JPH02293046A - Aluminosilicate deodorant - Google Patents

Abstract

PURPOSE:To effectively remove various offensive odors in man's living environment by using high silica zeolite and a metallic salt of aluminosilicic acid in combination as a deodorant. CONSTITUTION:High silica zeolite having >=30 molar ratio of SiO2 to Al2O3, e.g. Al-freed mordenite or hyper-stabilized Y-type zeolite and a metallic salt of aluminosilicic acid having 2 to 20 molar ratio of SiO2 to Al2O3, e.g. the Mn or Fe salt are used in combination as a deodorant. This deodorant effectively deodorizes various offensive odors emitted in man's living environment, e.g. from a toilet, garbage, cigarette smoke and butts and a house pet.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an aluminosilicate deodorizer. It is. [Prior Art] Deodorizing agents made of various aluminosilicates such as natural or synthetic zeolites are known. For example, 81
As a deodorizing agent made of zeolite with a high 02/Al■03 molar ratio, an organic odor deodorizing agent made of a zeolite whose ratio is estimated to be about 18 or more based on the adsorbed water capacity etc.
5113 (Japanese Patent Laid-Open No. 84-34440); an automobile deodorizer having a ratio of 20 or more has been proposed. Further, as a deodorizing agent made of an aluminosilicate of a metal other than an alkali metal, the above-mentioned high-silica zeolite may be used, such as Mg, Ca. La, Zn. Cd,
Automotive deodorizer consisting of salts such as Cu, Mn, Fe, Ni, Cr, Co (the latter six transition metals are considered to be effective ingredients); Zn, Ag. Cu,
A product for the purpose of deodorizing wastewater consisting of a salt recognized as an amorphous metal selected from Sn (Japanese Patent Application Laid-Open No. 64-79
No. 87); an ammonia deodorizer (Japanese Unexamined Patent Publication No. 55-47143), which is made of natural zeolite converted into a ferrous salt by ion exchange, has been proposed. [Problems to be solved by the invention] However, there are various sources of bad odors around us.
The odors generated therefrom are composed of a plurality of various odor-causing substances. It may not be possible to say that all the causative substances have been detected, but for example, hydrogen sulfide and methyl mercabutane are the main causative substances of the odor at garbage dumps. Methyl sulfide, ammonia trimethylamine. Alcohols, esters, etc. are listed; pigs, cows, etc. Hydrogen sulfide, methylmercabutane, methyl sulfide, ammonia, trimethylamine,
Nitrogen compounds and lower fatty acids have been detected. Thus, hydrogen sulfide, methyl mercabutane, methyl sulfide.
Some substances, such as ammonia and trimethylamine, are commonly detected, but others, such as alcohols, esters, nitrogen compounds, and lower fatty acids, may not be detected depending on the source. At home or in a car,
It's even more complicated, including the human body and mold. Pets, cigarettes, food, garbage. Odor-causing substances from multiple sources such as toilets are mixed together. However, although the conventionally known aluminosilicate deodorizers remove specific odor-causing substances mentioned above, they do not remove the bad odors mentioned above in human living spaces. is not enough. The object of the present invention is to provide a zeolite-based deodorizing agent that can effectively remove bad odors in the environment made up of a wide variety of substances. [Means and effects for solving the problem] The present invention provides S
Zeolite with i02/AI203 molar ratio of 30 or more (hereinafter referred to as high silica zeolite) and 810z/AI20
i of aluminosilicate with a molar ratio of 2 to 20, Mn, Pe.
Co. N1. The gist is a deodorizer consisting of a salt of one or more metals selected from Cu, Zn, AI and Sn (hereinafter, a deodorizer consisting of multiple deodorant components in this way is referred to as a composite deodorizer). It is something to do. As mentioned above, although the high silicate power or aluminosilicate metal salt alone in the present invention is insufficient to remove the above-mentioned bad odor in the living environment, it is possible to remove the bad odor by using them together. It becomes possible. Normally, when an adsorbent adsorbs water, it stops adsorbing other components, but in the composite deodorizer of the present invention, even if it itself contains water, the gas containing the malodorous substance is accompanied by a large amount of water. It selectively adsorbs and removes foul-smelling substances from the environment. The details of the present invention will be explained below. The high-siliency zeolite, which is one of the essential components in the deodorizer of the present invention, has a composition of S i O 2 / A l 2 0
Any zeolite having an s mole ratio of 30 or more may have an burr structure. High-silica zeolite can be prepared by using natural zeolite or synthetic zeolite as a starting material and subjecting it to dealumination treatment; or directly by mixing a silica source, an alumina source, and an alkali source, or further adding an organic mineralizing agent and crystallizing it. Synthesis methods etc. are known. The high-silica zeolite prepared by dealumination treatment includes dealumination mordenite (N.Y.
