completion process, the coarse material is dried to obtain an adsorbing element in which the adsorbent is supported on the support.

  The adsorbing element manufactured in this way is used for filtering contaminated water and the like, so that the adsorbate contained in the contaminated water and the like can be adsorbed on the adsorbent, and the contaminated water and the like can be purified. For example, if this adsorption element is used for storage water for growing aquatic organisms such as appreciation fish and edible fish, or filtration of conveyance water for conveying aquatic organisms alive, It is possible to purify the storage water by adsorbing adsorbate such as nitric acid and filth on the adsorbent. In this case, the life of aquatic organisms can be extended. It is also possible to ensure the transparency of water by decolorizing contaminated water. Furthermore, this adsorption element is used for filtering contaminated water contaminated with radioactive substances such as radioactive cesium, so that the adsorbent adsorbs radioactive substances as adsorbate and decontaminates the contaminated water. Is possible. Moreover, this adsorption element can adsorb | suck the bad smell component as adsorbate in pollutant gas, such as air which gives off a bad smell, to an adsorbent, and can deodorize pollutant gas.

Japanese Patent No. 4232131

  However, in the conventional adsorption element, part of the adsorbent may be detached from the support during use. If this happens during the filtration of contaminated water or the purification of contaminated gas, the adsorbate will be contained in the purified water or purified gas after filtration together with part of the adsorbent, and the filtration capacity and purification capacity will be reduced. Damaged.

  This invention is made | formed in view of the said conventional situation, Comprising: It is set as the problem which should be solved to provide the adsorption | suction element which was more excellent in filtration capability and purification | cleaning capability.

The adsorbing element of the present invention is an adsorbing element having a support and an adsorbent supported by the support and capable of adsorbing adsorbate containing adsorbed fine powder and fine fibrous cellulose,
The adsorbent is located inside, an adsorption main body formed with the adsorbed fine powder and the microfibrous cellulose,
It is characterized by comprising a finishing layer surrounding the adsorption main body and made of the microfibrous cellulose.

  In the adsorbing element of the present invention, an adsorbing main body formed by having adsorbing fine powder and microfibrous cellulose is surrounded by a finishing layer made of microfibrous cellulose. For this reason, it is difficult for a part of the adsorption main body, which is a conventional adsorbent, to be detached from the support during use. Further, the finishing layer surrounding the adsorption main body is made of microfibrous cellulose, and exhibits a certain degree of adsorption capability by itself and hardly impairs the adsorption capability of the internal adsorption main body.

  Therefore, the adsorption element of the present invention can exhibit higher filtering ability and purification ability.

  As the support, a nonwoven fabric sheet, a filter cartridge, a sponge filter having open cells, a porous ceramic having open cells, or the like can be used. When using an adsorbing element to filter contaminated water or purify contaminated gas, it is preferable to employ a nonwoven fabric sheet in which fibers are intertwined or a sponge filter having open cells as a support. . Contaminated water is impregnated in the flow path formed by continuous bubbles such as non-woven fabric sheets and sponge filters, etc., or contaminated gas penetrates, and more adsorbate such as contaminated water and foreign matter contained in the contaminated gas It is because it can adsorb suitably. Moreover, it is preferable that a support body is what is filled into the cartridge which can be attached or detached to filtration systems, such as a cartridge shell. This is because the support can be easily replaced.

  As the adsorbed fine powder, at least one of zeolite, silicotitanate, insoluble ferrocyanide, crystalline tetratitanic acid, titanosilicate, Prussian blue, diatomaceous earth, activated carbon, cation exchange resin, anion exchange resin, etc. is employed. be able to. These and their ratio are appropriately selected depending on the adsorbate to be adsorbed.

  As the microfibrous cellulose, “Cerish” (registered trademark) manufactured by Daicel Finechem Co., Ltd., “cellulose nanofiber” manufactured by Nippon Paper Industries Co., Ltd., and the like can be used. The fine fibrous cellulose can be pulverized while mixing to form a stable emulsion over a long period of time. For this reason, when forming the adsorption main body with the adsorbed fine powder, the fine fibrous cellulose exhibits a function of suitably holding the adsorbed fine powder on the support. Further, when the fine fibrous cellulose constitutes a finishing layer, it exhibits a function of preventing the adsorption fine powder of the adsorption main body from being detached from the support.

  The ratio between the adsorbed fine powder and the fine fibrous cellulose in the adsorbing body is appropriately selected depending on the use environment of the adsorbing element. The greater the content of microfibrous cellulose, the harder the adsorbed fine powder is detached. However, when the ratio of the microfibrous cellulose in the adsorption main body becomes high, the ratio of the adsorption fine powder in the adsorption main body becomes relatively low, and it becomes difficult to sufficiently exhibit the adsorption capacity of the adsorbate by the adsorption fine powder. The thickness of the finishing layer is also appropriately selected depending on the use environment of the adsorption element. The thicker the finishing layer, the harder the adsorbed fine powder is detached.

The method for producing an adsorbing element of the present invention is a method for producing an adsorbing element comprising a support and an adsorbent supported by the support and capable of adsorbing adsorbate including adsorbed fine powder and fine fibrous cellulose. ,
A first preparation step of preparing a dispersion system for an adsorption main body, in which a dispersion medium is water and a dispersoid is the adsorption fine powder and the fine fibrous cellulose;
A second preparation step of preparing a dispersion for a finishing layer, in which the dispersion medium is water and the dispersoid is the fine fibrous cellulose;
A first coarse material forming step of obtaining a first coarse material by bringing the support body dispersion system into contact with the support body;
A second coarse material forming step of drying the first coarse material and obtaining a second coarse material having an adsorption main body formed on the support;
A third coarse material forming step of obtaining a third coarse material by bringing the finishing layer dispersion into contact with the adsorption main body;
And a completion step of obtaining the adsorbing element in which the adsorbent is formed by drying the third coarse material and surrounding the adsorbing body with a finishing layer.

