JPS5940180B2 - How to store solid chlorine agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for safely preserving solid chlorine agents that tend to generate decomposed gases such as chlorine gas, nitrogen chloride gas, and chlorine oxide gas during storage.

Conventionally, solid chlorine agents include trichlorinated isocyanuric acid, dichlorinated isocyanuric acid, sodium salt or potassium salt of dichlorinated isocyanuric acid, bleaching powder, sodium chlorite, or these combined with an auxiliary agent. Compositions and the like are known, and these are widely used as disinfectants, disinfectants, bleaches, etc. in various fields in the form of powder, granules, granules, or tablets.

However, after these solid chlorine agents are produced in factories, it takes commercial routes such as land and sea routes and a considerable number of days, for example, 1 to 2 years, before they are put into practical use at the site of use. , transportation, transportation, etc. in sealed packaging containers made of materials such as paper, plastic, metal, etc.
During storage, decomposition gas generated from the sealed solid chlorine agent causes various undesirable
Especially in some cases, dangerous accidents have occurred. For example, the ink markings written on the outer surface of the packaging container may become unclear or erased, or in severe cases, the material of the container may be soaked or damage may occur due to increased internal pressure.
Further, the decomposed gas not only causes discomfort to the operator when the package is opened and put into use, but is also harmful to the human body, and there has been a strong desire in the technical field to solve these problems. Therefore, considerable research has been carried out to investigate the causes of these accidents and to take countermeasures.For example, in order to suppress the generation of decomposition gas from the solid chlorine agent mentioned above, it is necessary to reduce the moisture content in the product. There are several other proposals, such as that it is effective to completely block outside moisture and light during storage, but none of them are satisfactory.

For example, manufacturing completely anhydrous products is almost impossible in industrial production, and even if metal is used as a material for packaging containers that can completely block outside air and light, it will not last long during storage. Gradual accumulation of decomposed gas inside the container causes corrosion of the container wall or deformation or damage of the container due to increased pressure. There are also proposals to form solid chlorine agents into granules or tablets in order to reduce the specific surface area, but this is not an effective method for long-term storage. Furthermore, there has been a proposal to coat the surface of the solid chlorine agent with an inert substance, such as a film of paraffin or polyvinyl alcohol, but as above, the effect is not sufficient.
Moreover, when used for pool sterilization, it is not preferable to supply oil into the pool water. Furthermore, another proposal is to add and mix an ordinary desiccant, such as potash alum, into a solid chlorine agent, but the effect is not sufficient and in some cases may promote the generation of decomposed gas. This is not desirable.

Another proposal is to add and mix a stabilizer, such as limonene, to the solid chlorine agent in order to suppress its decomposition, but this method is also insufficiently effective and, on the contrary, promotes the generation of decomposed gas. Or even yellow coloration may occur. As a result of extensive experimental research with the intention of solving the above-mentioned problems, the present inventors surprisingly found that melamine powder was present in the vicinity of the solid chlorine agent in a closed container without coming into contact with it. At that time, they discovered that the generated cracked gas can be efficiently absorbed and fixed without promoting the generation of cracked gas, and have completed the present invention.

The object of the present invention is to store a solid chlorine agent containing trichlorinated isocyanuric acid, dichlorinated isocyanuric acid, sodium salt or potassium salt of dichlorinated isocyanuric acid, bleaching powder, or sodium zinc subate in a container. By efficiently absorbing and fixing the gas generated by natural decomposition without accelerating the generation of decomposition gas, the container surface and substrate will not be damaged or damaged, and harmful gases will be removed when the container is opened. It is an object of the present invention to provide a simple method for preserving the solid chlorine agent that does not emit odor or the like.

Still another object of the present invention is to stably store the solid chlorine agent in a container without deteriorating the performance of the solid chlorine agent, causing deterioration, coloring, etc., and without containing undesirable accompanying materials even in practical use. The purpose is to provide a method for storing information. The method for preserving a solid chlorine agent of the present invention includes a solid chlorine agent containing trichlorinated isocyanuric acid, dichlorinated isocyanuric acid, sodium salt or potassium salt of dichlorinated isocyanuric acid, bleaching powder, or sodium chlorite. It is characterized in that melamine, ammeline, or ammelide is present in the atmosphere surrounding the chlorine agent so as not to come into contact with the solid chlorine agent but in contact with the atmospheric gas. Furthermore, the second method for preserving a solid chlorine agent of the present invention includes a solid chlorine agent containing trichlorinated isocyanuric acid, dichlorinated isocyanuric acid, sodium salt or potassium salt of dichlorinated isocyanuric acid, bleaching powder, or sodium zinc. It is characterized in that a composition containing melamine, ammeline or ammelide finely dispersed in plastic is present in the atmosphere surrounding the chlorine agent. Solid chlorine agents to which the method of the present invention is applied include trichlorinated isocyanuric acid, dichlorinated isocyanuric acid, anhydrides and hydrates of sodium salts or potassium salts of dichlorinated isocyanuric acid, or the like. It is a solid drug in powder, granule or tablet form containing a mixture of as an active ingredient.

