JPS6331227B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a glyoxal-based deodorizing agent, and more particularly to a deodorizing agent comprising glyoxal, a buffer solution (PH 5 to 9), and expanded vermiculite. Glyoxal reacts well with odorous substances such as ammonia, mercaptan, or hydrogen sulfide to make them odorless, so it can be used as a deodorizing agent. Its specific uses include kitchen waste, house feces or human waste, poultry manure drying areas or toilet bowls, Used for deodorizing or preventing odors in toilets, etc. Since many of the above-mentioned odorous substances dissolve in water and exhibit basic or acidic properties, glyoxal should be mixed with a buffer solution to maintain its pH at a weakly acidic, neutral or weakly basic level of 5 to 9 during use. (Special Publication No. 3383, Showa 48, hereinafter referred to as Prior Invention 1) or adjust the pH (Special Publication No. 3383, Showa 53, hereinafter referred to as Prior Invention 1)
No. 43575, hereinafter referred to as Prior Invention 2),
In an acidic or basic atmosphere, the deodorizing effect is lost or significantly reduced. With the technology of maintaining and adjusting the pH, it has become possible to deodorize gases, liquids, human waste, etc. containing odor substances such as ammonia, mercaptans, or hydrogen sulfide for industrial or civilian purposes, and it has been put into practical use. . However, according to Prior Invention 1 or Prior Invention 2 (hereinafter both will be collectively referred to as prior invention), there are malodor-generating substances whose deodorizing effect is still insufficient.
That is, when the substance is a liquid or gas, it can be relatively easily and sufficiently brought into contact with the deodorizing agent of the prior invention, but the malodor-generating substance or the environment in which the substance exists or is sequentially generated, that is, For example, when attempting to simply prevent the accumulation of kitchen waste, undried house excrement, and other malodorous substances, or the malodor emitted by solid substances or the animal itself, such as in a house where breeding animals exist, the prior application The deodorizing agent of the invention has the problem that it is practically difficult to spray or mix it onto the target object, or even if it is not difficult, the frequency of spraying, etc. must be considerably increased in order to maintain the deodorizing effect. Ta. For example, granular activated carbon, which can be used in such cases, adsorbs not only the above-mentioned odorous substances but also a wide range of chemical substances, so it is necessary to spray a very large amount of it. In many cases, it is virtually impossible to use it to deodorize substances. In addition, glyoxal can be added to diatomaceous earth, acid clay,
It is also possible to make a powdered deodorizer by absorbing or adsorbing it onto sawdust, etc., to improve its dispersibility and the sustainability of its deodorizing effect, but in these cases, the amount of glyoxal that can be absorbed is relatively small; , the product absorbed in this manner is significantly inferior in quick-acting effect compared to when the same amount of glyoxal is sprayed in liquid form as in the prior invention, so it can only be used for limited auxiliary purposes. It turned out that. Therefore, as a result of intensive research, the present inventors have conducted intensive research into a functional form that allows glyoxal to act effectively and sustainably on the above-mentioned deposited or open-air malodor-producing substances or malodor-producing environments. A composition in the form of powder, granules, slurry, slurry, or plastic, which is obtained by mixing expanded vermiculite and absorbing all or part of the former into the latter, can be easily and effectively used. The present invention was completed by discovering that it can exert a deodorizing effect on substances or the environment. As is clear from the above description, the objects of the present invention are, firstly, to provide a glyoxal-based deodorizing agent for deodorizing solid, deposited, or odorous substances in an open atmosphere; It is an object of the present invention to provide a deodorizing agent capable of exhibiting a sustained deodorizing effect in an open atmosphere. Other purposes will become clear from the description