．． Chen. J. Phy. Chem. ．． 80. (1)
．． BO-84 (1978) ). Ultra-stabilized Y-type zeolite (JP-A-54-122700, Stud
ies in Surf'ace Sc-Ience
and Catalysts. Volume 5.20
3-210 (1980)) ultra-stabilized L-type zeolite (Japanese Unexamined Patent Publication No. 63-50312), etc. are known. High-siliency zeolites prepared by direct synthesis include ZSM-5 (Japanese Patent Publication No. 4B-10064), ZSM-11 (Japanese Patent Publication No. 53-23280), and ZSM-12 (Japanese Patent Publication No. 16079-1987). , ZSM-21 (Japanese Patent Publication No. 53-41857), ZSM-22 (Japanese Patent Publication No. 59-11191)
Publication No. 2). ZSM-23 (JP-A-51-149
Publication No. 900). ZSM-35 (JP-A-52-139
029 Publication), ZSM-38 (Japanese Patent Application Laid-Open No. 1983-134)
No. 798), ZSM-48 (Unexamined Japanese Patent Publication No. 56-22)
Publication No. 622). Silicalite (JP-A-54-7279
Publication No. 5), etc. are known. ? Any of these can be suitably used as a component of the present invention. As can be seen from the above, if this high-silica zeolite, that is, zeolite with a S10/^I20i molar ratio of 30 or more, is not included, only a small portion of the odor-causing substances can be adsorbed. cannot be removed sufficiently. The aluminosilicate metal salt, which is the other component of the present invention, may be either amorphous or crystalline, ie, zeolite. The chemical composition of this aluminosilicate metal salt is M2/-0'AI203''XS102 (where M is Mn, Fc, Co, Ni, Cu, Zn
, one or more metals selected from AI and Sn (
(hereinafter referred to as Zn, etc.), n is its valence, and X is a number from 2 to 20). For amorphous aluminosilicate salts such as Zn, first, an alkali silicate aqueous solution and an aluminum-containing aqueous solution are mixed, for example, in S102.
/Al203 equivalent molar ratio 5 to 10,? h e~8, Amorphous aluminosilicate alkali metal salt is obtained by simultaneously and continuously reacting at room temperature to 40°C, and this is ion-exchanged with ions such as Zn to remove some of the alkali metal ions. Alternatively, it is preferable to use a material manufactured by exchanging the whole material with ions such as Zn. Crystalline ones have a molar ratio of 8102/AI■03 of 2 to 20.
A natural or synthetic zeolite obtained by ion exchange treatment with ions such as Zn is preferably used. As natural zeolite, clinoptilolite type, mordenite type, chabasite type, etc. are generally known, and are suitably used as raw materials for producing salts of crystalline aluminosilicate such as Zn. In addition, synthetic zeolites include A type, faujasite type (X type, Y type), and L type. Mordenite type etc. are manufactured industrially, and these are specially 8102/
S1 except for those treated to increase the AI203 molar ratio
It has a molar ratio of 0■/AI203' of 2 to 20, and is similarly suitably used as a raw material for producing salts of crystalline aluminosilicate such as Zn. Anion side of aluminosilicate metal salt in the present invention (1)
The reason why the S 10 2 / A 1 20 s molar ratio is set to 2 to 20 is because if this ratio is too large, the amount of contained ions such as Zn will be small. This is because it cannot be done. In addition, the reason why the molar ratio is set to 2 or more is that crystalline products cannot have a crystal structure, and amorphous products have a rapidly decreasing ion exchange ability, so that in fact, the components of the present invention cannot be used. This is because they cannot wander around. In addition, the reason why the cation is Zn etc. is because the present inventor has confirmed that among the aluminosilicate metal salts in conventionally known deodorants, it not only has good deodorizing performance but also is inexpensive and has low oral toxicity. . Both exhibit sufficient synergistic action when used in the deodorizer of the present invention. The blending ratio of high silica zeolite and a salt of aluminosilicate such as Zn in the present invention is preferably changed depending on the main malodor-causing substance in the target malodor. For example, the main causes of bad odors are hydrogen sulfide and mercaptans. ammonia. In the case of amines, etc., the main component is a salt of aluminosilicate such as Zn, and a compound containing high silica zeolite exhibits good deodorizing performance. Also, methyl sulfide. Methyl disulfide, acetaldehyde, styrene, hydrocarbons, ketones, aldehydes, alcohols. Esters, nitrogen compounds, sulfur compounds. When lower fatty acids and the like are the main causative substances, a product containing high silica zeolite as the main component and containing a salt of aluminosilicate such as Zn exhibits good deodorizing performance. In particular, ketones. For bad odors whose main cause is compounds containing oxygen atoms such as alcohols, esters, and lower fatty acids,
