JPH03215267A - Solid deodorant - Google Patents

Abstract

PURPOSE:To obtain a deodorant generating no environmental pollution and exerting no unpleasant feeling and physiological adverse effect on a worker and regional residents by incorporating at least one compound selected from alkali metal carbonate or bicarbonate, an org. acid, alkali metal phosphate, alkali metal persulfate, alkali peroxomonosulfate and calcium peroxide, sodium sulfate and sodium secondary phosphate. CONSTITUTION:A solid deodorant is prepared by adding a lubricant and a molding binder to a mixture consisting of at least one kind of a compound selected from carbonates, bicarbonates, basic carbonates, oxides and hydroxides of Ca and Mg and/or alkali metal carbonate or bicarbonate, citric acid, L- ascorbic acid, succinic acid, DL-malic acid, D-gluconic acid, alkali metal primary phosphate, alkali metal persulfate, alkali metal peroxomonosulfate and calcium persulfate, sodium sulfate and/or sodium secondary phosphate. This deodorant immediately deodorizes acidic and basic malodorous substances in water by neutralization reaction upon the contact with water and generates double decomposition reaction to generate carbon dioxide to neutralize and deodorize basic malodorous substances in space.

Description

[Detailed Description of the Invention] [Main fields of application of the present invention] Under dry storage conditions at room temperature, including high temperatures such as under direct sunlight in the tropics, no chemical reactions occur and it is stable, and long-term storage is possible as long as moisture absorption is prevented, but chemical reactions occur immediately in water. This invention relates to a solid deodorant that decomposes and generates carbon dioxide gas to form harmless neutral salts.

The solid deodorant of the present invention can be used in a solid state such as powder or granules to divide into aqueous malodors or to temporarily add it to the sources of malodors generated from industrial waste and various organic putrefaction materials. When brought into contact with each other by methods such as spraying, mixing, etc., it is possible to simultaneously remove many types of malodorous substances that are acidic, basic, reducing, oxidizing, or polymerizable, and which would be considered difficult in common sense. It can effectively, economically and harmlessly deodorize. [Conventional technology] Many foul-smelling substances in liquid, wet solid, mud, or slurry form, including water, such as human waste, food scraps, putrefying protein waste, chemical pits, and other substances. Wastewater from processing plants, etc.
As typical conventional deodorizing methods for livestock wastewater, activated sludge before and after dehydration, livestock excrement, vomit, industrial waste, accidental carcasses, etc., the following methods, each with its own advantages and disadvantages, are generally adopted. I came here. (1) Use of fragrances (M fragrance) (e.g. human waste) cannot remove the odor itself; (2) Incineration (e.g. dehydrated activated sludge) requires equipment and fuel and the work is accompanied by an odor. (3) Drying [Example: Chicken manure] Generates a large amount of bad odor before it dries.

(4) Landfilling (e.g. dehydrated activated sludge, food waste) Adverse effects on the health of workers and release of foul-smelling toxic substances into the environment 2 (5) Use of chemical solutions (e.g. dehydrated activated sludge and human waste) Effective In many cases, the target odor substances are limited, they cause environmental pollution, and they are expensive.

[Problems to be Solved by the Present Invention] The present invention solves the problem of water-containing malodorous substances consisting of various chemical components.
It can be used temporarily, continuously, or intermittently by spraying, pouring, or mixing, without causing substantial environmental pollution, and without causing discomfort or physiological adverse effects on workers or local residents. The object of the present invention is to provide a novel solid deodorizer in powder, granular, or other molded form that eliminates or alleviates the problem. [Means for solving one problem] The present invention has the following features: 1. (a) At least one selected from carbonates, bicarbonates, basic carbonates, oxides, hydroxides of calcium and magnesium, and carbonates and bicarbonates of l or alkali metals; Citric acid, L-ascorbic acid, succinic acid, DL
(c) at least one selected from malic acid, D-gluconic acid, and primary phosphates of alkali metals; (c) at least one selected from alkali metal persulfates, caroates, and calcium peroxide; (2) contains sodium sulfate and/or dibasic sodium phosphate; and/or 2. A solid deodorant is provided by adding a lubricant and a molding binder to the above mixture.

