JP2012011348A - Liquid composition mainly composed of powder ion exchange resin, and powder ion exchange resin-including support - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique for preparing a homogeneous liquid composition mainly composed of a powder ion exchange resin, and a method for use thereof.SOLUTION: A liquid composition having an optional adhesive force is prepared by performing mixing and stirring treatment in a solution while adjusting the mixing ratio of a fine fibrous compound to the powder ion exchange resin, and this liquid composition is used to prepare a powder ion exchange resin-including processed product in which the powder ion exchange resin is adhered to a support. The liquid composition with a mixing ratio of the fine fibrous compound to the powder ion exchange resin of 5-100 wt.% is mixed and applied to the support followed by dehydration and drying, whereby an element for filtration machine or a deodorant sheet in which the powder ion exchange resin is inseparably fixed to a surface layer can be produced. By reducing the mixing ratio of the fine fibrous compound to 10 wt.% or less, a homogenous liquid composition mainly composed of the powder ion exchanged resin with reduced adhesive force to the support is prepared, and this liquid composition is used, whereby a hand spray enhanced in operability while preventing clogging of a spray nozzle can be produced.

Description

In the present invention, a liquid composition containing a powder ion exchange resin as a main component is prepared by adding a microfibrous compound to a powder ion exchange resin, particularly a used powder ion exchange resin. Using this liquid composition as a raw material, a processed product with high added value is manufactured. For example, an environmental purification agent for removing malodorous or harmful components contained in air or water, a purification agent for impure sugar liquid, and an alternative soil used in plant factories, etc., which uses the liquid composition Thus, a technique is disclosed that can be applied to a wide range of applications of used powder ion exchange resins ranging from everyday products to industrial fields.

Ion exchange resins have become established as a separation and purification technology for producing pure water by removing impurities contained in water. The ion-exchange resin is recycled and used for several hundred cycles, and then discarded. At present, the amount of ion exchange resin used in Japan is said to be around 20,000 cubic meters per year. Currently, only some sugar companies are recycling used ion exchange resin, and most used resin discharged from large plants such as electric power companies can be recycled without being recycled. It is treated as waste. Powder ion exchange resins have been used to remove radioactive pollutants in the condensate of nuclear power plants and decolorize impure sugar solutions, but the range of use has been extremely reduced due to the emergence of new technologies (membranes). . Under such circumstances, the production amount of new powder ion exchange resin is small, and it is expensive and the usage is limited. The used powder ion exchange resin can be produced at low cost if its use is expanded because it is a recycled product of the ion exchange resin. Although the function of the used powder ion exchange resin is not inferior to that of a new powder ion exchange resin, it is expected to develop from the viewpoint of effective use of resources, but it is hardly used at present.

As a processed product using a powder ion exchange resin as a raw material, for example, as described in Patent Document 1 or 3, 4, a porous support (eg, a porous body such as a nonwoven fabric or foam stone), a fine cellulose, and a powder By bringing the ion exchange resin into contact with water, the microcellulose and the powder ion exchange resin are agglomerated within the pores of the porous support, and the powder ion exchange resin is built into the pores of the porous support. Powder ion exchange resin inclusion support prepared by mixing powdered ion exchange resin solids with processed products and porous minerals, etc., but there are difficulties in the method of including powder ion exchange resin, and support with powder ion exchange resin The adhesive strength with the body was weak, and the range of use was limited to filter filters for closed aqueous solutions.

In order to expand the application range of used powder ion exchange resin, it is necessary to facilitate the manufacturing method of processed products using powder ion exchange resin as a raw material, for example, to remove ion exchange resin included against disturbance It is to produce a powder ion exchange resin-containing support excellent in functionality with no filter and a filter using the support as a filter element. The biggest technical difficulty in manufacturing powder ion-exchange resin-containing supports is that it is difficult to bond powder ion-exchange resin and the solid material to be used as a support, and it is impossible to use conventional chemical synthetic adhesives. Met. That is, the adhesive clogged the pores of the ion exchange resin, thereby impairing a fatal defect, that is, a function (regeneration, ion exchange action) unique to the ion exchange resin. It has been desired to solve this problem and establish a technique for adhering a powder ion exchange resin to the solid matter.

JP 2000-312881 A JP2003-245687 JP 2004-203988 A JP 2005-102673 A

The object of the present invention is to expand the application of powder ion exchange resin, to improve the function of processed products using powder ion exchange resin as a raw material, and to improve the convenience of use by devising the usage form of powder ion exchange resin It is to find the raw material of goods. For this purpose, it is important to produce a processed product in which the function of the powder ion exchange resin is maintained over a long period of time, in which the powder ion exchange resin is not easily bonded to the support and peeled off due to disturbance. For example, when used as a filtering agent for the purification of sugar liquid, powder ions that are firmly adhered to the support without detaching the powder ion exchange resin even in the regeneration operation with the most severe disturbance in the operation process. It is important to produce a filter support including an exchange resin and a filter using the filter support as a filter element.

The base of the ion exchange resin is a solid made of a polymer compound, and the powder ion exchange resin prepared by mechanically pulverizing the granular ion exchange resin is a solid fine powder, which has a great difficulty in the operability of the material itself. . In order to prepare a processed product with a wide range of applications using powder ion exchange resin as a raw material, a raw material in an easily usable form, that is, a liquid composition in which powder ion exchange resin mainly composed of powder ion exchange resin is uniformly dispersed Is to prepare. The liquid composition should have a solution, preferably a solution having a uniform composition in which the powder ion exchange resin is dispersed in water as a whole, and a solid which becomes a support when brought into contact with the solution. The powder ion resin is attached to the surface of the material, and the excess powder ion exchange resin and the solution that are not attached are separated by an operation such as centrifugation, and the powder ion exchange resin is attached to the surface of the support as much as possible. It is to produce a solid material (processed product) including a powder ion exchange resin. It is a liquid composition that can be easily applied to a solid material as a support, and can be applied even by a simple operation such as spraying, and can control the adhesive force between the applied powder ion exchange resin and the processed product. Finding a liquid composition and its usage, and processed products in which the powder ion exchange resin is occluded in the surface layer and voids of the porous support maintain the inherent impurity adsorption function (regeneration and ion exchange action) of the powder ion exchange resin. It is important to.

