JPH0822366B2 - Solid desiccant with deodorizing function - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to a solid state with a deodorizing function which simultaneously exhibits moisture absorption and odor absorption effects in a predetermined space and is provided with an indicator capable of accurately confirming the end of the moisture absorption capacity. Regarding desiccant.

"Prior Art" Common desiccants conventionally used include calcium chloride, silica gel, and a composite desiccant mainly containing them. However, calcium chloride becomes liquid due to deliquescent action due to moisture absorption, and there is concern that it will affect the material to be dried.Silica gel does not change due to moisture absorption, but its moisture absorption capacity is small and its performance as a desiccant is sufficient. Not satisfied. Therefore, research and development of composite desiccants have been promoted in various fields, but the following techniques have been disclosed as related techniques.

In order to significantly improve the hygroscopic ability, a dry dehumidifying material characterized by containing a Si source, a chloride and a binder has been developed (JP-A-59-160533).

High-temperature activation treatment of zeolite enhances hygroscopicity (JP-A-58-36918, JP-A-59-160533, JP-A-61-293548) Calcium chloride and There are commercially available desiccants that use a gelling method using a combination of water absorbent resins or a color changing method using a combination of silica gel and cobalt chloride. However, in all cases, the end of moisture absorption of the desiccant does not coincide with the indicator, and the present situation is that no one having satisfactory moisture absorption capacity has been proposed.

"Technical problem to be solved by the invention" As described above, many conventional desiccants have been developed for commercial and industrial use, and are multi-functional and end-of-effectiveness indicators that can be easily used in ordinary households. There were no functional and practical desiccants.

At present, not only humidity but also odor damage is a problem when storing and storing objects in an environmental space. However, it is considered that the problem of dehumidification and the problem of deodorization are different problems.The dehumidifying action is performed by the desiccant, and the deodorizing action is performed by the deodorant. The current situation is to prepare and deal with it. However, in general, there is no desiccant having an idea of simultaneously removing water (moisture) in a predetermined space and deodorizing.

Further, although attempts have been made to provide an indicator for judging the effectiveness of the desiccant, none of them has an indicator that can be accurately confirmed by any person without training for the end of moisture absorption.

The inventor has earnestly studied in order to realize a multifunctional solid desiccant that simultaneously solves these technical problems, and as a result, obtained the following findings.

It has been found that zeolite that is crushed and subjected to high temperature activation treatment so as to have a moisture absorption and an odor absorbing effect is suitable as a substance that simultaneously exhibits the moisture absorbing and odor absorbing effects in a predetermined space. Although there is a document that describes high-temperature activation treatment of zeolite as described above, JP-A-58-36918 discloses a zeolite NaA-type zeolite granule, a method for producing the same, and an insulating glass window for the same. The method used for the production of
The 533 publication describes the use of a heat-activated zeolite reformer in a method for removing a trace amount of carbon dioxide in industrial gas used for semiconductor production, and further, JP-A-61-29354.
No. 8 discloses only the use of a zeolite in which ions have been subjected to an ion exchange-supporting activation treatment as a carbon monoxide separating / adsorbing agent. None of the above-mentioned documents describes or contemplates a desiccant which is an extremely technical and industrial technique and exerts moisture absorption and odor absorption effects at the same time.

It was found that the powdery or granular material of calcium chloride crushed and subjected to high temperature treatment so as to have a hygroscopic effect simultaneously fulfills the following three roles.

First, the hygroscopic ability can be improved by combining with zeolite. Secondly, by kneading with an appropriate amount of water, it becomes a binder, and a binding force capable of maintaining a molded body is generated only by compression-molding zeolite or bentonite, which can serve as a binder. Furthermore the third
The combination of calcium chloride and bentonite can be used as an indicator of a swelling-disintegrating method capable of accurately confirming the end of the hygroscopic action of calcium chloride.