  According to the manufacturing method of the present invention, the adsorption element of the present invention can be manufactured.

  In the first preparation step, a mixture containing water as a dispersion medium, adsorbed fine powder and fine fibrous cellulose as a dispersoid is pulverized while mixing with a mill or the like to obtain a dispersion for an adsorbent body that is an emulsion. Is preferred. In the second preparation step, it is preferable that a mixture containing water as a dispersion medium and fine fibrous cellulose as a dispersoid is pulverized while being mixed by a mill or the like to obtain a dispersion for a finishing layer that has become an emulsion. In any mixture, various dispersants may be added so that the dispersoid is suitably dispersed in the dispersion medium.

  Adsorption fine powder is at least one of zeolite, silicotitanate, insoluble ferrocyanide, crystalline tetratitanate, titanosilicate, Prussian blue, diatomaceous earth, activated carbon, cation exchange resin and other positively charged adsorption with positive charge It is preferably composed of fine powder and negative charge adsorbing fine powder having a negative charge which is an anion exchange resin. The first preparation step includes a first positive charge preparation step for obtaining a positive charge adsorption main dispersion containing positive charge adsorption fine powder, and a first negative charge preparation step for obtaining a negative charge adsorption main body dispersion containing negative charge adsorption fine powder. It is preferable to consist of. In addition, the first coarse material forming step is a first intermediate coarse material forming step of obtaining a first intermediate coarse material by bringing one of the positive charge adsorption main body dispersion system and the negative charge adsorption main body dispersion system into contact with the support, Preferably, the first intermediate coarse material comprises a first coarse material completion step of contacting the other of the positive charge adsorption main body dispersion system and the negative charge adsorption main body dispersion system to obtain the first coarse material. In the second coarse material forming step, it is preferable to dry the first coarse material.

  When the adsorption main body dispersion system includes the positive charge adsorption fine powder and the negative charge adsorption fine powder, the adsorption main body dispersion system easily forms aggregates, and the adsorption main body dispersion system easily precipitates the dispersoid. In this case, it becomes difficult to manufacture the adsorption element. If a large amount of dispersant is used to prevent this, the function of the adsorbed fine powder or smile fibrous cellulose is likely to deteriorate. In this respect, if the adsorption element is manufactured as described above, the dispersion for positive charge adsorption main obtained in the first positive charge preparation step does not easily settle the dispersoid, and the negative charge obtained in the first negative charge preparation step. It is difficult for the dispersion system for charge adsorption to settle the dispersoid. For this reason, even if a large amount of dispersant is not used, the dispersion for positive charge adsorption and the dispersion for negative charge adsorption disperse the dispersoid over a long period of time, and it is relatively easy to manufacture the adsorption element. Become.

  In the first coarse material forming step, the adsorption main body dispersion system may be brought into contact with the adsorbent of the used adsorbent element in which the adsorbate is adsorbed on the adsorbent. In this case, it becomes difficult for the adsorbent of the used adsorbing element to be detached. Thus, the used adsorption element can be reused.

  The obtained adsorbing element can be used for filtration of contaminated water, nutrient water, carrier water, etc., decolorization of contaminated water, decontamination of contaminated water with radioactive substances, deodorization of contaminated gas, and the like, as with conventional adsorbing elements. Further, for example, while the contaminated water is being filtered by the adsorption element, a predetermined amount of the dispersion system for the adsorption main body that has become an emulsion can be injected upstream of the adsorption element, and the adsorption main body can be provided on the finishing layer. In this case, the finishing layer suitably holds the adsorption body. Thereby, the filtration capability and purification capability which were reduced by the continuation of filtration can be recovered by the new adsorption main body.

  According to the adsorption element of the present invention, higher filtering ability and purification ability can be exhibited.

FIG. 1 relates to the adsorption elements of Examples 1 and 2, FIG. (A) is an enlarged schematic cross-sectional view of a support, FIG. (B) is an enlarged schematic cross-sectional view of a first intermediate coarse material, and FIG. 1 is an enlarged schematic cross-sectional view of a coarse material, FIG. (D) is an enlarged schematic cross-sectional view of a second coarse material, FIG. (E) is an enlarged schematic cross-sectional view of a third coarse material, and FIG. (F) is an enlarged schematic cross-sectional view of an adsorption element. FIG. FIG. 2 is a process diagram illustrating a method for manufacturing the adsorption element of Examples 1 and 2. FIG. 3 is a schematic diagram of a filtration system using the adsorption elements of Examples 1 and 2. FIG. 4 is an enlarged schematic cross-sectional view showing a state in which contaminated water is filtered by the adsorption elements of Examples 1 and 2. FIG. 5 is related to the adsorption element of Example 3, FIG. (A) is an enlarged schematic cross-sectional view of a used adsorption element, FIG. (B) is an enlarged schematic cross-sectional view of the first coarse material, and FIG. The enlarged schematic cross-sectional view of the coarse material, FIG. (D) is an enlarged schematic cross-sectional view of the third coarse material, and FIG. (E) is the enlarged schematic cross-sectional view of the adsorption element to be reused. FIG. 6 is related to the adsorption element of Example 4, FIG. (A) is an enlarged schematic sectional view of a used adsorption element, FIG. (B) is an enlarged schematic sectional view of a first coarse material, and FIG. The enlarged schematic cross-sectional view of the coarse material, FIG. (D) is an enlarged schematic cross-sectional view of the third coarse material, and FIG. (E) is the enlarged schematic cross-sectional view of the adsorption element to be reused. FIG. 7 is a graph showing the ultraviolet absorption characteristics of water transported by squid.