Even when using liquid compositions based on powder ion exchange resins that maintain a uniform composition and ion exchange function as the main component, especially mixed powders of yin and yang powders, they are easy to handle. Accordingly, it is easy to collect a predetermined amount, in other words, the liquid composition can be commonly applied in various fields, and preferably retains the function of the powder ion exchange resin as it is, and is used for the regeneration operation of the ion exchange resin exchange group. It is required to be possible.

There is no prior art that discloses a liquid composition mainly composed of a powder ion exchange resin that can be applied to various fields. In particular, it is bonded to a solid surface layer while maintaining the inherent function of the powder ion exchange resin, and is based on the strength of the adhesive strength. There is no prior art relating to the production of processed products with a wide range of applications as needed. The present invention is a liquid composition and a processed product that maintain the functions inherent to the powder ion exchange resin, and liquids having different properties (adhesive strength and dispersibility) by changing the amount of the microfibrous compound added. Techniques and methods of use for preparing compositions and making processed products according to the properties of these compositions are disclosed.

When producing filter media (filters), the powder ion exchange resin and the filter support adhere firmly, maintain the properties of the ion exchange resin, and do not delaminate even in severe disturbances such as regeneration operations. On the other hand, in the case of producing a deodorant, it is desirable that a powder ion exchange resin and a spraying operation under the floor generating bad odor are easy, for example, an inexpensive hand spray can be used. In this case, it is important not to block the sprayer nozzle even if the adhesion between the powder ion exchange resin and the solid is weak. In order to expand the application range of the powder ion exchange resin, it is important to create liquid compositions having different adhesion of the powder ion exchange resin to the processed product and to apply them as needed. According to the present invention, it is easy to produce a processed product using a powder ion exchange resin as a raw material, and the application range of the powder ion exchange resin, which is the greatest problem, is expanded.

In order to prepare an industrially useful liquid composition based on powder ion exchange resin, firstly, it is necessary to prepare a liquid having a uniform composition that is inexpensive, easy to handle and easy to measure. It is. For example, when an anion / cation powder ion exchange resin is used in water, the formation of aggregates generated, the shape change that occurs during long-term storage, that is, the powder produced by gelation of the powder ion exchange resin aggregates precipitated at the bottom of the liquid A technique for avoiding a change in physical properties peculiar to an ion exchange resin has been desired.

A uniform liquid composition is obtained by adding a microfibrous compound to a powder ion exchange resin and mixing and stirring in a solution. However, as the mixing ratio of the microfibrous compound increases, a uniform composition is prepared. For this purpose, a long stirring operation is required. A powerful stirring operation, for example, high-speed rotation stirring, preferably homogenization treatment is performed to prepare a liquid composition in which both the compounds are uniformly joined and the functions inherent to the powder ion exchange resin are maintained. The liquid composition is a sol component that reacts with the solid surface layer and has a uniform composition of the powder ion exchange resin and the microfibrous compound. After attaching the sol to the surface of the support, it was found that the support and the solution bonded with the powder ion exchange resin can be easily separated by dehydrating by centrifugation or the like. After the liquid composition is applied to the support, the sol component composed of a uniform composition of the powder ion exchange resin and the microfibers is adhered to the support surface layer to cause the most part of the fine solid particles to be supported on the support surface layer. The liquid part containing the excess powder ion exchange resin that has not been adhered to the support is fractionated to prepare a powder ion exchange resin-containing solid. It was found that the powder ion exchange resin and the solid matter were firmly bonded by forcibly drying the powder ion exchange resin-containing solid matter. In this way, it has become possible to provide a processed product that does not peel and maintains an excellent function unique to the powder ion exchange resin. In the process of carrying out these operations, it was found that there is a large difference in the bonding force with the solid material by changing the mixing ratio of the powder ion exchange resin and the microfibrous compound. That is, a powder ion exchange resin-containing solid prepared by carrying out the same operation using a liquid composition having a small mixing ratio of the powder ion exchange resin of the microfibrous compound is dried to obtain a powder ion exchange resin and a support. The adhesive strength of the powder becomes weak, and by applying a disturbance (light vibration), the powder ion exchange resin is easily scattered and detached. The processed product prepared by forcibly drying after increasing the mixing ratio of the microfibrous compound did not leave the powder ion exchange resin even when a severe disturbance was applied. It has been found that it is possible to prepare a processed product including a powder ion exchange resin according to the purpose of use by utilizing this phenomenon.

The fine fiber compound of the present invention has a high moisture content, and ultrafine fiber particles having a fiber thickness of 1 micron, preferably 0.1 micron or less, and contains a large amount of water to prevent changes in physical properties. The powder ion exchange resin and the microfibrous compound are combined in a solution to form an aggregate, and adhere to the surface layer by being dispersed on a solid. The solution is centrifuged to obtain a solid substance containing a powder ion exchange resin. It was found that the powder ion exchange resin strongly adhered to the solid surface layer by forcibly drying the solid to dissipate moisture. The microfiber compound used in the present invention may be either a synthetic product or a product prepared by mechanically pulverizing plant fibers and forms a sol by binding with a powder ion exchange resin in a solution. Any compound having an ability may be used. For example, a certain amount of a microfibrous compound represented by microfiber cellulose (trade name: serisch) is present and homogenized in solution, so that the powder ion exchange resin and the microfiber cellulose particles are combined to form a powder ion exchange. It was found that a sol of resin and fine cellulose can be produced and dispersed throughout the solution to prepare a uniform liquid composition.