Bentonite, which is made of colloidal clay to swell and soften and disintegrate the molded body due to the hygroscopic effect, swells bentonite with an aqueous solution produced by deliquescent calcium chloride as the hygroscopic effect progresses, and the hygroscopic effect ends. At times, the molded body can be disintegrated by the swelling of bentonite.

Based on such findings, the present inventor pulverized and subjected to high temperature activation treatment to have a moisture absorbing and odor absorbing effect, and pulverized and subjected to high temperature treatment to have a moisture absorbing effect. Binders made by kneading calcium chloride powder or granules with water and bentonite made of colloidal clay to swell and soften and disintegrate the molded body due to moisture absorption are selected as materials and kneaded. To form a kneaded and blended material, which is then compression molded into an arbitrary shape and formed into a molded body by the binding force of the binder, thereby exhibiting moisture absorption and odor absorption effects at the same time, and moreover, it is possible to accurately confirm the end of the moisture absorption capacity. It has been found that a solid desiccant with a deodorizing function provided with an indicator of a swelling and disintegrating method can be embodied.

The technique described in JP-A-59-160533 is a dehumidifying material in which chloride is supported, but the hygroscopic performance is improved, but since the chloride becomes an aqueous solution due to moisture absorption, the dehumidifying material retains water. Performance has a great influence on the moisture absorption capacity of the dehumidifying material. Therefore, we selected a water-retaining Si source as the dehumidifying material,
By supporting chloride on this, the moisture absorption capacity of the dry dehumidifying material is significantly improved, and the other is that the binder may exert an adhesive function, either an organic binder or an inorganic binder. .

The publication describes zeolite as an example of Si source, calcium chloride as an example of chloride, and bentonite as an example of binder. However, there is no specific description when these three materials are combined. Therefore, the reasons for selecting the three materials and the technical contents of the dry dehumidifying material in which these three materials are combined can be understood to be the same as the technical contents of the other embodiments described in the specification. That is, the technology disclosed in the publication is to produce a zeolite molded body (honeycomb or linear) in which a deliquescent dehumidifying agent calcium chloride is supported on a water-retaining Si source dehumidifying agent zeolite to obtain chloride It is considered to be a technology that can solve the technical problems caused by deliquescent and realize a dry dehumidifying material with improved hygroscopicity as a whole. Regarding the role of the binder bentonite, it is disclosed that it is used as a sintering aid when firing the zeolite molded body according to a conventional method. Because, in order to form and maintain a molded body of a predetermined shape while maintaining the function of zeolite using bentonite as a binder, there is no other way than sintering with bentonite as a sintering aid with heat of 700 degrees or less, which is the usual method. He. Further, in the specification, "in the case of a dry dehumidifying machine that recycles by heating and regenerating, it is preferable to select an inorganic binder from the viewpoint that there is no deterioration of the binder component by heating.
10 claim) ”, and it is described that a zeolite molded body (honeycomb, linear) is fired using an inorganic binder bentonite. This clearly plays the role of the inorganic binder bentonite as a sintering aid at the time of firing, maintains the strength that the zeolite molded body does not break even if the moisture absorption action starts after firing, and regenerates it many times. It is not intended to be used. As you know, bentonite is
It has the property of becoming an insoluble substance when fired at a prescribed temperature or higher, and does not destroy the zeolite molded body, so that it functions as a binder forever. Bentonite does not have a strong adhesive force as it is, and when it absorbs moisture, it swells and its shape becomes large, rather it becomes an element that collapses the constitutional structure of the molded body, and its suitability as a binder is
There is nothing but a sintering aid.

That is, from the publicly known literature, about the fact that the dehumidifying and deodorizing functions of zeolite by high-temperature activation treatment occur, calcium chloride also serves as a binder, and bentonite swells due to the hygroscopic effect to soften and disintegrate the molded body. Also, regarding that it becomes an indicator that can accurately confirm the end of the hygroscopic effect of the desiccant,
There is no description at all.