  Hereinafter, the present invention is embodied in the adsorption elements of Examples 1-9. Moreover, the effect of the adsorption element of Examples 1-9 was confirmed by verification 1-6 by the comparison with Comparative Examples 1-11.

<Verification 1>
Example 1
As shown to FIG. 1 (A), the nonwoven fabric sheet as the support body 1 is prepared. The fibers 1a entangled with each other in the nonwoven fabric sheet are made of polyester.

  Also, cation exchange resin powder as positive charge adsorption fine powder (PK316 manufactured by Mitsubishi Chemical Corporation, water content 50%) and anion exchange resin powder as negative charge adsorption fine powder (PA316 manufactured by Mitsubishi Chemical Corporation, water content 50%) And prepare. Furthermore, microfibrous cellulose (Delcel Fine Chemical Co., Ltd. serisch (registered trademark), water content 90%) is prepared.

  And as shown in FIG. 2, 1st preparation process S10 is performed. The first preparation step S10 includes a first positive charge preparation step S11 and a first negative charge preparation step S12.

  In the first positive charge preparation step S11, first, 100% by mass of cation exchange resin powder and 10% by mass of microfibrous cellulose are added to 1000% by mass of distilled water to obtain a mixture. This mixture is pulverized for 1 minute at room temperature by a “juice mixer TM8100” manufactured by Tescom Co., Ltd. to obtain a dispersion 3 for a positively charged adsorbing body that is an emulsion.

  In 1st negative charge preparation process S12, 100 mass% of anion exchange resin powder and 10 mass% of micro fibrous cellulose are thrown into 1000 mass% distilled water, and a mixture is obtained. This mixture is pulverized in the same manner as the positive charge adsorption main body dispersion 3 to obtain an emulsion of the negative charge adsorption main body dispersion 5.

  Moreover, 2nd preparation process S20 is performed. In the second preparation step S20, 100% by mass of microfibrous cellulose is added to 1000% by mass of distilled water, and this is pulverized in the same manner as the dispersion system 3 for the positive charge adsorption body and the dispersion system 5 for the negative charge adsorption body. A dispersion 7 for the finishing layer in the form of an emulsion is obtained.

  Then, 1st coarse material formation process S30 is performed. The first coarse material forming step S30 includes a first intermediate coarse material forming step S31 and a first coarse material completion step S32.

  In the first intermediate coarse material forming step S31, the positive charge adsorption main body dispersion system 3 is first diluted 10 times with distilled water to obtain a diluted solution. And as shown in FIG.1 (B), the support body 1 is immersed in the dilution liquid, and the 1st intermediate | middle coarse material 9 is obtained. At this time, the positive charge adsorption main dispersion system 3 is difficult to precipitate the cation exchange resin powder and the fine fibrous cellulose as the dispersoid without using a dispersant. For this reason, the 1st intermediate | middle coarse material 9 can be obtained comparatively easily.

  Moreover, also in 1st rough material completion process S32, the dispersion system 5 for negative charge adsorption main bodies is diluted 10 times with distilled water, and it is set as a dilution liquid. And as shown in FIG.1 (C), the 1st intermediate coarse material 9 is immersed in the dilution liquid, and the 1st coarse material 11 is obtained. Also in this case, the negative charge adsorption main dispersion system 5 is difficult to precipitate the anion exchange resin powder and the fine fibrous cellulose as a dispersoid without using a dispersant. For this reason, the 1st coarse material 11 can be obtained comparatively easily.

  In Example 1, the first intermediate coarse material 9 was dipped in the negative charge adsorption main body dispersion 5 to obtain the first coarse material 11 without drying the first intermediate coarse material 9, but the first intermediate coarse material 9 was once dried. Then, the first coarse material 11 may be obtained by immersing in the negative charge adsorption main body dispersion 5.

  Next, as shown in FIG. 2, a second coarse material forming step S40 is performed. Here, as shown in FIG. 1D, the first coarse material 11 is dried at 80 ° C. for 1 hour to obtain the second coarse material 13. The second coarse material 13 includes a support 1 and an adsorption main body 15 formed on the support 1. The adsorption main body 15 includes a first adsorption main body 3a formed by drying the positive charge adsorption main body dispersion 3 on the support 1, and a negative charge adsorption main body dispersion 5 dried on the first adsorption main body 3a. The second adsorption main body 5a is formed. However, the first adsorption main body 3a and the second adsorption main body 5a contain a certain amount of water. The first adsorption main body 3a thus obtained has a mass ratio of 4: 1 between the cation exchange resin powder and the microfibrous cellulose. The second adsorption main body 5a has a mass ratio of 4: 1 between the anion exchange resin powder and the microfibrous cellulose.

  Moreover, as shown in FIG. 2, 3rd coarse material formation process S50 is performed. Here, as shown in FIG. 1 (E), the second coarse material 13 is immersed in the finishing layer dispersion 7 to obtain the third coarse material 17.