below. The present invention provides: (1) A deodorizer comprising glyoxal, a buffer (PH 5 to 9), and expanded vermiculite. (2) The deodorizer according to (1) above, wherein the expansion ratio of expanded vermiculite is 5 to 50 times. (3) The deodorizer according to (1) above, wherein the expanded vermiculite has an average particle size of 0.05 mm to 7 mm. (4) The granular deodorizer of (1) above, in which glyoxal and a buffer are absorbed into expanded vermiculite particles. (5) The deodorizer according to (1) above, wherein glyoxal and a buffer solution form a slurry with expanded vermiculite particles. (6) The deodorizing agent according to (1) above, in which glyoxal and a buffer solution form a slurry or plastic material with expanded vermiculite particles. The structure and effects of the present invention will be explained in detail below. B. Glyoxal used in the present invention is a 40% aqueous solution (PH1
~3) may be used, but lower concentrations, higher concentrations, or anhydrous ones may be used. In the deodorizer of the present invention, it must be mixed with the buffer described below to have a pH of 5 to 9. (b) The buffer used in the present invention has a pH of 5 to 9, and must be able to maintain the pH of 5 to 9 even after mixing with glyoxal used in the present invention. Therefore, the weight ratio of glyoxal (converted to 100%) and the buffer (water contained in the raw material glyoxal is also considered for convenience) is:
A ratio of about 1:100 to 200:100, preferably about 5:100 to 100:100 is easy to use. Practical buffer solutions include an acidic carbonate aqueous solution, a combination of potassium dihydrogen phosphate and disodium hydrogen phosphate (Salenyan's buffer solution), as described in the prior invention (Japanese Patent Publication No. 3383/1983). ),
Combinations of potassium dihydrogen phosphate and caustic soda (Clark, Labs' buffer solution), combinations of potassium dihydrogen phosphate and borax (Koltoff's buffer solution), and combinations of citric acid and sodium dihydrogen phosphate (pine kirvaine's buffer solution) ) etc. The reason for using the buffer solution is to maintain deodorizing power by avoiding changes in pH during use, as described in Prior Invention 1. C. The expanded vermiculite used in the present invention is
Powdered or small granular vermiculite (there are commercially available products with a particle size of about 0.5 mm to 7 mm) is heated to about 800°C for a very short time, and the volume magnification is doubled to 50. Preferably 5 times
It is expanded to about 20 times. Various other methods are known for expanding vermiculite, such as peroxide treatment (Japanese Patent Publication No. 18352/1983), heating at low temperature after impregnation with urea, or irradiation with electromagnetic waves (Japanese Patent Publication No. 1571/1971). However, it should be noted that, except for products treated with peroxide (Special Publication No. 48-48280), expanded vermiculite itself has no deodorizing power. Further, although peroxide-treated vermiculite has deodorizing power against ammonia or ammonia odor, it is significantly weaker than the deodorizing agent of the present invention. The particle size of expanded vermiculite after expansion is also
A deodorizer of about 0.5 mm to 7 mm and about 0.5 mm to 3 mm is convenient because it can be easily sprayed or mixed onto an object after being used as the deodorizing agent of the present invention. Sizing is preferably carried out before the expansion of vermiculite, and crushing or sieving after expansion destroys the laminated layer structure within the expanded vermiculite particles, which is not preferred. D. Preparation of deodorizer: Although the order of mixing glyoxal, buffer solution, and expanded vermiculite used in the deodorizer of the present invention is not particularly limited, usually glyoxal and buffer solution are mixed, and the amount of the mixed liquid is If the amount is equal to or more than the expanded vermiculite, the expanded vermiculite may be added sequentially to the mixed liquid in a mixer while stirring or rolling. In the opposite case, the mixed solution may be added to the vermiculite in the mixer by sequentially sprinkling or the like. Mixing temperature is 0℃ to 80℃