8102/AI203 A deodorizing agent whose main component is high silica zeolite, which is a salt of alkali metal or alkaline earth metal with a molar ratio of up to several hundred, and which has good deodorizing performance by mixing with a salt of aluminosilicate such as Zn. . As mentioned above, the optimal mixing ratio of high silica and salts of aluminosilicate such as Zn varies depending on the type of malodor to be treated, but it is usually a weight ratio of 1/20 to 20, often 1/2 Selected from the range from to to 10 ha. As mentioned above, the deodorizing performance of the deodorizing agent of the present invention is not impaired by moisture, so there is no need to remove moisture from the zeolite crystals during use, and malodorous gas containing moisture can be treated as is. Therefore, it can be easily used as a deodorizer. When using the deodorizing agent of the present invention in the form of granules, particles, beads, honeycomb, etc., the actual usage conditions such as powder properties (dust, fluidity, bulk ratio m), workability, strength, etc. Alternatively, clay minerals or stable inorganic compounds may be mixed and processed into those shapes in order to match the processing conditions. As the clay mineral, kaolin clay minerals, montmorillonite clay minerals, and the like are preferably used. In the case of inorganic compounds, insoluble substances such as dicalcium phosphate, barium sulfate, and gypsum are preferably used. At this time, crystalline cellulose. Methylcellulose. Carboxymethyl cellulose. If organic additives such as polyvinyl alcohol are used together, the powder characteristics will change depending on actual usage conditions or processing conditions. Workability. Control of strength etc. becomes easy. [Effects of the Invention] The bad odors that occur in our living environment are composed of a plurality of various odor-causing substances. While conventionally known aluminosilicate-based deodorizers cannot sufficiently remove such bad odors, the deodorizer of the present invention can sufficiently remove such bad odors. The deodorizer of the present invention effectively acts on the target bad odor by changing the combination and blending ratio of its components, high silicate zeolite and salts such as Zn of aluminosilicate, and has outstanding deodorizing performance. shows. The deodorizer of the present invention can be used even if the deodorizer itself is in a water-containing state, and even if the gas containing the malodorous substance is accompanied by a large amount of water.
Selectively adsorbs and removes malodorous substances. A bad odor that occurs in or around your home is the smell of garbage. Toilet odor, disposable diaper odor, house mold odor, cigarette odor, pet odor, refrigerator odor, pickle odor, shoe odor. The smell of a dirty box. Locker odor, body odor, menstrual odor, odor attached to cooking utensils (microwave oven, oven range, etc.), burning odor, cooking odor, odor inside the car, paint odor from furniture, etc., odor from garbage collection area, construction There are odors from the work site, sewage and water, etc. In addition, small-scale sources of bad odors are mainly service industries such as restaurants and hospitals, while medium-sized or large-scale sources of bad odors include livestock industries, food manufacturing factories, chemical factories, and other industries. Examples include manufacturing plants. The deodorizer of the present invention can effectively remove all of these bad odors by changing the combination and blending ratio of high silicate zeolite and salts of aluminosilicate such as Zn. Further, the deodorizing agent of the present invention can be directly sprayed on places where odors occur, such as household garbage or triangular corners. Of course, by processing it into granules or honeycomb shapes, it can be used as a deodorizer for small spaces such as refrigerators, boxes, closets, lockers, etc., or for commercial use. It can be used as a deodorizing agent for industrial purposes. In addition, new functions can be developed by combining it with other materials. When combined with detergent, it becomes a deodorizing cleanser or soap. It can also be used as a stationary deodorizer by combining it with a binding material such as plaster and processing it into shapes such as dolls or eggs. When combined with building materials such as wall materials, the house itself can be given a deodorizing function. When combined with a fragrance, it becomes an aromatic deodorizer. By mixing it with a film, it becomes a deodorizing garbage bag, a deodorizing waste disposal bag, etc. When combined with paper, deodorizing paper can be obtained, which can be used as wrapping paper, cardboard, sliding doors, wallpaper, shoji paper, and calendars. poster, food tray insole,
Can be used as memo paper, notebooks, etc. If used in paper diapers, it can be used to replace deodorizing disposable diapers, and if used in sanitary products, it can be used as deodorizing sanitary products. If used in filters for air conditioning equipment, it can both collect dust and deodorize at the same time. Furthermore,
It is also possible to combine it with clothing, shoe insoles, slippers, bedding (pillows, blankets, futons, etc.), sheets for patients, jutan, curtains, etc. [Example] Specific examples of this invention are shown below. The zeolites used for these are as follows. High-silica zeolite> Hereinafter, those indicated by the symbols uns-usy use artificially synthesized Y-type zeolite as a starting material, and are repeatedly subjected to ion exchange with ammonium salts and hydrothermal calcination, resulting in a lattice constant of 24. It was obtained by stabilizing up to 3 people and then performing dealumination treatment with mineral acid. What is designated by the code E-189 uses artificially synthesized mordenite-type zeolite as a starting material, undergoes dealumination treatment with mineral acid, is hydrothermally calcined at 700°C, and is further subjected to dealumination treatment with mineral acid? This is what I was able to do. Those indicated by Z5-54 are directly synthesized ZSMs.