  Next, as shown in FIG. 2, a completion step S60 is performed. Here, as shown in FIG. 1 (F), the third coarse material 17 is dried at 80 ° C. for 1 hour to obtain the adsorption element 19.

  As shown in Table 1, the adsorption element 19 of Example 1 obtained in this way is composed of a support 1 and an adsorbent 21 supported by the support 1. The adsorbent 21 includes an adsorption main body 15 and a finishing layer 7 a formed on the adsorption main body 15. The adsorption main body 15 is located inside and formed with adsorption fine powder and fine fibrous cellulose. The adsorption element 19 of Example 1 employs a cation exchange resin and an anion exchange resin as adsorption fine powder. The finishing layer 7 a is formed by drying the finishing layer dispersion 7 on the adsorption body 15. However, the finishing layer 7a also contains a certain amount of water. The finishing layer 7a surrounds the adsorption main body 15 and is made of fine fibrous cellulose.

  The adsorption element 19 of Example 1 is used in the filtration system shown in FIG. 3, for example. In this filtration system, a pipe 33 extending from the bottom of the tank 31 is connected to the bottom of a cartridge shell (imported by Taki Engineering Co., Ltd.) 35, and a pipe 37 extending from the top of the cartridge shell 35 is connected via a pump 39. It is provided up to the upper side of the tank 31. The cartridge shell 35 has a detachable cartridge 35a, and the adsorption element 19 is filled in the cartridge 35a. Contaminated water is stored in the tank 31.

  When the pump 39 is operated, the contaminated water in the tank 31 is supplied to the cartridge shell 35 through the pipe 33 at a constant flow rate. The contaminated water supplied to the cartridge shell 35 is filtered at a constant flow rate by the adsorption element 19 in the cartridge 35a. At this time, as shown in FIG. 4, the contaminated water comes into contact with the adsorbent 21 formed on the surface of each fiber 1 a, and foreign matter is adsorbed by the adsorbent 21. Thus, the filtration of the contaminated water by the adsorption element 19 is repeated, and the contaminated water in the tank 31 is gradually purified.

(Example 2)
The adsorption element 19 of Example 2 employs cation exchange resin powder and Prussian blue as positive charge adsorption fine powder. As shown in Table 1, the first adsorption main body 3a shown in FIGS. 1D to 1F has a mass ratio of cation exchange resin powder, Prussian blue, and fine fibrous cellulose of 4: 1.6: 1. Since other configurations and manufacturing methods are the same as those in the first embodiment, the detailed description will not be repeated.

(Comparative Examples 1 and 2)
The adsorption elements of Comparative Examples 1 and 2 are manufactured without going through the second preparation step S20, the third rough shape forming step S50, and the completion step S60. That is, the adsorption elements of Comparative Examples 1 and 2 correspond to the second coarse material 13 shown in FIG. 1D, and the adsorption main body 15 is not surrounded by the finishing layer 7a. In the adsorption main body (adsorbent) of Comparative Example 1, the first adsorption main body has a mass ratio of cation exchange resin powder and microfibrous cellulose of 4: 1, and the second adsorption main body has anion exchange resin powder and microfiber. The mass ratio with fibrous cellulose is 4: 1. On the other hand, in the adsorption body (adsorbent) of Comparative Example 2, the first adsorption body has a mass ratio of cation exchange resin powder, Prussian blue, and microfibrous cellulose of 4: 1.6: 1, 2 The adsorption body has a mass ratio of 4: 1 between the anion exchange resin powder and the microfibrous cellulose.

(Test 1)
In order to confirm the filtration capacity of the adsorption elements of Examples 1 and 2, the following Test 1 was performed together with the adsorption elements of Comparative Examples 1 and 2. In Test 1, the filtration capacity of contaminated water contaminated with radioactive cesium was compared.

  In Test 1, the above filtration system was used to circulate contaminated water at a flow rate of about 5 L / min. The contaminated water in the tank 31 contains 140 Bq / Kg of cesium 134 and 500 Bq / Kg of cesium 137. The radiation concentration in the contaminated water was measured by a spectrometric analysis method using a germanium semiconductor detector. As a turbidity measuring instrument, a SEC-EMS type manufactured by Seiko EG & G Co. was used. The pH of the contaminated water before filtration and the pH of the contaminated water after filtration using each adsorption element were also measured. The results are shown in Table 2.

  As shown in Table 2, although the adsorbing element of Comparative Example 1 exhibits a certain effect in turbidity, cesium 134 and cesium 137 in the contaminated water cannot be reduced so much. Further, the adsorption element of Comparative Example 2 exhibits a higher effect than the adsorption element of Comparative Example 1.

  On the other hand, in the adsorption elements of Examples 1 and 2, both cesium 134 and cesium 137 in the contaminated water can be lowered to the measurement limit or less (ND). They also reduce the turbidity of the contaminated water to 0.1.

  The inventors considered the difference in filtration capacity between the adsorption elements of Examples 1 and 2 and the adsorption elements of Comparative Examples 1 and 2 as follows. That is, in the adsorption elements of Comparative Examples 1 and 2, the adsorbent is composed only of the adsorption main body. For this reason, it is considered that a part of the adsorbent fine powder separated from the support during use. Thereby, cesium 134 and cesium 137 are included in the contaminated water after filtration together with a part of the adsorbent, and it is considered that the above results were obtained. In addition, it is considered that the turbidity of the contaminated water could not be sufficiently reduced.