INDUSTRIAL APPLICABILITY The present invention utilizes the knowledge based on the research on the characteristics of the selected materials and the combination effect as described above, and simultaneously performs both the amount of the hygroscopic action and the deodorizing action, and the indicator of the end of the hygroscopic action coincides. The aim is to provide a functional solid desiccant.

"Means for Solving the Problem" The present invention takes the following means in order to solve the above problems.

100 parts by weight of zeolite powder or granules that have been crushed and subjected to high temperature activation treatment to have a hygroscopic and odor absorbing effect, and pulverized and subjected to high temperature treatment to give a hygroscopic effect of calcium chloride powder Bentonite consisting of 16-30 parts by weight of a body or granules and 15-25 parts by weight of water and 15-40 parts by weight of a binder, and a colloidal clay for swelling and softening and disintegrating a molded body due to a hygroscopic effect 10-40 parts by weight The kneading and blending material obtained by kneading the parts with each other is compression molded into an arbitrary shape to form a molded body by the binding force of the binder, and bentonite swells with the aqueous solution produced by deliquescent calcium chloride as the hygroscopic action progresses. However, it is a solid desiccant having a deodorizing function, characterized in that at the end of the moisture absorption reaction, the molded body is made to disintegrate due to swelling of bentonite.

[Examples] Hereinafter, the present invention will be described in detail based on illustrated examples.

The present invention is an invention of a solid desiccant having a deodorizing function.

FIG. 1 is a perspective view showing a solid desiccant having a deodorizing function according to the invention of the present application, and FIG. 2 is an enlarged cross-sectional explanatory view showing a constitutional state of the desiccant.

In the figure, 1 is a powder or granular material of zeolite that has been crushed and subjected to a high temperature activation treatment so as to have a hygroscopic and odor absorbing effect, and 2 is swollen by the hygroscopic effect to soften and collapse the molded body. Bentonite composed of colloidal clay for making the powder 3 is a powdery or granular body of calcium chloride crushed and subjected to high temperature treatment so as to have a hygroscopic effect. The calcium chloride 3 is kneaded with an appropriate amount of water. Then, it is used as a binder for binding these constituent materials. Zeolite 1 having the moisture absorbing and odor absorbing effects is obtained by pulverizing and performing high temperature activation treatment. Zeolite 1 has peculiar properties such as strong hygroscopic action, deodorizing action, ion exchange ability, and catalytic action when subjected to high temperature activation treatment. The present invention focuses on the strong and strong hygroscopic action and deodorizing action among the characteristics of such zeolite 1, and does not embody a desiccant that simultaneously performs moisture absorbing and deodorizing action by using this as a seed material. is there. Conventionally, it is not without exception that it is a desiccant that utilizes the hygroscopic effect of the zeolite 1.
There is a fact that it is used as an industrial desiccant. However, since these are for business use, it is always required to maintain a predetermined strong hygroscopic capacity, and they are usually used in combination with a maintenance service by a specialist. For this reason, the crushed zeolite 1 is used as it is as a desiccant raw material without being specially processed, such as by being stored in a container, and the change in its moisture absorption capacity is measured with a dedicated instrument or device and kept constant. Replace it with a new desiccant as soon as it falls below the standard, or replace it with a new desiccant as soon as possible after a certain period of time depending on usage conditions, regardless of whether the moisture absorption capacity actually drops. Is used.