Although it has been described in paragraph “0004” that the processed product obtained by bonding the powder ion exchange resin with a commonly used polymer adhesive loses the adsorption function inherent to the powder ion exchange resin, it is described in the paragraph “0004”. As a raw material, I learned that it is possible to produce a processed product that maintains the unique functions of the powder ion exchange resin without causing the powder ion exchange resin and the support to adhere firmly and peel off.

In order to prepare the processed product, although it varies depending on the shape of the support of the powder ion exchange resin, the mixing ratio of the microfibrous compound and the powder ion exchange resin is important. The amount used is preferably 0 to 200% by weight, preferably 5 to 100% by weight, based on the weight of the powder ion exchange resin. The total concentration of the powder ion exchange resin and the microfibrous compound (hydrated product) is suitably 1 to 50% by weight with respect to the solvent weight. It is necessary to prepare a uniformly dispersed solution by stirring in a state where the powder ion exchange resin and the microfibrous compound are present in the solution at the mixing ratio described above. In order to disperse the fine fibrous compound having a high concentration in the solution, it is difficult to perform normal gentle stirring, and in order to prepare a liquid material having a uniform composition required in the present invention, strong stirring is preferable. It is important to homogenize. It was found that the homogenization treatment joined the powder ion exchange resin and the microfibrous compound to form a sol dispersed throughout the solution.

As the support of the powder ion exchange resin used in the present invention, as the surface area increases, a solid material having a shape that can easily hold the powder ion exchange resin is preferable. For example, a nonwoven fabric, felt, a nonwoven fabric sheet, diatomaceous earth, zeolite, activated carbon Foam stone, foam resin, etc. are used. It has been found that a significant difference occurs in the adhesive force between the liquid composition and the solid material by increasing or decreasing the amount of the fine fibrous compound added. That is, as the amount of the microfibrous compound added is decreased, the adhesion with the support decreases, and it has been found that it is difficult to form a long-term stable sol uniformly dispersed in the solution. By adjusting the addition amount of the microfibrous compound, it is possible to select, for example, firm fixation with solid matter, loose fixation, adhesion for only a short time, etc., as required, and this phenomenon is utilized. As a result, it was found that the application range of the powder ion exchange resin was expanded, and the present invention was achieved.

When spraying the liquid composition of the present invention, there was a clogging of the spray nozzle as the biggest difficulty, but by reducing the amount of microfibrous compound added to 10% or less of the amount of powder ion exchange resin , Found to prevent nozzle clogging. For example, in the case of using a powder ion exchange resin sprayed on the floor surface in anticipation of a deodorizing effect, the amount of microfibrous compound added is minimized and used by spraying to prevent clogging of the sprayer nozzle, I learned that there is no scattering of the powder ion exchange resin during the spraying operation, and that the floor surface can be easily cleaned, which is effective in practical use.

The solution used is advantageously water from an economic standpoint, but a hydrophilic organic solvent such as alcohol may be used, which not only prevents the growth of bacteria by using alcohol, but also powder ion exchange. It was found that the dispersibility of the resin was increased and the storage stability was improved. If necessary, plant extract components, fragrances, titanium oxide powder (nm size, photocatalyst), reverse soap, antiseptic / disinfectant, effective bacteria, and the like may be added. In particular, when used as a plant culture medium, mixing microbial pesticides, EM bacteria, fertilizers, and the like is a good method for increasing the added value as a product.

The microfibrous compound of the present invention is a compound having a characteristic that it is smaller than the specific gravity of the powder ion exchange resin, has a large specific surface area, is suspended and dispersed in a solution, and rapidly joins the powder ion exchange resin. A liquid composition prepared by vigorously stirring, preferably homogenizing, a mixture of a powder ion exchange resin and a microfibrous compound in a solution prevents precipitation of the powder ion exchange resin solid, A liquid composition is obtained in which an aggregate of gaseous compounds is uniformly dispersed in a solution. The microfibrous compound is excellent in that the adhesive force can be weakened by adhering the powder ion exchange resin and the solid without reducing the inherent function of the ion exchange resin, and reducing the mixing ratio of the microfibrous compound. Through experiments, it has been clarified that these characteristics are achieved.

A liquid composition capable of maintaining the functions unique to the powder ion exchange resin and controlling the adhesive force has been prepared, and by adhering the liquid composition to the support, the powder ion exchange resin can be used as required. A processed product with a wide range of applications that maintains the functions (regeneration and ion exchange). Using the liquid composition thus prepared as a raw material for processed products not only facilitates the production of processed products, but also, for example, as shown in Example 7, a significantly streamlined sugar manufacturing technology and powder ions As a result, the range of applications of powder ion exchange resins has been expanded, including technologies that facilitate the spraying of exchange resins.

Powder ion exchange resin, preferably a powder anion exchange resin and powder cation exchange resin, and a liquid composition that can be prepared for the first time by vigorously stirring, preferably homogenizing, a microfibrous compound in a solution and / or A processed product using the liquid composition as a raw material. For example, the powder ion resin-containing solid material prepared by applying the liquid composition to the surface layer of the powder ion exchange resin support, preferably spraying, is an easy-to-use air or water having an excellent function unique to the powder ion exchange resin. It is used in a wide range of purification agents such as toilet deodorants, pet deodorants, fish culture water purification materials, filter materials for purifying impure sugar solutions (such as sucrose solution and honey), and plant cultivation media.

The liquid composition of the present invention is a paste fluid that has a high content of powder ion exchange resin and is easy to handle, and adheres to the surface layer by mixing and stirring with a solid substance. To do. The solid substance containing powder ion exchange resin prepared by centrifugation after separating water by centrifugation is firmly bonded to the surface of the solid substance using the microfibrous compound as a medium without peeling. A filtration layer (membrane) having voids excellent in ventilation and water permeability is formed.