  On the other hand, in the adsorption elements of Examples 1 and 2, the adsorbent 21 is composed of the adsorption main body 15 and the finishing layer 7a, and the adsorption main body 15 is surrounded by the finishing layer 7a. For this reason, some adsorption | suction fine powder of the adsorption | suction main body 15 becomes difficult to detach | leave from the support body 1 in use. Further, the finishing layer 7a surrounding the adsorption main body 21 is formed of microfibrous cellulose, and exhibits a certain degree of adsorption capability by itself, and does not impair the adsorption capability of the internal adsorption main body 21. For this reason, it is considered that both cesium 134 and cesium 137 in the contaminated water were reduced to below the measurement limit. Moreover, it is thought that the turbidity of the contaminated water also decreased to 0.1.

  In the adsorption element 19 of the first and second embodiments, the adsorption main body 15 is composed of the first adsorption main body 3a and the second adsorption main body 5a, but the adsorption main body 15 is composed of the first adsorption main body 3a or the second adsorption main body 5a. You may comprise only. Further, the adsorption main body 15 is composed of the first adsorption main body 3a, the second adsorption main body 5a and the first adsorption main body 3a, or the first adsorption main body 3a, the second adsorption main body 5a, the first adsorption main body 3a and the second adsorption main body. It may be multi-layered such as 5a.

(Example 3)
In the adsorption element of the third embodiment, as shown in FIG. 5A, a used adsorption element 41 is employed instead of the support 1 in the adsorption element 19 of the first embodiment. The used adsorption element 41 includes each fiber 41a of the support and an adsorbent 41b formed on the surface of each fiber 41a. Adsorbate such as foreign matter is already adsorbed on the adsorbent 41b.

  In addition, as in Examples 1 and 2, adsorbed fine powder and fine fibrous cellulose are prepared. And as shown in FIG. 2, 1st preparation process S10 is performed and the dispersion | distribution system 43 for adsorption bodies is obtained. Moreover, 2nd preparation process S20 is performed and the dispersion system 7 for finishing layers is obtained.

  Thereafter, the first coarse material forming step S30 is performed, and as shown in FIG. 5B, the used adsorption element 41 is immersed in the diluted liquid of the adsorption main body dispersion system 43 to obtain the first coarse material 45.

  Next, as shown in FIG. 2, the second coarse material forming step S <b> 40 is performed, and as shown in FIG. 5C, the first coarse material 45 is dried to obtain the second coarse material 47. The second coarse material 47 includes a used adsorption element 41 and an adsorption main body 43 a formed on the used adsorption element 41. The adsorption main body 43 a is formed by drying the adsorption main body dispersion system 43 on the used adsorption element 41.

  Further, as shown in FIG. 2, a third coarse material forming step S50 is performed, and as shown in FIG. 5D, the second coarse material 47 is immersed in the finishing layer dispersion system 7 to immerse the third coarse material 49. Get.

  Next, as shown in FIG. 2, a completion step S <b> 60 is performed, and as shown in FIG. 5E, the third coarse material 49 is dried to obtain the adsorption element 51.

  The suction element 51 according to the third embodiment that is reused in this manner includes a used suction element 41 and an adsorbent 53 formed on the used suction element 41. The adsorbent 53 includes an adsorption main body 43a and a finishing layer 7a formed on the adsorption main body 43a. In this adsorption element 51, the adsorbent 41b of the used adsorption element 41 is difficult to separate. Thus, the used adsorption element 41 can be reused.

Example 4
In the adsorption element of the fourth embodiment, as shown in FIG. 6A, a used adsorption element 61 is employed instead of the used adsorption element 41 of the third embodiment. The used adsorption | suction element 61 consists of each fiber 1a of the support body 1, and the adsorbent 63 formed on each fiber 1a. The adsorbent 63 includes an adsorption main body 63a and a finishing layer 63b formed on the adsorption main body 63a. Adsorbate such as foreign matter is already adsorbed on the adsorbent 63. In other words, the used suction element 61 is a temporary use of the suction element 19 of the first and second embodiments.

  Moreover, adsorption fine powder and micro fibrous cellulose are prepared similarly to Examples 1-3. And as shown in FIG. 2, 1st preparation process S10 is performed and the dispersion | distribution system 65 for adsorption bodies is obtained. Moreover, 2nd preparation process S20 is performed and the dispersion system 7 for finishing layers is obtained.

  Thereafter, the first coarse material forming step S30 is performed, and as shown in FIG. 6B, the used adsorption element 61 is immersed in the dilution liquid of the adsorption main body dispersion system 65 to obtain the first coarse material 67.

  Next, as shown in FIG. 2, a second coarse material forming step S <b> 40 is performed, and as shown in FIG. 6C, the first coarse material 67 is dried to obtain a second coarse material 69. The second coarse material 69 includes a used suction element 61 and a suction main body 65 a formed on the used suction element 61. The adsorption main body 65 a is formed by drying the adsorption main body dispersion system 65 on the used adsorption element 61.

  Further, as shown in FIG. 2, the third coarse material forming step S50 is performed, and as shown in FIG. 6D, the second coarse material 69 is dipped in the finishing layer dispersion system 7 and the third coarse material 71 is immersed. Get.

  Next, as shown in FIG. 2, a completion step S <b> 60 is performed, and as shown in FIG. 6E, the third coarse material 71 is dried to obtain the adsorption element 73.

  The suction element 73 according to the fourth embodiment that is reused in this manner includes a used suction element 61 and a suction material 75 formed on the used suction element 61. The adsorbent 75 includes an adsorption main body 65a and a finishing layer 7a formed on the adsorption main body 43a. In this adsorption element 73, it becomes difficult for the adsorbent 63 of the used adsorption element 61 to be detached. In this way, the used adsorption element 61 can be reused.