The deodorant of the present invention is stable under normal storage conditions that do not substantially contain water, but once it comes into contact with water, it immediately deodorizes acidic and basic malodorous substances in the water through a neutralization reaction. In addition, a double decomposition reaction occurs, generating carbon dioxide gas, neutralizing and deodorizing basic malodorous substances present in the space, and furthermore, a small to trace amount of hydrogen peroxide is generated in the aqueous phase, which improves reducing and polymerizable properties. The following method has been devised to simultaneously deodorize the foul-smelling substances.

1) For basic harmful malodorous substances such as ammonia and trimethylamine in the aqueous phase, the solid organic acids they contain dissolve in water and immediately neutralize and deodorize them. The carbon dioxide gas generated by the reaction of magnesium carbonate, bicarbonate, and basic carbonate with organic acids neutralizes and deodorizes the basic, harmful, and malodorous substances present in the aqueous phase and airspace. 2) The carbon dioxide gas generated at this time stirs the foul-smelling substances in the water and airspace, contributing to the uniformity of the deodorizing reaction and preventing the deodorant from solidifying in the water.3) Contains calcium and magnesium. Carbonates, bicarbonates, basic carbonates, oxides, etc., react with the organic acids in the formulation and become water-soluble,
This undergoes a double decomposition reaction with acidic and harmful malodorous substances such as hydrosulfuric acid and alkyl mer-butanoates in water, resulting in low volatility or It precipitates as a water-insoluble salt and deodorizes it. 4) In addition, acetic acid, valeric acid, nitrous acid, and many other organic and inorganic harmful and malodorous acidic substances present in the aqueous phase and industrial waste are alkali metal compounds. Class 《The effect is immediate. 》, calcium compounds, magnesium compounds, 《The effects are long-lasting because they are not washed away by water from the reaction system. 》 etc., which causes a direct neutralization reaction, deodorizing and making it non-toxic. 5》 The stoichiometrically optimal combination formulation for the malodorous substances in the malodor source can be accurately determined by quantitative analysis of the malodorous substances according to the conditions of use described below, but even if it is not the optimal equivalent combination formulation. However, since the various deodorizing chemical reactions described above occur simultaneously in the aqueous phase and the gas phase, quickly and to a considerable extent, extremely efficient deodorization and reduction of the toxicity of the source of malodor can be achieved.

6) The above-mentioned various peroxides polymerize and deodorize polymerizable malodorous substances such as styrene, acrylate, and acrylic esters in water. In this case, if mercabutanes, which are sources of bad odors, coexist in the aqueous phase even in small amounts, the peroxides will be easily decomposed by the redox mechanism, exhibiting a strong polymerization initiation effect even at low temperatures of 10°C or less, and greatly increasing the deodorizing efficiency. improve.

These oxidizing agents also react with protein malodorants, as in the case of hypochlorite, to form chloramide compounds, which are known to be mutagenic and potentially carcinogenic. There is no fear.

7) The above peroxides contained in the deodorant of the present invention are:
It is relatively safe to handle, quantitatively oxidizes reducing malodorous substances such as mercabutan tablets, aldehydes, and sulfides in water, and reliably deodorizes them even when used in small quantities. 8> Such neutralization and double decomposition reactions between various reactive bases and carbonates and bicarbonates of strong bases and organic acids do not occur in a system where water does not exist, so the reaction during storage is difficult. Anhydrous sodium sulfate (capable of containing up to 10 molecules of water of crystallization,
) or dibasic sodium phosphate (can have up to 12 molecules of water of crystallization). ]. 9. Although it is possible to use these various ingredients alone, adding a small amount of lubricant such as silicone oil or fatty acid amide gives the powder type deodorant fluidity and makes storage easier. It is possible to prevent caking inside, to mix a molding binder such as wax or low-molecular polyethylene, and to make it easier to use by compression molding it into granules or other shapes, or to reduce the rate of decomposition by water to a certain extent during use. It can be adjusted. The mechanism of action of the solid deodorant of the present invention is outlined above, and the specific raw materials used, blending ratios, and purposes of use are shown in Table 1.