In this case, it is not possible to use it for general household use because it requires a large number of instruments and devices and requires specialized knowledge, and it has not been able to be commercialized as a solid type desiccant molded into an appropriate shape that is easy to handle. Especially zeolite 1
Only by itself, even if the moisture absorbing action progresses and the saturated state is reached and the moisture absorbing action ends, the shape hardly changes, so it is difficult to understand from the outside. For this reason, it is easy to find out when to replace it, and it is easy to use it without knowing until after the end of the moisture absorption action. Due to such inadequacy of handling, even when various troubles such as generation of mold occur, it is easy to misunderstand that the desiccant itself has a defect in the product.
Therefore, for example, the present invention has commercialized a swelling-disintegrating type solid desiccant which can be easily used by ordinary people such as housewives, children, and the elderly to easily understand the progress of the hygroscopic effect and the odor absorbing effect. is there. That is, an attempt was made to commercialize a solid desiccant which is easy to handle, while zeolite having moisture absorbing and odor absorbing functions is provided with an accurate and easy-to-understand indicator function by swelling and disintegration which is easily understood even by an amateur. That is, the solid desiccant 4 of the present invention is mainly composed of a powdery or granular material of zeolite 1 which has been crushed and subjected to high temperature activation treatment, and a bentonite composed of colloidal clay having water retention and swelling properties. 2 was added, and the mixture was subjected to high temperature treatment, and a powdery or granular material of calcium chloride 3 having a strong hygroscopic effect and deliquescent property was kneaded with water to give a binding force, and calcium chloride 3 was used as a binder for zeolite 1 or The bentonite 2 is bound to form a correct solution. As described above, calcium chloride 3 has a strong hygroscopic property and also has a property of producing a binding force by kneading with an appropriate amount of water,
It has the property of liquefying due to deliquescent action as the moisture absorption action progresses.
Therefore, the strong hygroscopicity of the calcium chloride 3 and the hygroscopicity of the above-mentioned zeolite to be combined can provide the desiccant with a strong hygroscopic force and a large hygroscopic ability. Further, by utilizing the property that a binding force is generated when kneading calcium chloride 3 with an appropriate amount of water, a material such as zeolite 1 or bentonite 2 can be simply compression molded by using this as a binder to form a solid compact. can do. Further, by combining calcium chloride 3 having the property of gradually deliquescing and liquefying with the progress of moisture absorption and bentonite 2 having the property of swelling by retaining water of the liquid, the progress of moisture absorption deliquescent action of calcium chloride 3 and bentonite Calcium chloride 3
Preparation is made so that the end of the moisture absorption deliquescent action of and the collapse of the molded body due to the swelling of bentonite 2 occur almost at the same time. That is,
The swelling of the bentonite 2 is a phenomenon that is caused by sucking in the water which has absorbed moisture of the zeolite 1 and exceeded the saturated state, and the liquid in which the moisture absorbing action of the calcium chloride 3 has progressed to become liquid and which has no further moisture absorbing ability. Therefore, the disintegration of the molded body due to the swelling of bentonite 2 can be an indicator that accurately indicates that the moisture absorption effect of zeolite 1 and calcium chloride 2 has ended.

The present invention further matches the collapse of the molded body due to the swelling of bentonite 2 with the timing at the end of the moisture absorption reaction of zeolite 1 and calcium chloride 2 as much as possible, so that an accurate indicator function is always exhibited. In order to do so, we are making various preparations. It is a kneading compounding material in which the main constituent materials are powdery or granular, the compounding weight ratio of each constituent material is numerically limited, and these are well kneaded to be uniform.
The kneaded and blended material was compression-molded by the binding force of calcium chloride 3 to obtain a molded body. In other words, it is a molded product which is accurately disintegrated by a decrease in binding force due to deliquescent calcium chloride 3 and swelling of bentonite 2.

The mixing ratio of each material at this time is 100 parts by weight of the powdery or granular material of zeolite 1 which has been crushed and subjected to high temperature activation treatment so as to have a moisture absorbing and odor absorbing effect. A binder obtained by kneading 16 to 30 parts by weight of a powdery or granular material of calcium chloride 3 with 15 to 25 parts by weight of water and having a hygroscopic effect, and swelling due to the hygroscopic effect to soften the molded body. This is a kneading compounding material by kneading with 10 to 40 parts by weight of bentonite made of colloidal clay for disintegration. If the amount of calcium chloride 3 is larger than that of zeolite 1, the water absorbed by calcium chloride 3 and the water A liquefied by the deliquescent action cannot be adsorbed and retained on zeolite 1 and flow out as excess water. Further, since the water content A plays a role of dispersing calcium chloride 3 and a role of binder of zeolite 1, bentonite 2 and calcium chloride 3, an appropriate addition amount is determined according to the blending ratio of these raw materials. It is a thing. Further, the bentonite 2 uses the swelling and softening property due to the moisture A generated by its hygroscopic action as the first
Therefore, the above-mentioned compounding ratio is within the allowable range.