The temperature range is not particularly limited, but it can be carried out at room temperature unless there is a special need, and the pressure can be carried out at atmospheric pressure unless there is a special need. but,
To prevent contamination of the working environment or for other reasons, there is no problem in carrying out the test at 1 Kg/cm ² to -0.5 Kg/cm ² G in a closed container. The mixing time is determined by the rate of absorption of the mixture by the expanded vermiculite, and is completed in 5 minutes to 5 hours at room temperature and atmospheric pressure, and often in 10 minutes to 3 hours. Expanded vermiculite has a specific volume and liquid absorption capacity that vary widely depending on its expansion rate, but it has an expansion rate of about 10 times, and a mixture of glyoxal and buffer solution of about the same weight can be used. can be fully absorbed. If the mixed liquid volume ratio is even higher, the composition will be in a wet state with reduced fluidity, and if the liquid volume ratio is still higher, the composition will be muddy or slurry-like. Depending on the purpose of use, the deodorizer of the present invention can be in the form of powder or granules (flowable), wet granules or mud (not fluid but with dispersibility), or slurry (when stationary, the liquid part and mud form). (separated into parts). Furthermore, if the object to be deodorized is a sticky lump or a wall surface that requires coating, the deodorizing agent of the present invention may be applied to a mud-like substance such as gelatin, glue, alginic acid or clay. It is also possible to dissolve, disperse, or mix a gelling agent in water to form a plastic composition that is easy to mix or apply. At that time, adhesives such as starch glue and french can also be mixed with the composition. E. Usage method and effects of the deodorizing agent; As mentioned above, the deodorizing agent of the present invention has a powder, granular, mud, slurry, or plastic form; A glyoxal buffering agent that can be easily sprayed, mixed, coated, mixed, kneaded, etc. on odorous substances in a dry or open atmosphere, and is present on the surface of the expanded vermiculite particles or outside the particle portion in the deodorizer. (PH5-9), it has a quick effect, and the large amount of glyoxal buffer held within the particles provides a long-lasting deodorizing power. ``The reason why the deodorizing power lasts is that glyoxal held within the stack of vermiculite particles often comes into contact with the odor substances that are generated sequentially, but it rarely comes into direct contact with the microorganisms that degrade glyoxal. For example, add the powdered deodorizer of the present invention to 5 kg of raw chicken manure.
Even when a mixture of 500g (consisting of 250g of vermiculite, 100g of glyoxal, and 150g of pH7 buffer) is sprayed and mixed and dried by heating, the foul odor characteristic of dry exhaust gas is hardly felt. In addition, when 2 kg of kitchen waste is mixed with 200 g of the deodorizer of the present invention, the odor suppression period lasts more than twice as long as when the same amount of kitchen waste is mixed with a corresponding amount of liquid deodorizer (30 g of glyoxal, 70 g of PH7 buffer). do. Furthermore, if an appropriate amount of the granular or granular deodorizing agent of the present invention is sprinkled on the floor of a storage shed for family storage, the bad odor during cleaning can be significantly alleviated or the frequency of cleaning can be reduced. In addition, when the slurry deodorizer of the present invention is sprayed on frequently used toilet tanks such as pump-type public toilets and school toilets, it lasts much longer than the liquid deodorizer, and the number of times it is sprayed can be reduced. Examples (manufacturing example 1, usage example) are shown below,