These are usually industrial products that are difficult to obtain completely anhydrous, and even in a closed container, they will gradually generate decomposed gases such as chlorine and nitrogen chloride due to the small amount of water they contain, or they will be made of plastic bags or paper. Decomposition gas is likely to be generated in containers with some air permeability, such as drums. Furthermore, these solid chlorine agents often contain various auxiliary components depending on the intended use. Furthermore, solid chlorine agents to which the method of the present invention is applied include bleached powder of calcium hypochlorite, sodium chlorite, other N-chloroimides,
Examples include N-chloroamides. As melamine, ammewan, or ammelide used in the method of the present invention, commercially available industrial products are sufficient, and powders are usually sufficient.
Furthermore, these may also be made into granules or tablets.

The lower the water content, the better. Furthermore, they can also be used as finely dispersed compositions in plastics.

Preferred plastic components of the composition include polyethylene, copolymers of ethylene and propylene, butene, vinyl acetate, etc., polyolefin resins such as polypropylene or mixtures thereof, polyvinyl chloride, vinyl chloride and ethylene, propylene, vinyl acetate, and other copolymers. Examples include polyvinyl chloride resins such as copolymers with polymerizable simple substances, and polymers or copolymer resins of vinylidene chloride. In particular, the composition used in the second invention of the present application is preferably a composition obtained by kneading the above plastic and the above melamine, ammeline or ammelide while the plastic is melted, and then cooling to room temperature to solidify. If necessary, it can be used in the form of granules, fibers, films, sheets, or plates by molding. The method of the present invention includes melamine,
To make ammeline or ammelide (hereinafter referred to as a stabilizer) exist in an atmosphere surrounding a solid chlorine agent in such a way that it does not come into contact with the solid chlorine agent, but is in sufficient contact with the atmospheric gas. is the requirement. In the present invention, the atmosphere surrounding the solid chlorine agent is usually the inside of a closed container, and the atmosphere includes air, decomposed gas generated from the solid chlorine agent, and a container wall with some air permeability. There is outside air passing through the container. In addition, airtight containers are containers that are normally used for packaging, storage, transportation, transportation, etc., and include paper bags or boxes, plastic film bags, molded containers, metal cans, and fiber drums. However, in some cases, equipment and containers such as reaction cans, mixers, etc. at the production site of solid chlorine agents may not be forced to vent even if they have ventilation holes with outside air. When temporarily storing the solid chlorine agent in a device, container, etc. after completing the process operation, an atmosphere surrounding the solid chlorine agent is formed to form a state equivalent to a hermetically sealed container. do. When the stabilizer is present in the atmosphere of the solid chlorine agent to be stored so as to be in contact with the solid chlorine agent, for example, the stabilizer and the solid chlorine agent are uniformly mixed, or the stabilizer is mixed with the solid chlorine agent, or When coating the particle surface of a solid chlorine agent, the decomposition of the solid chlorine agent is accelerated.
The amount of decomposed gas generated increases, and the effect contrary to the purpose of the present invention is promoted. Furthermore, if the stabilizer does not come into contact with the gas in the atmosphere of the solid chlorine agent to be stored, the object of the present invention cannot be achieved. That is, when the stabilizer comes into contact with the decomposition gas generated from the solid chlorine agent, it captures and captures the gas.
Although it exhibits a strong ability to immobilize solid chlorine agents, when it comes into contact with solid chlorine agents, it has the effect of promoting the decomposition of solid chlorine agents, exceeding its ability to absorb and fix the generated cracked gas. However, when the stabilizer is present in the atmosphere without contacting the solid chlorine agent, the decomposition of the solid chlorine agent is not promoted and only the gas generated by natural decomposition is strongly absorbed and fixed. This unexpected new fact was discovered by the present inventors. Thus, when using the method of the present invention, deterioration, coloring, etc. of the solid chlorine agent to be stored hardly occur during storage. The above-mentioned stabilizers exhibit the above-mentioned specific effects, for example, activated carbon, activated clay, sodium chloride, sodium sulfate, calcium fluoride, aluminum hydroxide, ferric oxide, sodium acid phosphate, etc. , the object of the invention is not achieved. According to the method of the invention, it is usually sufficient for the stabilizer used to be used in an amount within a few percent of the solid chlorine agent to be stored.