<Verification 2>
(Comparative Example 3)
A nonwoven fabric sheet as a support 1 and zeolite as an adsorbed fine powder were prepared. In Comparative Example 3, as shown in Table 3, the nonwoven fabric sheet is used as an adsorption element as it is, and does not have an adsorbent (adsorption body).

(Comparative Example 4)
The adsorption element of Comparative Example 4 corresponds to the second coarse material 13 shown in FIG. 1 (D), and an adsorbent made of zeolite and fine fibrous cellulose is formed on the support 1. The mass ratio of zeolite to microfibrous cellulose is 4: 1.

(Comparative Example 5)
The adsorption element of Comparative Example 5 corresponds to the second coarse material 13 shown in FIG. 1 (D), and an adsorbent made of zeolite, cation exchange resin powder, and microfibrous cellulose is formed on the support 1. It is. The mass ratio of the adsorbent zeolite, cation exchange resin powder and microfibrous cellulose is 2: 2: 1.

(Comparative Example 6)
The adsorbing element of Comparative Example 6 corresponds to the second coarse material 13 shown in FIG. 1 (D), and the first adsorbing body 3a made of zeolite, cation exchange resin powder, and fine fibrous cellulose is provided on the support 1. After the formation, the second adsorption main body 5a made of zeolite and fine fibrous cellulose is formed on the first adsorption main body 3a. The mass ratio of the zeolite of the first adsorption body 3a, the cation exchange resin powder and the microfibrous cellulose is 2: 2: 1, and the mass ratio of the zeolite of the second adsorption body 5a and the microfibrous cellulose is 4: 2. 1.

(Comparative Example 7)
A 20 ° C. phosphoric acid aqueous solution containing sodium monohydrogen phosphate (Na ₂ HPO ₄ ) at a concentration of 1% was prepared. The adsorption element of Comparative Example 7 is obtained by immersing the adsorption element of Comparative Example 1 in this phosphoric acid aqueous solution and drying it.

(Comparative Example 8)
The adsorbing element of Comparative Example 8 corresponds to the second coarse material 13 shown in FIG. 1D, and after the first adsorbing body 3a made of zeolite and fine fibrous cellulose is formed on the support 1, the first adsorbing element 3a is formed. The second adsorption main body 5a made of zeolite and fine fibrous cellulose is again formed on the adsorption main body 3a. The mass ratio of zeolite and microfibrous cellulose in the first adsorption main body 3a is 4: 1, and the mass ratio of zeolite and microfibrous cellulose in the second adsorption main body 5a is 4: 1.

(Example 5)
The adsorption element of Example 5 is obtained by applying the third coarse material forming step S50 and the completion step S60 to the adsorption element of Comparative Example 8. As shown in FIG. 1 (F), the adsorption element includes a support 1 and an adsorbent 21 formed on the support 1. The adsorbent 21 includes a first adsorption main body 3a, a second adsorption main body 5a formed on the first adsorption main body 3a, and a finishing layer 7a formed on the second adsorption main body 5a. Since other configurations and manufacturing methods are the same as those in the first embodiment, the detailed description will not be repeated.

(Test 2)
The following model tests were conducted. First, 100 g of test fresh water in which 100 ppm of non-radioactive cesium was dissolved was prepared. Moreover, 100 g of simulated seawater for test (containing Na, Mg, and K) in which 100 ppm of non-radioactive cesium was dissolved and diluted 20 times was prepared.

  The adsorbing element of Example 5 and the adsorbing elements of Comparative Examples 3 to 8 were permeated into fresh water for testing and allowed to stand for 24 hours. This was repeated 10 times, and then the non-radioactive cesium concentration in the fresh water for test was measured by ICP emission spectroscopy (ICP-AES). Moreover, each adsorption element was similarly immersed in the simulated seawater for testing, and the non-radioactive cesium concentration in the simulated seawater for testing was measured in the same manner. The decontamination rate (%) was determined from each concentration.

  In addition, a 50 mm × 30 mm test piece was cut out from each adsorption element, and these were put into a tall beaker and subjected to ultrasonic treatment (40 Hz, 10 minutes). Thus, the separation rate (%) of the adsorbed fine powder was determined. The results are shown in Table 4.

  As shown in Table 4, it can be seen that the adsorption element of Example 5 and the adsorption elements of Comparative Examples 4 to 8 can decontaminate non-radioactive cesium at a high rate. However, it can be seen that the adsorbing elements of Comparative Examples 4 to 8 are separated from the adsorbed fine powder. On the other hand, it can be seen that the adsorbing element of Example 5 is difficult to remove the adsorbed fine powder.

  Therefore, the above-mentioned consideration of the inventors is correct, and it can be seen that the adsorption element of Example 5 can exhibit higher filtering ability.

<Verification 3>
(Reproduction processing)
A test piece of 50 mm × 30 mm was cut out from each adsorbing element subjected to test 2, put into a tall beaker, put into 100 ml of a 0.1N concentration, 70 ° C. diluted hydrochloric acid aqueous solution, and stirred for 5 minutes with a magnetic stirrer. Thereafter, each test piece was taken out, washed with water, and dehydrated. The test piece was put into 100 ml of a 0.1N concentration, 70 ° C. aqueous NaH ₂ PO ₄ solution and stirred in the same manner as described above.