Compounds other than 1 do not contain water, do not react with peroxides such as the above-mentioned per[1 salts, or promote decomposition,
Although they can be added as long as they do not interfere with the deodorizing effect described above, it is not preferable to use iron compounds or heavy metal compounds because they accelerate the decomposition of peroxides such as persulfates. Additionally, the use of low-molecular-weight hydrocarbons, including certain fragrances, should be avoided as they may become explosive when mixed with peroxides. Additives other than these, which are particularly necessary, are used in continuous activated sludge dehydration equipment, silos, etc.
It is also a rust preventive agent for metal parts of transportation vehicles, etc. As anhydrous, particulate compounds, mono- and di-potassium phosphates, guanidine phosphate, etc. are suitable for this purpose.

The mixing method and order of addition of these various raw material compounds are as follows:
Although there are not many restrictions, first place anhydrous sodium sulfate or dibasic sodium phosphate, which will be used for dry dissection, into a stirring device.
A method in which various raw materials are suitably added one by one, stirred, and then the next raw material is mixed is a desirable method in order to minimize the influence of a small amount of intervening moisture, but there are no particular restrictions. As for mixing equipment, it is suitable to use a cement stirrer or hand mixing for small quantity production, and a Henschel mixer for large quantity production. Many combinations suitable for each purpose are possible within the range of the preferred formulation of each raw material shown in [Table 1]. The matters necessary for determining prescriptions for typical uses are listed in [Second Edition]
Table]. Due to such modification of the formulation for each application, the use of the solid deodorant of the present invention may cause environmental pollution,
It can prevent unnecessary cost increases and inconveniences in use, and
In the case of composting activated sludge, it is also possible to significantly improve productivity and product value by promoting fermentation by adding exothermic properties. Analysis method of malodorous substances generated from malodor sources〉What is extremely important in determining the formulation for each application is the accurate analysis of malodorous substances generated from each malodor source, as shown in each example. Perform quantitative analysis and accurately measure the concentration of various major malodorous substances1. For deodorizing feces with a moisture content of 65% 1) A large amount of basic malodorous substances such as ammonia and trimethylamine are generated, and a small amount of reducing malodorous substances is generated. 2
》 When commercialized as fertilizer, it is dried. It also contains too much nitrogen and phosphorous, and is low in potassium. 2 For deodorizing activated sludge with a moisture content of 85% discharged from a ham factory (disposed of by landfill fl) 1) [Generates a large amount of reducing odor substances such as hydrogen chloride and methyl mercabutane, and produces ammonia and organic amines. The amount of basic chemical substances produced by similar vines is small. 38 For deodorizing textile products and rinse water for commercial cleaning 1) Complex substances such as body odor, sweat odor, and fecal matter remain in trace amounts that cannot be measured with a detection tube. 4. For use by spraying on putrid matter such as protein foods, vomit, rotting corpses, feces, etc.1》 Often results in slurry-like or strong foul-smelling liquid spills. 2) Many malodorous substances such as basic, reducing, and acidic substances are often generated at the same time. 1》 [Table 1] Calcium salts of carbonates and bicarbonates listed in item (a) help to insolubilize phosphorus and make them useful as universal fertilizers. Gas can be used to efficiently perform cylindrical treatment. 2》 Peroxide is.
It is sufficient to use a small amount of 100 ppmli degree or less. 3) As a desiccant, dibasic sodium phosphate is preferred from the viewpoint of fertilizer value, and if quicklime is added to form crystal water, the reaction heat will improve the drying rate. 1) Calcium is solubilized and reacted with these reducing and acidic malodorous substances to deodorize it as an insoluble salt through double decomposition precipitation, and the peroxides listed in item ``C'' of [Table 1] are added, especially in the summer. is used in amounts of 1,000 pprn or more to ensure deodorization and to provide a long-lasting effect.
2) Since it is added just before the sludge is dehydrated, enough carbon dioxide gas is generated to prevent the desiccant such as sodium bicarbonate from condensing in the water. 3) Add phosphate to prevent rust on metal parts of processing equipment. 1) Calcium content, which would deteriorate the feel and appearance of the fibers, is not added. 2) In order to provide a deodorizing effect and a soda killing effect, the peroxides listed in [Table 1] item ``C'' were added to 3. Add more than OOOppm. 3) - Blend the water after the reaction is completed so that the pH is 7.0 to 7.5, so that the decomposition of hydrogen peroxide is completed in a short period of time in the dark, and a decrease in the strength of the fibers is prevented. 1) Reduce the amount of carbon dioxide gas generated and increase the amount of anhydrous sodium sulfate, etc.
It partially solidifies due to the formation of water of crystallization, making removal work easier. 2) When indoors, avoid using calcium to prevent whitening. 8 The analysis method adopted by the present inventors was as follows.