The liquid composition adheres the powder ion exchange resin to the surface layer by contacting the solid composition. At this time, it was found that the adhesive strength increases as the content of the microfibrous compound increases. For example, the liquid composition of the present invention containing 5% by weight or more of a microfibrous compound (hydrate) with respect to a powder ion exchange resin is reacted with the support and the powder ion exchange resin is attached to the surface of the support. It was found that, after removing the moisture by centrifugation or the like, the powdered ion exchange resin was firmly adhered to the support surface by forced drying, for example, blow drying at 60 ° C. or higher. By utilizing the powder ion exchange resin-containing support prepared in this manner as a filter element, a sugar production technology employing a new sugar refinement system was invented. That is, there is provided a powder ion-exchange resin-containing support that not only allows the flow of Bx70 high-viscosity sugar solution but also does not desorb due to severe disturbance, and a filter using the support as a filter element. provide.

When the liquid composition of the present invention becomes easy to handle, for example, when producing a filtration adsorbent that can be regenerated, a liquid composition with a high mixing ratio of the microfibrous compound is used as a filtration support (solid matter). ) And mixing and stirring. The powder ion exchange resin-containing solid material prepared by dehydrating the liquid containing the mixture with a centrifuge is subsequently dried with hot air (60 ° C.), so that the powder ion exchange resin is firmly adhered and detached. It became possible to prepare a filter material for decolorizing and purifying no sugar solution in a short time. Furthermore, the liquid composition of the present invention having a low mixing ratio of the microfibrous compound can be easily used as a deodorant by putting it in a spray. Used.

The liquid composition of the present invention can be applied to many solid materials including a porous support (eg, diatomaceous earth sintered product) while maintaining the purification function of the powder ion exchange resin. In addition to exhibiting its purification function efficiently and over a wide range, for example, by applying the processed product of the present invention, it can be applied to processes that were not possible with the prior art. For example, innovative sugar production technology ( Example 7) is provided.

By using an apparatus for applying the liquid composition, preferably a spraying apparatus, an operator can easily perform, for example, a work for providing a purification function of the powder ion exchange resin over a wide range inside the building. .

The present invention will be described in detail by the following examples, but is not limited by these examples.
Example 1

Powder cation exchange resin (trade name PK216: moisture about 50%, average particle size 17 microns, manufactured by Mitsubishi Chemical) prepared by mechanically pulverizing granular ion exchange resin and powder anion exchange resin (trade name PA312: about moisture) 50%, average particle size 15 microns, manufactured by Mitsubishi Chemical Co., Ltd.) 100 g was collected, and microfiber cellulose (trade name, serisch :) was added to an aqueous solution in which powder ion exchange resin mixed with 1,000 ml of water was suspended. After changing the amount to the following conditions: (A) 1,000 g, (B) 400 g, (C) 200 g, (D) 20 g, (E) 0 g, the mixture is stirred and preferably homogenized to produce powder ions A liquid composition comprising an exchange resin and a microfibrous cellulose was prepared. For each liquid composition, the physical property change at the time of storage was observed, and a basic experiment was conducted in order to produce a solid material including a powder ion exchange resin. The test results of (A), (B), (C), (D), and (E) are displayed.
Test results

Changes in physical properties of liquid compositions based on powder ion exchange resins

A
-Although it is difficult to prepare a uniform liquid composition with a normal stirrer, a uniform liquid composition is made in a short time by homogenization treatment.
-By homogenizing, a powder resin is uniformly dispersed in a sol, and the volume expands including bubbles, but the volume decreases with time, and the water is naturally dried to evaporate the powder. Firmly adheres to the solid and does not peel off.
・ The chemical adsorption / physical adsorption function of the powder ion exchange resin is great, but it is difficult to handle as a raw material because the sol shrinks and changes its volume.
-By blowing and drying (60 ° C.) the powder ion exchange resin-containing solid matter, the powder ion exchange resin adheres firmly and does not peel even when rubbed strongly.

B
-By homogenizing, a liquid composition in which the powder resin is uniformly dispersed can be easily formed, and the uniformity is maintained even after storage for several months, so it is easy to use as a raw material. There is no change in volume, and a processed product that adheres when in contact with a solid substance and is naturally dried does not peel off the powder ion exchange resin due to disturbance, but peels off when rubbed strongly.
・ Chemical adsorption and physical adsorption functions of powder ion exchange resin are large and can be easily regenerated.
-By blowing and drying (60 ° C.) the powder ion exchange resin-containing solid matter, the powder ion exchange resin adheres firmly and does not peel even when rubbed strongly.

C
・ Forms a liquid composition in which the powder resin is uniformly dispersed, but the powder ion exchange resin does not separate and settle even after long-term storage. The ion exchange resin has a large chemical adsorption / physical adsorption function and can be regenerated. However, at the time of regeneration, a part of the powder ion exchange resin is detached by backwashing and mixing operations.
-Adhesive strength with solids is weaker than A and B, and some powder ion exchange resins peel off by natural drying.
-By blowing and drying (60 ° C.) the powder ion exchange resin-containing solid matter, the powder ion exchange resin adheres firmly and does not peel even when rubbed strongly.

D
Forms a liquid composition in which the powder resin is uniformly dispersed, but when stored for several days or more, the aggregate of the anion / cation exchange resin separates and settles at the bottom of the solution, but disperses quickly by applying vibration to the solution. And become uniform.
-Adhesive strength with solids is weak and the chemical adsorption / physical adsorption function of the ion exchange resin is large, but most of the powder ion exchange resin is released by the regeneration operation.
-It has been found that there are significant operational advantages, such as not causing clogging of the spray nozzle when spraying on solids.
-Powdered ion exchange resin that has been sufficiently moistened and moistened is attached to the solid matter, but when it is dried and dissipates moisture, the adhesive strength is weakened and easily peeled off when rubbed.