  Thereafter, each test piece was taken out, washed with water, dehydrated, and regenerated. About the test piece after a reproduction | regeneration process, the residual amount of radioactive cesium was measured, but the residue was not recognized.

  Moreover, when this was used repeatedly, it was confirmed that the amount of radioactive cesium adsorbed was not inferior to 90% or more of the initial value. For this reason, it turns out that the adsorption element of Example 5 can be used repeatedly.

<Verification 4>
(Comparative Example 9)
A nonwoven fabric sheet (25 cm × 25 cm) as the support 1 and activated carbon (150 mesh, Taiho) as the adsorbed fine powder were prepared. The adsorbing element of Comparative Example 9 corresponds to the second coarse material 13 shown in FIG. 1 (D), and an adsorbing body 15 made of activated carbon and fine fibrous cellulose is formed on the support 1. As shown in Table 5, the mass ratio of the activated carbon of the adsorption main body 15 to the microfibrous cellulose is 4: 1.

(Comparative Example 10)
The adsorbing element of Comparative Example 10 corresponds to the second coarse material 13 shown in FIG. 1D, and after the first adsorbing body 3a made of activated carbon and fine fibrous cellulose is formed on the support 1, the first adsorbing element 3a is formed. A second adsorption main body 5a made of activated carbon, anion exchange resin powder, and fine fibrous cellulose is formed on the adsorption main body 3a. The mass ratio of activated carbon and microfibrous cellulose in the first adsorption body 3a is 4: 1, and the mass ratio of activated carbon, anion exchange resin powder and microfibrous cellulose in the second adsorption body 5a is 1:10: 4.

(Comparative Example 11)
The adsorbing element of Comparative Example 11 corresponds to the second coarse material 13 shown in FIG. 1D, and the first adsorbing body 3a made of activated carbon, anion exchange resin powder, and fine fibrous cellulose is formed on the support 1. After the formation, the second adsorption main body 5a made of activated carbon and fine fibrous cellulose is formed on the first adsorption main body 3a. The mass ratio of the activated carbon of the first adsorption body 3a, the anion exchange resin powder, and the fine fibrous cellulose is 1: 10: 4, and the mass ratio of the activated carbon of the second adsorption body 5a and the fine fibrous cellulose is 4: 1.

(Example 6)
The adsorption element of Example 6 is obtained by performing the third coarse material forming step S50 and the completion step S60 using the adsorption element of Comparative Example 9 as the second coarse material 13 shown in FIG. Since other configurations and manufacturing methods are the same as those in the first embodiment, the detailed description will not be repeated.

(Test 3)
Each adsorbing element was sealed at the bottom of a sealed container made of polypropylene having an internal volume of 200 L, and the deodorizing ability was measured. The initial concentration was set at a constant 60 ppm by injecting a predetermined amount of the odor component into the sealed container and allowing it to stand for 1 hour to diffuse the odor component. A detector tube was set in the sampling hole every predetermined time, and the deodorizing ability of each adsorption element was measured. Assuming that the organic acid is an odor component, the synergistic action between the activated carbon and the anion exchange resin powder was confirmed. The results are shown in Table 6.

  As can be seen from Table 6, the adsorption elements of Comparative Examples 9 to 11 also exhibited high deodorizing ability, but the adsorption element of Example 6 exhibited higher deodorizing ability.

<Verification 5>
The adsorption element of Example 6 and the adsorption elements of Comparative Examples 9 to 11 were prepared. Moreover, the adsorption element of Examples 7-9 was prepared. The adsorption element of Example 7 is obtained by performing the third coarse material forming step S50 and the completion step S60 using the adsorption element of Comparative Example 10 as the second coarse material 13 shown in FIG. The adsorption element of Example 8 is obtained by performing the third coarse material forming step S50 and the completion step S60 with the adsorption element of Comparative Example 11 as the second coarse material 13 shown in FIG. The adsorption element of Example 9 is obtained by performing the regeneration process on the adsorption element of Example 8. Table 7 shows the configurations of the adsorbents of the adsorbing elements of Examples 6 to 9 and Comparative Examples 9 to 11.

(Test 4)
A sugar solution (light absorbance 420 nm, 1 cm: 0.150, 720 nm, 1 cm: 0.005) in which 100 g of raw sugar (Natal sucrose) is dissolved in 1 L of tap water is put in a beaker, and each adsorbing element is cut (1 cm). 1 g) was introduced. Then, it stirred with the Magneck stirrer in the 60 degreeC thermostat for 1 hour, and was set as the process liquid. Thereafter, the absorbance of the treatment liquid at 420 nm, 10 mm (yellow brown) and T720 nm, 10 mm (turbidity) was measured using a spectrophotometer. In this way, the decoloring test was implemented.

  Cut materials were collected from each treatment solution, washed with tap water, and dehydrated. The obtained cut material was transferred to a beaker, 1 L of 0.1 N hydrochloric acid was added, the mixture was heated to 70 ° C., and stirred for 10 minutes using a magnetic stirrer. Thereafter, the hydrochloric acid solution was neutralized with sodium carbonate, and the absorbance of each solution was examined. Thus, the amount of desorbed dye was measured. The results are shown in Table 8.

  As can be seen from Table 8, in the adsorption elements of Comparative Examples 9 to 11, a small amount of adsorbed fine powder was removed due to disturbance (stirring), but in the adsorbing elements of Examples 6 to 9, the adsorbed fine powder was extremely separated. Has decreased. In particular, in the adsorbing elements of Examples 7 to 9, there was no separation of adsorbed fine powder.