A solid desiccant 4 having a deodorizing function is formed by compressing and forming this mixed compound material into an arbitrary shape with a mold or the like so as to surely disintegrate at the timing when the hygroscopic action is completed.

<Examples> 12 sets of raw materials are prepared as follows.

Zeolite powder or granules 100 crushed and subjected to high temperature activation treatment to have a moisture absorbing and odor absorbing effect
Twelve sets of 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight of bentonite made of colloidal clay for swelling and softening and disintegrating the molded body due to moisture absorption are prepared. Prepared a total of 12 sets each containing 3 parts added, 3 sets of 16 parts by weight of calcium chloride dissolved in 15 parts by weight of water, 3 sets of 23 parts by weight of calcium chloride dissolved in 20 parts by weight of water, water Prepare a total of 12 sets of 3 sets in which 25 parts by weight of 30 parts by weight of calcium chloride are kneaded.

Then, the above is combined and kneaded to prepare a kneading compound material having 12 kinds of compounding ratios, which is compressed by a mold to form a molded body, and 12 kinds of solid desiccants are prepared. Then, the moisture absorption rate and the swelling and disintegrating property of the solid desiccant in each test section were examined.

 The results are shown in Table 1.

As a result of the above experiment, it was found that all of them can be commercialized as a solid drying agent having a deodorizing function. That is, the raw material was pulverized and subjected to a high temperature activation treatment to obtain 100 parts by weight of a powder or granules of zeolite which had a hygroscopic and odor absorbing action, and pulverized and subjected to a high temperature treatment to have a hygroscopic action. 16 to 30 parts by weight of calcium chloride powder or granules, 15 to 25 parts by weight of water, and 10 to 40 parts by weight of bentonite made of colloidal clay for swelling and softening and disintegrating the molded body due to hygroscopic action. It has been found that a mixing ratio of 1 part is preferable.

Next, a method for manufacturing the solid desiccant will be described.

First, as a raw material, a powdered or granular material of zeolite crushed and subjected to high temperature activation treatment so as to have a moisture absorbing and odor absorbing effect, and calcium chloride crushed and subjected to high temperature treatment to have a moisture absorbing effect A powdery or granular material, water, and bentonite made of colloidal clay for swelling due to a hygroscopic effect to soften and collapse the molded body are prepared.

Next, 16 to 30 parts by weight of calcium chloride powder or granules that have been crushed and subjected to high temperature treatment to have a hygroscopic effect, and kneaded by adding 15 to 25 parts by weight of water to obtain an appropriate hardness. Make a sticky paste.

Next, a kneaded product obtained by kneading the powdery or granular material of calcium chloride with appropriate water, pulverized and subjected to high temperature activation treatment to have a moisture absorption and odor absorbing effect. By weight, 10 to 40 parts by weight of bentonite, which is made of colloidal clay for swelling and softening and disintegrating a molded body due to a hygroscopic effect, is added, and these are well kneaded to form a kneading compounding material.

After that, the kneading compound material is compression-molded into an arbitrary shape by various methods such as a shape die, a rolling mill, a cutting blade, and the like to form a molded body by the binding force of the binder, and calcium chloride is added as the hygroscopic action progresses. The bentonite swells due to the moisture A generated by absorbing moisture or deliquescing. Then, at the end of the moisture absorption reaction of calcium chloride, the molded product is prepared so as to be disintegrated by the large swelling of bentonite to obtain a solid desiccant having a deodorizing function.