The appropriate amount to use may vary slightly depending on the material of the container in which the solid chlorine agent is sealed, storage temperature, storage period, etc., but for example, when storing the solid chlorine agent tightly in a metal container, It is sufficient to include about 1% of the stabilizer in the package, and when the package is opened after being stored at room temperature for 30 days, the operator will hardly notice any odor of decomposed gas. In addition, in the present invention, as a method for causing the stabilizer to exist in the atmosphere surrounding the solid chlorine agent so as not to come into contact with the solid chlorine agent but to be in contact with the atmospheric gas, there is a method in which the stabilizer is allowed to leak out. It is sufficient to place the contents in a breathable container such as a cloth bag, perforated plastic bag or container, and place it around the solid chlorine agent to be stored. Therefore,
When storing a solid chlorine agent in a closed container, this can be easily done by enclosing a package containing the stabilizer together with the solid chlorine agent contained in an inner bag. As the stabilizer, other arbitrary substances may be added as long as the purpose of the present invention is achieved, but it is better to avoid the combined use of highly hygroscopic substances. Instead of using a package containing the stabilizer in the leak-proof and breathable plastic container, the present invention uses a composition obtained by melt-kneading the plastic and the stabilizer and then cooling and solidifying the plastic. This is a preferred embodiment of the second invention, and the object of the present invention can be achieved more easily.

In addition to the stabilizer, the composition may contain any additives such as processing aids, fillers, etc. as long as the purpose of the invention is achieved.
There is no problem even if it contains stabilizers for plastics. Typically, the composition contains about 10-60% of the stabilizer therein.
It can be contained to some extent. Further, the above-mentioned kneading can be easily carried out by using a mixing roll, a screw extruder, or the like. Particularly preferable shapes of the above composition include granules, fibers, films, sheets, plates, etc. Furthermore, when using bags, containers, etc. formed from these, the solid chlorine agent is placed therein. If the contents can be stored and the storage period is short, it can be transported or stored in its original state.
Transportation, storage, etc. can be carried out. Also, if necessary,
A bag, container, etc. formed from the above composition containing a solid chlorine agent can also be placed in a stronger outer container and stored in a sealed container. Thus, according to the method of the present invention, the solid chlorine agent does not undergo deterioration or coloring, does not contain undesirable accompanying substances, and furthermore does not cause damage or breakage to the container surface or material of the solid chlorine agent. The solid chlorine agent can be stored in a sealed state extremely safely and stably for a long period of time without causing any damage. Moreover, when opened after storage, no harmful gases or unpleasant odors are emitted and there is no need to confuse workers. Above all, the simplicity of the method of the present invention makes it a significant contribution to the technical field. Examples and comparative examples will be described below, but the technical scope of the present invention is not limited thereto. Example 1 As a solid chlorine agent, particle size is 0.25-1.4m77! , trichlorinated isocyanuric acid (A) with a moisture content of 0.15% and an available chlorine content of 90.3%, a particle size of 0.1 to 0.35%, a moisture content of 0.24%, and an available chlorine content. Rate 68.04%
Reagent grade 1 highly bleached powder (B) and particle size 0.3-1.0
mm1 moisture content 0.11%, active ingredient content 69.7
% of reagent first grade sodium chlorite (C) was prepared.

Next, three three-necked glass containers with an internal volume of 200 m1 were prepared, and the solid chlorine agents (A), (B) and (
507 of each of C) were added separately.