E

・ By gently stirring, a liquid composition in which the powder ion exchange resin is uniformly dispersed can be easily formed, but the powder ion exchange resin begins to separate and settle immediately after the stirring is stopped. A lump is formed.
-When a powder cation exchange resin alone or a powder anion exchange resin was used alone, it was found that even if it was gently stirred, it was dispersed in the solution for several hours or more to maintain uniformity.
・ When spraying the liquid composition of the present invention containing powdered ion exchange resin as a main component using a nebulizer, there is no need to pack the nozzle by using it after stirring before use. .
-Powdered ion exchange resin that is sufficiently moistened and moistened is attached to the solid matter, but when it is dried and dissipates moisture, it is easily scattered by disturbance.


(Example 2)

Powdered cation exchange resin (trade name PK216: moisture about 50%, average particle size about 17 microns, manufactured by Mitsubishi Chemical) and powder anion exchange resin (trade name PA312: moisture) prepared by mechanically pulverizing granular ion exchange resin 100 g of about 50%, average particle size of about 15 microns, manufactured by Mitsubishi Chemical Corporation and 200 g of microfibrous cellulose (trade name, serisch: moisture 90%, FD-1000, Daicel Corporation) were added to 1000 ml of pure water. Thereafter, the mixture was homogenized with a high-speed rotary mixer for 2 minutes to prepare a liquid composition excellent in preservability and containing a powder ion exchange resin uniformly.

After storage for 1 month or more, a predetermined amount of 100 ml of the liquid composition corresponding to 20 g of powdered ion exchange resin is collected and applied to the surface of a non-woven sheet (polyester, 10 mm × 500 mm × 250 mm). A powder ion-exchange resin-containing sheet is prepared by air drying for hours. In order to verify the function of the composition of the present invention, the adsorption characteristics of typical malodorous components of ammonia, formic acid and formaldehyde were determined using this sheet (stored for 1 month after preparation). As a control, a test section using 20 g of a commercially available deodorized Bincho charcoal (the same amount as the powder ion exchange resin) and a powder cation exchange resin 20 g, and a single powder cation exchange resin use section prepared according to the above specifications, And the deodorizing effect in each test section was examined using a single use section of 20 g of powder anion exchange resin prepared in the same manner. As a control, 20 g of Bincho charcoal, which has been evaluated as a deodorant having an excellent deodorizing function, was used.
(experimental method)

A mixture of 10 g of the powder anion exchange resin and 10 g of the powder cation exchange resin prepared in Example 1, 20 g of the powder cation exchange resin alone, and the powder anion exchange resin at the bottom of a sealed container made of polypropylene having an internal volume of 200 liters An experimental group in which the sheet of the present invention prepared using 20 g alone was enclosed and a comparative experimental group in which 20 g of deodorized Bincho charcoal were installed were prepared. A predetermined amount of each odor component was injected into the sealed container of the experimental group, and a deodorizing sheet according to the present invention, an anion resin alone, a cation exchange resin alone, and a comparative test with the experimental group using Bincho charcoal were conducted. The initial concentration was set as an initial value by injecting a predetermined amount into a sealed container, allowing it to stand for 1 hour and then diffusing into the room, and measuring the value when it became constant. At predetermined intervals, a detection tube was set in the sampling hole, and the fluctuation of the odor component content in each experimental section container was measured.
(Test results)

・ Adsorption characteristics of ammonia

Elapsed time Initial concentration
10 minutes
20 min
Half an hour

Charcoal
500ppm
0.5ppm
0.3ppm
0.025ppm

Yin Yang powder ion exchange resin mixture
500ppm
0.04ppm
0.02ppm
ND

Powder cation exchange resin alone
500ppm
0.3ppm
0.1ppm
0.01ppm

Powder anion exchange resin alone
500ppm
0.5ppm
0.3ppm
0.025ppm

2. Formic acid adsorption characteristics

Elapsed time Initial concentration
10 minutes
Half an hour
60 minutes

Charcoal
60ppm
0.9ppm
0.85ppm
0.85ppm

Yin Yang powder ion exchange resin mixture
60ppm
0.3ppm
0.2ppm
0.1ppm

Powder cation exchange resin alone
60ppm
1.5ppm
1.3ppm
1.2ppm

Powder anion exchange resin alone
60ppm
0.3ppm
0.2ppm
0.1ppm

3. Formaldehyde adsorption characteristics

Elapsed time Initial concentration
Half an hour
60 minutes
120 minutes

Charcoal
5ppm
0.8ppm
0.6ppm
0.4ppm

Yin Yang powder ion exchange resin mixture
5ppm
0.4ppm
0.1ppm
0.1ppm

Powder cation exchange resin alone
5ppm
0.8ppm
0.6ppm
0.4ppm

Powder anion exchange resin alone
5ppm
0.6ppm
0.2ppm
0.2pm

(Discussion)

As is clear from the test results, the sheet prepared by spraying the composition of the present invention mainly composed of a mixture of anion and cation powder ion exchange resin has the best deodorizing ability, powder cation exchange resin, powder anion It was found that the sheet prepared using the exchange resin alone was also superior to the Bincho charcoal adsorption function.

For all components such as ammonia, formic acid and formaldehyde, the sheet containing powder ion exchange resin is not only a mixture of powder anion exchange resin and powder cation exchange resin, but also powder anion exchange resin alone, powder cation exchange The adsorption function of either resin alone exceeded that of Bincho charcoal, and it was found that there was no significant difference due to the difference in exchange groups. This indicates that the bad odor adsorption function by the powder ion exchange resin is larger than the chemical adsorption by the ion exchange action by the ion exchange group, and the physical adsorption action by the fine structure is larger. It was a good result. Even when the mixing ratio of both ion exchange resins was 1:10 to 10: 1, the adsorption capacity did not change greatly.