■》 The solid content of the malodor source was measured by constant temperature drying method (108°C, 2 hours).

2> Dilute the solid content of the source of the bad odor to 5% with distilled water and place it in a constant temperature bath at 5℃, 20℃, and 40℃ for at least 3 minutes.
After 0 minutes, measure the pH with a glass electrode pH meter and determine whether the main malodorous substances generated are acidic or basic.
This served as a guideline for prescription decisions and subsequent analyses.

3) Place a certain amount of a bad odor source with a known solid content into a polyethylene bag that can be sealed and does not leak liquid, along with the required amount of water.
Knead the bag well to distribute it evenly, then seal the opening of the bag with a rubber band and use a Kitagawa gas detector to
01 fresh air was injected into the bag between the rubber bands and heated to 5°C.
At least 30℃ in a constant temperature bath at 20℃ and 40℃
After putting it in the bag for a few minutes, insert a Kitagawa gas detection tube suitable for the purpose made by Komei Rikagaku Kogyo Co., Ltd. between the rubber bands of the bag.
The gas concentration of the target malodorous substance was accurately measured. Here, the deodorization rate was calculated using the following formula. (A) Detection amount when using one deodorant Alcohol alcohol rate = 100X Detection amount when no deodorant is used (A) 4) If the amount of malodorous substances from each malodor source is abnormally small, the accuracy is better than that of a detection tube. We also conducted a sensory test based on the following 6-level odor display system adopted by the Environment Agency, which relies on the sense of smell, which is said to have a high level of odor. Smell that can be feared (detection value) 2 A weak odor that tells you what kind of smell it is (cognitive value) 3 Smell that can be easily detected 4 Strong odor 5 By accumulating experiments on strong odors and beyond, the inventors have: We were able to establish a reproducible and accurate analytical method, and this technology greatly contributed to the completion of the present invention. [Advantages of the solid deodorant of the present invention] The optimum combination formulation and optimum usage amount of the solid deodorant of the present invention are determined based on the accuracy of the main malodorous substances and their concentrations emitted from the target malodor source, as described above. It can be determined by method analysis and sensory testing. A deodorant based on the preferred formulation determined in this way has the following advantages.

1) As mentioned above, the deodorizing chemical reaction is immediate, continuous, targets a wide range of malodorous substances, and is extremely efficient.

2) The product has excellent storage stability.

3) It should be extremely stable in a sealed state, provided that routine handling such as adding water or liquid substances that are easily oxidized in a sealed container is avoided.

4》 In addition to the solid peroxides listed in the claims above, hypochlorites, chlorites, perchlorates, perboric acids, (e.g., alkali metal salts, etc.) Even if peroxide compounds have the same effect as the alkaline earth salts and have excellent deodorizing effects, they may pose physiological toxicity or danger to workers and may cause environmental pollution. being excluded.

5》 In the case of turning activated sludge into fertilizer, etc., when using potassium salt or calcium salt instead of sodium salt,
It is possible to select a combination formulation that does not cause sodium damage to plants and eliminates the drawbacks of excessive nitrogen.