Separately, a perforated polyvinyl chloride bag with a film thickness of 0.12 m71 was filled with melamine powder 27, and the 10th container was sealed with a rubber stopper suspended from the bottom. A glass stopper with an on-off valve was installed in the 20th container, and a conduit for passing dry N2 gas was attached to it. A glass stopper with an on-off valve is also installed in the 30th container, and furthermore,
After connecting the conduit to 100 ml of 1% orthotolidine hydrochloride aqueous solution, all valves were closed and the container was heated to 35°C.
It was left still in a constant temperature room for 5 days. Next, both valves of the container were opened, N2 gas was immediately introduced from the 20th port, exhaust was exhausted from the 30th port, and the generated decomposed gas was collected by passing it into the orthotolidine solution. The orthotolidine solution turned yellow as the decomposed gas was captured, so the amount of decomposed gas generated was measured by measuring the absorbance of light with a wavelength of 440 mμ using a spectrophotometer.
The amount of decomposed gas generated was converted into the total amount of chlorine gas, and the results shown in Table 1 were obtained. Comparative Example 1 An experiment was carried out in the same manner as in Example 1 except that the bag containing melamine was suspended in a glass container, and the results shown in Table 1 were obtained.

Example 2 A package was prepared in which melamine powder 27 was contained in a polyethylene pouch having a film thickness of 0.15 mm and a pore of 40 mm x 50 mm in length and width.

Next, 0.15mm thick 1 vertical and horizontal 150mm x 20
0m7! A L-sized bag made of high-density polyethylene was prepared, and the solid chlorine agent (A) 1007 and the package containing the melamine powder were put therein and then heat-sealed. The bag containing the solid chlorine agent and stabilizer as described above is 100m77 in length, width, and height! x150mm x 200mm 1 thickness 3m77! After placing the sample in a cardboard box made of kraft paper, the box was closed and stored in a constant temperature and humidity chamber at 40° C. and 80% relative humidity for 40 days.

Immediately after the above period had passed, the box was taken out and the following items were measured, and the results shown in Table 2 were obtained. (1) Deterioration condition of the box Observe the brittleness of the paper by the finger pressure of the worker.

(2) Observe the chlorine, nitrogen chloride, and chlorine oxide gases present in the decomposition gas bag using a detection tube.

(3) Degradation of solid chlorine agent The amount of available chlorine is measured for the sample before and after the storage test using the iodometry method. ).

Comparative Example 2 An experiment was carried out in the same manner as in Example 2, except that the melamine powder packet in Example 2 was not enclosed, and the results shown in Table 2 were obtained.

Example 3 After melting and kneading 100 parts of high-density polyethylene and 20 parts of melamine powder, a sheet with a thickness of 0.15 mm was formed, and three bags measuring 150 x 250 mm in length and width were made from this sheet.
I made one.

Next, the solid chlorine agents (A), (B) and (C) are added to this bag.
1007 of each sample were individually charged, heat-sealed, and then allowed to stand for 30 days in a constant temperature and humidity chamber at 40° C. and equivalent humidity of 80%. Next, after the above period had elapsed, the bag was taken out and the concentration of the decomposed gas generated and the decomposition rate of the active ingredient were measured in the same manner as in Example 2, and the results shown in Table 3 were obtained. Comparative Example 3 An experiment was carried out in the same manner as in Example 3, except that a bag containing no melamine powder was used, and the results shown in Table 3 were obtained.

Examples 4 and 5 An experiment was conducted in the same manner as in Example 1 except that ammeline was used in Example 4 in place of melamine in Example 1, and ammelide was used in Example 5. The results are shown in Table 1. Got the results.

All of the examples of the present invention were found to be good.

Claims (1)

[Claims] 1. In an atmosphere surrounding a solid chlorine agent containing trichlorinated isocyanuric acid, dichlorinated isocyanuric acid, sodium salt or potassium salt of dichlorinated isocyanuric acid, bleaching powder, or sodium chlorite. A method for preserving the solid chlorine agent, characterized in that melamine, ammeline, or ammelide is present in the solid chlorine agent without contacting with the atmospheric gas. 2. The method for preserving a solid chlorine agent according to claim 1, wherein melamine, ammeline, or ammelide is in the form of powder, granules, or tablets. 3. Melamine, ammeline or 1. A method for preserving a solid chlorine agent, characterized in that a composition in which ammelide is finely dispersed in plastic is present. 4 Claims in which the plastic is a polymer or copolymer of ethylene, a polymer or copolymer of propylene, a polymer or copolymer of vinylidene chloride, a polymer or copolymer of vinyl chloride, or a mixture thereof. The method for preserving the solid chlorine agent according to item 3. 5. The method for preserving a solid chlorine agent according to claim 3 or 4, wherein the composition is in the form of granules, fibers, films, sheets, or plates.