In parallel with this experiment, several types of sheets were prepared by varying the amount of microfibrous cellulose used, and the adhesion to solids was investigated. When dried, the powder ion exchange resin is easily peeled off, and the powder ion exchange resin is scattered by disturbance. By increasing the amount of fine cellulose used to nearly the same amount as that of the powder ion exchange resin, the adhesion is remarkably improved, it does not peel even when a disturbance is applied, and the amount of fine fibrous cellulose added is 10% or less. It was found that the amount of adhesion was significantly reduced. Prepare solid powder ion exchange resin-containing solid that adheres firmly and is stable, or prepare powder ion exchange resin-containing solid that adheres only for a short period of time and easily peels off by applying a disturbance. It has been found that it is important to adjust the mixing ratio of fibrous cellulose.

When an anion / cation powder ion exchange resin is mixed in an aqueous solution, both of them aggregate, and for example, when a sprayer is used as a coating device, the nozzle may be clogged. In this case, the powder ion exchange resin can be used alone, or the mixing ratio can be reduced to make it difficult to form aggregates, or the mixing ratio of the microfibrous compound to the powder ion exchange resin can be reduced. It was found that the operational difficulties caused by clogging were eliminated.
(Example 3)

Strong basic powder ion exchange resin (water content about 50%, average particle size about 15 microns, Mitsubishi Chemical PA316) 8kg and strongly acidic powder ion exchange resin (water content about 50%, average particle size about 17 microns, Mitsubishi Chemical PK216) ) 2 kg of microfibrous compound (trade name, serisch, FD1000, Daicel Industrial Co., Ltd.) was added to 10 l of tap water and homogenized with a high-speed rotary mixer for 1 minute to uniformly disperse the water. An inventive liquid composition was prepared. 10 ml of the liquid composition was sampled, diluted to 100 ml with water, and then sprayed on 1 kg of porous mineral (diatomaceous earth sintered granulated product: average particle size 0.5 mm, Showa Chemical Industry Co., Ltd.) to exchange powder ions It was found that a resin-containing adsorbent can be easily manufactured.

When the liquid composition of the present invention is sprayed on the diatomaceous earth sintered granulated product, the liquid composition is occluded instantaneously inside the pores, and the powder ion exchange is a particulate solid simultaneously with the absorption of water. The resin and the microfibrous compound are occluded inside the pores, and the powder ion exchange resin is not leaked. In order to remove excess moisture occluded inside the pores, by carrying out air drying at 60 ° C., the powder ion exchange resin is firmly adhered to the surface layer / pores inside the diatomaceous earth flow product, and the surface layer is Even when a disturbance such as rubbing was applied, the powder ion exchange resin was not peeled off in the outside air.

By using the powder ion exchange resin-containing liquid composition, the spraying device, and the diatomaceous earth sintered granulated product disclosed in the present invention, the industrial value of facilitating the production of the powder ion exchange resin-containing processed product is great. .

This deodorant has a good appearance and is excellent in removing ammonia odor, organic acid odor, formaldehyde odor, especially butyric odor, which is a typical bad odor, and sealed space (dog house, pet house for cats, hospitals, toilets) When used in a refrigerator, etc.), it exhibits an excellent deodorizing function, and when used in water, it functions as an excellent filter medium for removing pigments and suspensions.
Example 4

For the purpose of effective use of resources, a cheaper powder ion exchange resin-containing filter adsorbent was manufactured using ion exchange resin recycled products and felt recycled products.
10 g of strongly basic powder anion exchange resin (water content 50%, average particle size 15 microns), which is a recycled product of used granular strong basic ion exchange resin, and strongly acidic product, which is a recycled product of used granular strong acid ion exchange resin After adding 10 g of powder cation exchange resin and 2 g of a microfibrous compound (trade name, serisch, moisture 90%, Daicel Corporation) to 200 ml of water, the liquid composition of the present invention is prepared by homogenization treatment. The liquid composition is sprayed on felt pieces having a length of 50 to 100 mm, and a powder ion exchange resin is included inside the felt gap. (The felt shredded pieces are recycled products out of the frame form of automobile seats, which are generated in large quantities as industrial waste, and effective use is strongly desired).

The felt is dehydrated with a centrifugal separator and then blown and dried at 70 ° C. to produce a powder ion exchange resin-containing filter adsorbent. The mixing ratio of the microfibrous compound used in the adsorbent is minimized with respect to the weight of the powder ion exchange resin, so that the powder ion exchange resin adhering to the surface layer easily peels off due to severe disturbance, for example, ion The powder ion exchange resin is removed by backwashing and mixing operations in the regeneration operation of the exchange resin. (By increasing the mixing ratio of the microfibrous compound, the detachment of the powder ion exchange resin can be prevented, but the powder ion exchange resin and felt crushed pieces used in the present invention are recycled products as cheap as possible. The emphasis was on being able to produce a cheaper filter medium for using a disposable powder ion exchange resin-containing filter adsorbent as a deep-layer filter medium.)

5,000 ml of the powder ion exchange resin-containing filtration adsorbent was packed in a stainless column (inner diameter: 10 cm × height: 25 cm), and passed through the artificial hot spring / bath water at a flow rate of 500 l / h. As a result, the turbidity is remarkably reduced, and the turbidity of the feed water is about 10 or less. After 3 months, the quality of the column effluent does not change and the clarified liquid can be produced stably. I understood that. It is difficult to apply under severe disturbance conditions, but exhibits excellent functions as a water purifier when it passes only in a gentle laminar flow area without accompanying severe disturbance operation (regeneration operation of powder ion exchange resin). In addition, it has been found that the economic effect of effective use of resources is great. For example, when applied to purification of hot spring water, circulating bath water, and pool circulating water as a deep-layer filter material, it is clear that the water quality with excellent clarity is maintained over a long period of time without detachment of the powder ion exchange resin. Became.
(Example 5)

10 g of used strongly acidic powder ion exchange resin (water content about 50%, average particle size about 17 microns, Mitsubishi Chemical PK216) and used strong basic powder ion exchange resin (water content about 50%, average particle size about 15 microns, 10 g of Mitsubishi Chemical PA316) was added to 1,000 ml of water, and the liquid composition (A) in which the microfibrous compound (trade name serisch, 90% water, Daicel Corporation) was completely removed, and 2 g of the microfibrous compound were used. Using the test group with (B), 5 g added: (C), with the test group added with 10 g: (D), homogenized, mixed and stirred to prepare 4 types of liquid compositions To do. 200 ml of this liquid composition is collected in a small manual sprayer, and a small amount of about 10 ml is sprayed once a day around the small animal breeding box to produce malodors such as ammonia odor generated from the excrement of small animals. And the ability to remove butyric acid odor was investigated.