In order to commercialize this, the solid desiccant 4 is stored in a moisture-permeable film or non-woven fabric bag, which is further packaged in a moisture-impermeable film-like packaging bag, box or container. To distribute. When this is used, the solid desiccant 4 contained in a moisture-permeable film or non-woven fabric bag is taken out from the packaging container and placed in a space to be dried for use. Simultaneously with the installation, the deodorizing action and the moisture absorbing action start, and the calcium chloride begins to deliquesce and gradually swells and softens (see Fig. 3). And, at the end of moisture absorption, the bentonite swells,
The arbitrarily formed solid desiccant swells and disintegrates and loses its shape to accurately notify the person watching the end of the hygroscopic effect (see FIG. 4).

[Advantages of the Invention] As described above, the present invention uses, as a main raw material, a powdery or granular material of zeolite which has been crushed and subjected to high temperature activation treatment so as to have a moisture absorption and odor absorbing effect, and crushed and subjected to high temperature treatment. By combining calcium chloride powder or granules that have a hygroscopic effect, it becomes possible to simultaneously perform a hygroscopic effect and an odor absorbing effect, and damage such as mold, mites or rust caused by moisture in the space. And odor can be prevented. In particular, the hygroscopic effect is greatly improved by the synergistic effect of the combination of zeolite and calcium chloride, and the performance is higher than that of the conventional desiccant.

In addition, since the raw material calcium chloride acts as a binder by forming a binding property by simply kneading an appropriate amount of water, it is not necessary to prepare a binding material again, and only by compression molding, a molded body of any shape can be obtained. Can be manufactured easily.

However, the combination of calcium chloride that deliquesces with the progress of the hygroscopic action and bentonite that swells by absorbing moisture such as water and liquid, causes the calcium chloride to deliquesce along with the progress of the hygroscopic action. Swelling bentonite, calcium chloride completely deliquesces, liquefying,
When the moisture absorption reaction was completed, the bentonite swelled, and the bound compact could not be maintained and collapsed. Such collapse of the molded body is a sure news that can be recognized by anyone at a glance. Moreover, since this swelling and disintegration occur at a timely timing due to the end of the moisture absorption reaction of the constituent material of the desiccant, it is possible to exert an indicator function that accurately notifies the end of the effectiveness of the desiccant and the time for replacement.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view showing a solid desiccant having a deodorizing function according to the present invention, and FIG. 2 is an enlarged cross-sectional view of an essential part showing a composition structure state of the desiccant. FIG. 3 is an enlarged cross-sectional explanatory view of an essential part showing a state in which the composition structure of the desiccant absorbs water, deliquesces and swells, and FIG. 4 shows the composition structure of the desiccant at the end of moisture absorption. FIG. 4 is an enlarged cross-sectional explanatory view of a main part showing a swollen and collapsed state. "Explanation of main signs" 1 …… Zeolite 2 …… Bentonite 3 …… Calcium chloride 4 …… Solid-state desiccant with deodorizing function 5 …… Bag A …… Water

Claims (1)

[Claims] 1. 100 parts by weight of a powdery or granular material of zeolite which has been crushed and subjected to high temperature activation treatment so as to have a hygroscopic and odor absorbing effect, and pulverized and subjected to a high temperature treatment to have a hygroscopic effect. Calcium chloride powder or granules 16-30 parts by weight 15-25
A kneading compounding material prepared by kneading a binder kneaded with 1 part by weight of water and 10 to 40 parts by weight of bentonite made of colloidal clay for swelling and softening and disintegrating the molded body due to a hygroscopic action is optional. To form a compact by the binding force of the binder by compression molding into the shape of, and bentonite swells with the aqueous solution generated by the deliquescent of calcium chloride as the hygroscopic action progresses, and at the end of the moisture absorption reaction, the compact swells with bentonite. A solid desiccant having a deodorizing function, characterized in that it is disintegrated by.