6) Can be manufactured using only easily available and inexpensive raw materials. 7) It is possible to create a combination formulation that does not inhibit the effects of enzyme-based deodorants when used in combination, but rather produces a synergistic effect. 8) Sodium sulfate and dibasic sodium phosphate, which are blended as drying and stabilizing agents in the present invention, have a large ability to form water of crystallization. Aqueous polymer compounds containing glyoxal and enzymes can be added to a certain extent without impairing storage stability.

9) By adding a small amount to the rinsing water, it is possible to very efficiently deodorize and easily sterilize foul odors that are ingrained in cloth, without reducing the strength of the cloth. 10》 When sprayed on unpleasant decomposing corpses, decaying remains of animals and plants, and excrement, it can not only deodorize but also block them from view.

11) Since the aqueous solution does not contain colored metal ions such as iron ions, it will not deteriorate the water quality in the area where this deodorant is used, nor will it cause discoloration of laundry, etc. 12》 Like vomit, diarrheal stool, rotten juice from garbage,
liquid or. It is possible to formulate a mixture that solidifies a slurry-like source of bad odor, 13) A variety of malodorous substances with completely opposite chemical properties such as acidic and basic, reducing and oxidizing (e.g. chlorine gas) At the same time, it is possible to quickly deodorize and, in many cases, reduce or eliminate toxicity.14.
Unlike perfume-type deodorants, it does not cause discomfort due to the sense of smell becoming accustomed to it, nor does it have irritating or chemical odors, and can be completely and completely deodorized. Other additives> In addition to the above-mentioned raw materials of the present invention, enzymes, surfactants, colorants, fragrances, or other known deodorants can be mixed in powder or liquid form as necessary. There are cases. Some examples of such formulations are given in the Examples below. <Examples of bad odor substances to be deodorized) (1) Acidic malodorous substances acetic acid, acetic acid, [11. Hydrogen chloride, various nitrogen oxides, hydrogen sulfide (transient), valeric acid, cresols, alkyl sulfides, probionic acid, mercaptans (reducing)
．． Chlorine gas (oxidizing). Oxides of fatty acids, etc. (2) Basic malodorous substances ammonia, alkyl amines, indols, etc., (3) Aldehyde malodorous substances formaldehyde, crotonaldehyde, probionaldehyde, etc., (4) Polymerizable compound acrylic acid Esters, styrene, etc.

(5) Corpses and excreta of living things, which are composites of these,
Or body odor, activated sludge, waste from various industries, rotten food and waste, etc. [Example] Next, the present invention will be further explained by giving examples.

Reference 1-6 and Actual IMI-3 Wastewater containing solid waste from a certain ham manufacturing factory was treated with normal aeration-type activated sludge treatment, and then dehydrated with a suction method.The solid content of the sludge was When measured by drying for 2 hours at 108°C, it was 85.1%, and when redispersed with distilled water to a solid content of 5.0%, the pH was 6.75 at 15.0°C. In the above sensory test, a strong foul odor which was clearly rated 5 was detected. A fixed amount of this dehydrated activated sludge was added with a fixed amount of the solid deodorizer of the present invention prepared in different formulations in accordance with the concentration of malodorous substances generated under different temperature conditions [Reference Example 1-3] under humid conditions. The malodorous substance concentration measured under the same conditions [Example 1-3] and the results of the sensory test are shown in [Table 3]. For these tests, a certain amount of dehydrated activated sludge was accurately weighed into each polyethylene bag with a capacity of approximately 1,000 ml, the mouth was sealed with a rubber band, and 500 ml of air was injected into each bag.[Table 3] After maintaining the conditions shown above, measure the concentration of malodorous substances using the method described above. Each of the solid deodorants mentioned above is a white powder with excellent fluidity, and as long as it is stored in a closed container, it will not solidify at all and will maintain its fluidity even if stored for 100 days under a pressure of 20g/1. did. Furthermore, even if a Log solid deodorant was placed on a 3mm thick iron plate and a 2kg iron weight was dropped from a height of 2m, no abnormality such as smoke or explosion was observed, indicating that it is safe. Ta. Tratane Katsu A After completing the deodorization test of [Example 3], 500 ml of air was again put into the same bag, and after keeping it at 40°C for 1 hour, the same malodorous substances as in [Table 3] were added again. When we analyzed the
The values detected by the detector tube were all O, and the sensory test results remained unchanged, indicating that the deodorizing effect was long-lasting. Thoughts 7-9 and Facts 4-9 Fresh chicken manure was obtained from a poultry farm, dried at 108℃ for 2 hours, and the solid content was 65%.
It was uniformly dispersed with water to a concentration of 0%, and the pH measured at 20°C was 8.2. Water was added to this chicken manure to reduce the solids content to 25.0%, and then 50g of it was used to extract malodorous substances in the same manner as in [Reference Example 1-6] and [Example 1-3]. A deodorization experiment was conducted to determine the amount of odor produced, and the test method and results are shown in Table 4.