The liquid composition mainly composed of the powder ion exchange resin according to the present invention has a small spray amount and the test section (A), (B) or (C), (D) in which the microfibrous compound addition ratio is changed. There was no significant difference in deodorizing ability, and even in the case of additive-free (A), the deodorizing effect was not inferior, and the powdered ion exchange resin was not easily scattered by the movement and flapping of the concerned small animals. In the case of this experiment, it was an experiment for verifying the function of a small hand spray, and it was used after shaking the liquid composition in any test section. (D) In the test section, the number of sprays was increased. Each time it took 10 ml to spray and the fifth spray sprayed the spray nozzle.

A small amount of spraying is required, and when using the liquid composition of the present invention based on the powder ion exchange resin as a main component by using a spray, it is not necessary to strongly fix the powder ion exchange resin to the solid to be sprayed. It has been found that it is practical to apply a liquid composition in which the addition amount of the microfibrous compound is reduced, and the adhesive force with the solid substance can be controlled by adjusting the addition amount of the microfibrous compound. Therefore, when it is disposable and does not require strong adhesion, use the liquid composition of the present invention in which the addition amount of the microfibrous compound is reduced as much as possible, and the powder anion exchange resin alone or the powder cation exchange It has also been found that by using a liquid composition in which the formation of aggregates is suppressed by using the resin alone, clogging of the spray nozzle is suppressed. In order to expand the application range of the powder ion exchange resin, it is important to apply the liquid composition of the present invention as necessary.

As is clear from the test results of Example 2, the deodorizing ability of the powder ion exchange resin is not inferior even if it is superior to Bincho charcoal, even if the cation exchange resin alone or the anion exchange resin is used alone. When the liquid composition of the present invention is used as a deodorant using a hand spray, a fine fiber can be obtained by using a powder anion exchange resin alone or a powder cation exchange resin alone with little aggregation and adhesion of fine powder. It was found that the use of a liquid composition containing a powdered ion exchange resin without adding a glassy compound was a good usage method that solved the difficulty in operability.
(Example 6)

1 g of H-type strongly acidic powder ion exchange resin (water content about 50%, average particle size about 17 microns, Mitsubishi Chemical PK216) and OH type strongly basic powder ion exchange resin (water content about 50%, average particle size about 15 microns, 20g of Mitsubishi Chemical PA316) and fine fibrous compound (water 90%, FD-1000, Daicel Corporation, 1g) and 0.5g of benzoic acid (preservative) are added to 100ml of ethanol and processed for 2 minutes with a high-speed rotary mixer. Thus, a liquid composition is obtained in which the yin / yang powder ion exchange resin is uniformly dispersed in water.

The liquid composition is diluted with water at the time of use to a concentration suitable for spraying, for example, 1,000 ml. The diluted solution was put into a spraying device, and a predetermined amount could be sprayed and used in places where bad odors were generated (such as spoiled odor generated from the trash can). The composition of the present invention is a liquid fluid and can be easily measured. The composition of the present invention can be easily collected and used in an appropriate amount as required. As it becomes easier to spray the required amount as needed, the application range of powder ion exchange resin is expanded and supports various sheets and floors, including filters that remove harmful components of air and water. It is now possible to use powder ion exchange resin by spraying it over a wide range of bad odor occurrence sites such as the body, containers and toilet walls. As is apparent from the above-described embodiments, the liquid composition and processed product of the present invention for purifying water and air containing a wide range of malodors are provided.
(Example 7)

(experimental method)
Chlorine type strongly basic powder anion exchange resin (water content about 50%, average particle size 15 microns) 100g
In addition, 100 g of a microfibrous compound (90% moisture, an equal mixture of PC110S and FD1000, Daicel Industrial Co., Ltd.) was mixed with 10,000 ml of water and homogenized for 2 minutes to prepare a liquid composition of the present invention. The liquid composition is charged with 10,000 ml (100 g) of a radial spherical felt made of polyester nonwoven fabric (specially developed by Aoyama Sangyo Co., Ltd., diameter, about 10 mm), and gently mixed to form the interior space of the nonwoven fabric. After applying the powder ion exchange resin to the surface layer, it was blown and dried at 80 ° C. for 2 hours after dehydration to prepare a spherical support in which the strongly basic powder ion exchange resin was firmly adhered to the felt fiber surface layer. It was also found that this support contained a large amount of powder ion exchange resin and did not peel off, and it was possible to treat a high concentration sugar solution of Bx70. In this way, a non-woven filter material (A) having a purification function unique to powder ion exchange resins that was not found in existing filter media was prepared.

Powdered anion / cation exchange resin (average particle size 20 microns) and fine fibers prepared by mechanically grinding 10 kg of strong basic ion exchange resin used in refined sugar factories and 2 kg of weak acidic cation exchange resin Cellulose 0.2 kg was mixed in 20 l of water and homogenized to prepare a liquid composition (a) of the present invention. A liquid composition (b) corresponding to an aqueous solution (predetermined concentration) containing 1% of the used strong basic anion exchange resin is obtained by collecting 2 l of the liquid composition (a) and diluting with water to 100 l. ) Was prepared.