The present invention is not limited to this. Example 1 (Production Example 1) While stirring 1 kg of vermiculite with an average particle size of 1 mm and a swelling rate of 10 times in an open atmosphere at room temperature in a mixing tank, 1 kg of a saturated solution of sodium hydrogen carbonate containing 400 g of glyoxal was sequentially sprinkled. The deodorizer was absorbed in one hour to obtain a fluid powder deodorizer. Example 2 (Production Example 2) 1 kg of vermiculite with an average particle diameter of 0.5 mm and a swelling factor of 5 times was mixed with 4 kg of a saturated solution of sodium hydrogen carbonate containing 400 g of glyoxal while stirring in an open atmosphere at room temperature in a mixing tank. By mixing for hours, a wet to muddy and dispersible deodorizer was obtained. Example 3 (Production Example 3) 1 kg of vermiculite with an average particle size of 0.5 mm and a swelling factor of 5 times was mixed with 10 kg of a saturated solution of sodium hydrogen carbonate containing 400 g of glyoxal while stirring in an open atmosphere at room temperature in a mixing tank. The mixture was mixed for 1 hour to obtain a slurry-like deodorizer. Example 4 (Production Example 4) 5 kg of deodorizer produced in the same manner as in Example 2, 1 kg of clay, and 3 kg of water in which 300 g of french was dissolved were kneaded in a mixing tank at room temperature in an open atmosphere to form a plastic material. A deodorizer was obtained. Example 5 (Usage Example 1) Sprinkle and mix 500 g of the deodorizer produced in Example 1 on 5 kg of raw chicken manure in the form of small lumps (85-90% moisture), and leave the mixture for 1 hour. Place the mixture in a dryer with a capacity of 10. temperature
It was dried for 3 hours at 110°C and an air flow rate of 10/hr. During drying, almost no bad odor was detected in the exhaust air. On the other hand, when drying was done in the same way without spraying the deodorizer, a unique strong odor was felt. Example 6 (Use Example 2) 2 kg of kitchen waste consisting of 600 g of leftovers, 600 g of leftover rice, and 800 g of field scraps was mixed with 200 g of the deodorizer produced in Example 2,
At room temperature in a 5 capacity polyethylene bucket with a lid.
Stored for 14 days. The malodor suppression status is shown in Table 1 below. Comparative Example 1 (Comparative Use Example 1) 2 kg of the same kitchen waste used in Example 6 was mixed with 160 g of a saturated solution of sodium hydrogen carbonate containing 16 g of glyoxal used in Example 2, and stored in the same manner as in Example 6. did. The results are shown in Table 1 below. Control Example The same procedure as in Example 6 was carried out except that no deodorizer was used. The results are shown in Table 1 below.

[Table] Moderate odor, D. Unpleasant odor, E Strong unpleasant odor Example 7 (Use example 7) When 3 kg of the slurry deodorizer produced in Example 3 was sprayed on the toilet tank of a 1,000-capacity toilet (school toilet), ammonia was immediately released. The sulfide odor disappeared and the product became odorless. 1 more every 10th day
We were able to keep it odor-free by spraying it in kilograms at a time. Comparative Example 2 (Comparative Use Example 2) In Example 3, instead of 3 kg of the slurry deodorizer, 2.7 kg of a saturated solution of sodium hydrogen carbonate containing 120 g of glyoxal was sprayed, and the ammonia sulfide odor immediately disappeared and the product became odorless. To keep it odor-free, apply an additional 0.9 every 5th day.
Kg was required to be distributed. The reason why the deodorizing efficiency per glyoxal is significantly inferior to that of Example 7 is that the slurry deodorizer of Example 7 has the ability to stay close to the surface of the waste in the toilet tank due to the presence of porous vermiculite powder. This is understood to be due to the strong Example 8 (Use Example 3) 15 kg of the plastic deodorizer produced in Example 4 was applied approximately evenly onto the wall of a fresh fish processing plant having a wall area of 30 m ² . Compared to the case where only water washing of the floor surface after fresh fish treatment was carried out in the same manner, the odor was significantly reduced for 5 days after the application.

Claims (1)

[Claims] 1. A deodorizer comprising glyoxal, a buffer (PH 5 to 9) and expanded vermiculite. 2. The deodorizer according to claim 1, wherein the expanded vermiculite has an expansion ratio of 5 to 50 times. 3. The deodorizer according to claim 1, wherein the expanded vermiculite has an average particle size of 0.05 mm to 7 mm. 4. The granular deodorizer of claim 1, in which glyoxal and a buffer are absorbed into expanded vermiculite particles. 5. The deodorizer according to claim 1, wherein glyoxal and a buffer solution form a slurry with expanded vermiculite particles. 6. The deodorizer according to claim 1, wherein the glyoxal and the buffer form a slurry or plastic with the expanded vermiculite particles.