Xsentan 1A A dry, finely powdered form of sodium bicarbonate and 84g of citric acid was used to treat the feces of five adult patients who were unable to go to the toilet on their own.
60g monobasic sodium phosphate
10g per[eIi potassium
2g of Shin-Etsu Silicone KF96-10, 15g of methylene blue (coloring agent), and 828g of Ig anhydrous sodium sulfate were uniformly mixed together as a highly fluid powder, and 200g of the powder was evenly sprinkled on a changing container after defecation. In all cases, the bad odor with an odor intensity of 5 became 0, which was completely odorless, and did not cause any discomfort to the occupants of the room, so it was judged that this would give favorable results to the treatment effect for the patient. In addition, when the feces treated in this way were flushed into a flush toilet, they did not solidify, but were easily dissolved, and did not have any adverse effect on the flush system.

2-
The odor produced when left for 3 days had an odor intensity of at least 4 within about 30 meters, often 5 in the summer. On the surface of this excrement, add 20g of quicklime, 100g of calcium carbonate, and 100g of citric acid.
200g potassium persulfate 2
0 g monobasic potassium phosphate 50 g yeast powder 10 g anhydrous dibasic sodium phosphate 600 g of mixed powder was spread to a thickness of approximately 1 m, and the odor intensity decreased to 1 m, so complaints from local residents were resolved. , and the value of this manure as fertilizer has improved.

lLf! A restaurant's wastewater septic tank, which was not functioning properly due to the high inflow of LL oil and fat, was emitting a large amount of foul odor with an odor intensity of 5 throughout the year. So, 126g of sodium bicarbonate citric acid
100g potassium monophosphate
50g potassium persulfate 5
Qg paraffin wax 15g Lemon fragrance and emulsifier mixture 5g (I use Deozol DI from Inabata Fragrance Co., Ltd.) Anhydrous sodium sulfate
654 g of the homogeneous mixture was compressed into granules and transferred through a manhole into a 160 m'/t shoulder tank with an intersection at a rate of 30 kg. When it was added at a rate of 7 days, the odor intensity was as low as 0-1. The styrene and acrylic acid ester neck of No. 1 remained. Therefore, [Reference example 3
] By putting the deodorizer of , basic, reducing, oxidizing, polymerizing, and other harmful substances can be deodorized simultaneously, instantly, and continuously.

Claims (1)

[Scope of Claims] 1. (a) At least one selected from calcium and magnesium carbonates, bicarbonates, basic carbonates, oxides, hydroxides, and/or alkali metal carbonates and bicarbonates. 1
seeds, (b) at least one selected from citric acid, L-ascorbic acid, succinic acid, DL-malic acid, D-gluconic acid, and primary phosphates of alkali metals, and (c) persulfates of alkali metals. , at least one selected from calcium peroxide, and (d) sodium sulfate and/or dibasic sodium phosphate. 2. A solid deodorant obtained by adding a lubricant and a molding binder to the deodorant according to claim 1.