The non-woven filter medium (A) including the powder ion exchange resin is packed in a filter tower (inner diameter: 8 cm × height: 50 cm), and the filter medium (A) has a layer height of about 40 cm and a garnet with a layer height of 5 cm at the bottom. A laid filter bed was provided. Using concentrated juice, which is an intermediate sugar solution of sugarcane raw sugar factory, as a supply liquid, a liquid passing test was carried out using a metering pump in the filtration tower under the following conditions.

Concentrated juice purification step: About 20 liters of the concentrated juice was heated at a temperature of 70 ° C. in a downward flow, and passed at a flow rate of 2 (l / hr) using a metering pump. A filtrate from the filtration tower is obtained. While measuring the color value of the filtrate discharged from the filtration tower, the liquid composition (b) is added using a metering pump to produce a clean sugar solution maintaining a certain quality (in the prior art, this is the case). It was difficult to filter the impure sugar solution). That is, by supplying the liquid composition in a variable amount of about 0.1 to 0.5 (l / hr), a supply sugar solution of the nonwoven fabric filtering material (A) maintaining a predetermined quality is prepared.

Add a small amount of liquid composition (b) consisting of used powder ion exchange resin, which is an inexpensive recycled product, and use it for only one cycle, then dispose of it, and powder ion exchange resin A purification system for an impure sugar liquid characterized in that it is passed through the main process using the filter medium (A), which is regenerated and repeatedly used, and is a new sugar-making technology disclosed for the first time.

After passing through the solution for about 10 hours, the purification step is completed, followed by desugaring by a conventional method, followed by backwash mixing. In this step, the used powder ion exchange resin used in the liquid composition (b) is discharged together with backwash water without being reused. Subsequently, it moves to the regeneration process of the powder ion exchange resin included in the filter medium (A).

Regeneration process: As a regenerant, 20 l of 0.1% hydrochloric acid aqueous solution heated to 70 ° C. is passed in an upward flow using a metering pump. By this operation, most of the impurities such as pigments and suspensions are desorbed from the filtration adsorption layer to regenerate the powder ion exchange resin. In the washing operation, sodium carbonate is added to increase the washing efficiency and adjust the pH of the effluent to neutral. Such a purification / regeneration process was repeated to conduct a flow test for 10 cycles. The test results are shown as an average value of 10 cycles.
(Test results)

Bx
pH
Ash content Color value
ICUMSA
OD
T720nm1cm
Pure sugar rate Inverted sugar S.S amount
on solid

Supply liquid sugarcane sugar concentrate
59.5
5.7
4.0
21,390
0.293
87.6
2.4
0.29

Purified liquid according to the present invention
59.6
6.5
3.6
4,780
0.010
88.5
2.4
0.001

(Discussion)

The operation of filtering and cleaning sweet potato sugar juice has been required for a long time, but there was no appropriate method from an economic point of view.

In the processed product of the present invention, the amount of the microfibrous cellulose is increased to almost the same amount as the weight of the powder ion exchange resin, so that the joined product of the powder ion exchange resin and the microfibrous cellulose has a nonwoven fabric support as a core. This is probably due to the fact that an incompressible filtration adsorbent bed that adheres firmly and does not peel off due to a disturbance caused by a regeneration operation and allows the passage of a high-viscosity sugar solution with a large amount of impurities.

By using the liquid composition of the present invention, it has become easy to accurately add a strongly basic powder ion exchange resin essential for cleaning a sugar solution. By increasing or decreasing the amount of powder ion exchange resin added according to the properties in the supply liquid and using an inexpensive used powder ion exchange resin for the liquid composition (b), it is efficient at low cost. It is possible to adsorb and remove impurities such as pigments and suspensions, and to produce a purified sugar solution that maintains the required quality (this process uses the liquid composition of the present invention). This made it possible for the first time since quantitative sampling of powder ion exchange resin became easier.

It has been found that the filter medium of the present invention maintains the purification ability over many cycles without causing the powder ion exchange resin to peel off and disengage even in a regenerating operation involving severe disturbance (back washing). By applying the filtration adsorption tower of the present invention that retains the unique function of powder ion exchange resin and has low flow resistance, a sugar solution containing a large amount of difficult-to-filter impurities that was previously impossible It has become possible to carry out a decoloration purification filtration operation of sugar solution, crude honey and the like. Industrial value by applying this operation is great.
-The purified liquid of the present invention provides a new type of liquid sugar, saccharose.
・ It can be easily estimated that it is possible to apply it to various juices in mixed sugar juices and refined sugar factories, which are dilute sugar liquids, because it has become feasible with sugarcane sugar concentrates.

Claims (3)

A liquid composition comprising a powder ion exchange resin as a main component, wherein a mixture containing a powder ion exchange resin and a microfibrous compound is mixed and stirred in a solution and uniformly dispersed. A powder ion exchange resin characterized in that the powder ion exchange resin is adhered to the surface layer of the previous support by contacting and reacting with the solid material to be the support of the substrate, adhering to the previous support, and then dehydrating and drying. Processed product consisting of inclusion support. The liquid composition according to claim 1 is a liquid composition prepared by stirring a mixture in which a fine fibrous compound (hydrate) is prepared in an amount of 5 to 100% by weight in a powder ion exchange resin in an aqueous solution. The liquid composition is contacted and reacted with the support, and after the powder ion exchange resin is adhered, the powder ion exchange resin is firmly adhered to the surface layer of the support by dehydration and forced drying. The powder ion exchange resin-containing support according to claim 1 is used as a filter element to pass through an impure sugar solution to decolorize and purify, and the powder ion exchange resin is regenerated to repeat multiple cycles. A method for purifying a sugar solution, characterized by being used. The liquid composition according to claim 1 is a liquid composition prepared by stirring, in an aqueous solution, a mixture in which a fine fibrous compound (hydrated material) is prepared to 10% by weight or less with respect to a powder ion exchange resin. A method of using a powder ion exchange resin, wherein the liquid composition is sprayed and used.