<Verification 6>
Conventionally, as a measure for transporting live squid, it has been carried out by placing the squid together with transport water made of seawater into a container made of styrene foam having a capacity of about 30 L and transporting it by truck. However, the squid in transit could not be alive until the next day, and had smudged ink. For this reason, long-distance transportation cannot be carried out while surviving the squid, and countermeasures have been desired.

  For this reason, the adsorption element of Example 1 was suspended in the transport water in the container containing the squid and transported by truck. As a result, out of 10 cups, only 1 cup of squid died and ink was not spit out.

  Moreover, the ultraviolet absorption characteristic was calculated | required about the conveyance water at the time of carrying a squid with the adsorption | suction element of Example 1 suspended, and the conveyance water at the time of carrying a squid with nothing put in conveyance water. The results are shown in FIG. The vertical axis in FIG. 7 indicates the wavelength range (nm), and the horizontal axis indicates the absorbance.

  It can be seen from FIG. 7 that the adsorbing element of Example 1 exhibits excellent filtering ability and purification ability. This filtering ability and purification ability are exerted as a pharmacological action if an aquatic organism is used. The same effect was confirmed for the shrimp.

  In the above, the present invention has been described with reference to the first to ninth embodiments. However, the present invention is not limited to the first to ninth embodiments, and can be appropriately modified and applied without departing from the spirit of the present invention. Needless to say.

  For example, a sponge filter having open cells can be used as the support. In addition to cation exchange resin, anion exchange resin, Prussian blue, zeolite, silicotitanate, insoluble ferrocyanide, crystalline tetratitanate, titanosilicate, diatomaceous earth, etc. may be adopted as the adsorbed fine powder. Is possible.

  The adsorption element of the present invention can be used for purification of contaminated water, purification of contaminated gas, and the like.

DESCRIPTION OF SYMBOLS 1 ... Support body 21, 53, 75 ... Adsorbent 15, 43a, 65a ... Adsorption body 7a ... Finishing layer 19, 51, 73 ... Adsorption element 3, 5 ... Dispersion system for adsorption bodies (3 ... Dispersion for positive charge adsorption books System, 5 ... dispersion system for negative charge adsorption body)
S10: First preparation step (S11: First positive charge preparation step, S12: First negative charge preparation step)
7 ... Dispersion system for finishing layer S20 ... Second preparation step 11 ... First coarse material S30 ... First coarse material formation step (S31 ... First intermediate coarse material formation step, S32 ... First coarse material completion step)
DESCRIPTION OF SYMBOLS 9 ... 1st intermediate | middle coarse material 13 ... 2nd coarse material S40 ... 2nd coarse material formation process 17 ... 3rd coarse material S50 ... 3rd coarse material formation process S60 ... Completion process 41, 61 ... Used adsorption element

Claims (4)

An adsorbing element having a support and an adsorbent supported by the support and capable of adsorbing adsorbate containing adsorbed fine powder and fine fibrous cellulose,
The adsorbent is located inside, an adsorption main body formed with the adsorbed fine powder and the microfibrous cellulose,
An adsorbing element characterized by comprising a finishing layer surrounding the adsorbing body and formed of the microfibrous cellulose. A method for producing an adsorbing element comprising a support and an adsorbent supported by the support and capable of adsorbing adsorbate containing adsorbed fine powder and fine fibrous cellulose,
A first preparation step of preparing a dispersion system for an adsorption main body, in which a dispersion medium is water and a dispersoid is the adsorption fine powder and the fine fibrous cellulose;
A second preparation step of preparing a dispersion for a finishing layer, in which the dispersion medium is water and the dispersoid is the fine fibrous cellulose;
A first coarse material forming step of obtaining a first coarse material by bringing the support body dispersion system into contact with the support body;
A second coarse material forming step of drying the first coarse material and obtaining a second coarse material having an adsorption main body formed on the support;
A third coarse material forming step of obtaining a third coarse material by bringing the finishing layer dispersion into contact with the adsorption main body;
A method for producing an adsorption element, comprising: drying the third coarse material to obtain an adsorption element formed with the adsorbent in which the adsorption main body is surrounded by a finishing layer. The adsorbed fine powder is a positive charge having a positive charge which is at least one of zeolite, silicotitanate, insoluble ferrocyanide, crystalline tetratitanate, titanosilicate, Prussian blue, diatomaceous earth, activated carbon, cation exchange resin and the like. Adsorbed fines,
It consists of negative charge adsorption fine powder with negative charge which is an anion exchange resin,
The first preparation step includes a first positive charge preparation step for obtaining a positive charge adsorption main dispersion containing the positive charge adsorption fine powder;
A first negative charge preparation step of obtaining a negative charge adsorption main body dispersion containing the negative charge adsorption fine powder,
In the first coarse material forming step, one of the positive charge adsorption main body dispersion system and the negative charge adsorption main body dispersion system is brought into contact with the support to obtain a first intermediate coarse material formation step. When,
A first coarse material completion step of obtaining the first coarse material by bringing the first intermediate coarse material into contact with the other of the positive charge adsorption main body dispersion and the negative charge adsorption main body dispersion;
The method for manufacturing an adsorption element according to claim 2, wherein in the second coarse material forming step, the first coarse material is dried.   The method of manufacturing an adsorption element according to claim 2 or 3, wherein, in the first coarse material forming step, the adsorption main body dispersion system is brought into contact with the adsorbent of the used adsorbent element in which the adsorbate is adsorbed on the adsorbent. .

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