-5 type zeolite was calcined at 500°C for 3 hours. These S10■/A1■O determined by atomic absorption spectrophotometry
, molar ratio and water content are shown in Table 1. Aluminosilicate metal salt> Those indicated by the symbol Cu-Y are obtained by ion-exchanging artificially synthesized Y-type zeolite with copper sulfate. Those indicated by the symbols Cu-G and Zn-G are amorphous aluminosilicate (chemical composition: Na20 = 3.1vt%
, A l ■0, -5. Ovt%, S 102 −
29.9 wt%, ie, S10z/AlzOi molar ratio 10), was obtained by ion-exchanging with copper sulfate and zinc sulfate, respectively. Table 2 shows the metal content and water content determined by atomic absorption spectrophotometry. Deodorizing agent of the present invention> The compound indicated by the symbol 1^ was prepared by weighing 22 g and 31 g of Z5-54 and Zn-G, respectively, and thoroughly mixing them in an agate mortar. What is indicated by the compound 1B code is UHS-US
Weighed 22g and 27g of Y and Cu-Y, respectively.
Prepared by thoroughly mixing in an agate mortar. The compound-C code indicates IE-189 and Cu-G.
558 g, 783 g and 135 g of dicalcium phosphate dihydrate (indicated as Rinkal in the table), respectively.
Weigh out 3 g, add pure water to prepare 10 kg of slurry, and mix with 40 g of carboxymethyl cellulose.
It was prepared by spray drying. The water content of Composite-C was 19vt%. Other Adsorbents> Two types of commercially available adsorbents were prepared for comparison with the deodorizer of the present invention. The zeolite indicated by the symbol Kunimine is a natural zeolite manufactured by Kunimine Industries, and a powder X-ray diffraction test revealed that it was a mordenite type zeolite. For bone ash, a reagent manufactured by Kanto Kagaku was used. Table 1 Table 2 Preparation of deodorizing performance evaluation> In order to evaluate the performance of the deodorizing agent prepared by the above method, the following four types of odor liquids were prepared. Each of the prepared odor liquids (1d) was injected with a syringe into a bag (manufactured by Gascro Industries) containing 31 odorless air, and the bags were left to stand for 30 minutes and smelled, and all were judged to have strong odors. This odor was given an odor intensity of 4. When this malodorous gas with an odor intensity of 4 was diluted with odorless air, it became odorless after being diluted exactly 40 times. The standard odor for comparing the performance of deodorizers was established as follows. In other words, the odor with odor intensity 4 is multiplied by 2.5 times, C times. Those diluted with odorless air 15 times and 39 times were used as reference odors with odor intensities of 3.2.1 and 0, respectively. The method for preparing each odor liquid is as follows.

[Preparation of rotten fish odor liquid]

200 g of sardines were cut into pieces, too much pure water was added, and the mixture was run in a household juicer mixer for 5 minutes to form a slurry. 100h+j of this sardine slurry! It was transferred to a bolibin, covered with a breather stopper equipped with a plastic bag, and kept at 30°C for one week to rot. This rotten sardine slurry was set in a centrifugal sedimentation machine and allowed to settle and separate at 3000 rpm for 30 minutes, and only the aqueous layer was separated. Add this solution to pure water
The solution diluted to 0 times was used as a rotten fish odor liquid.

[Preparation of chicken feces odor liquid]

200 g of pure water was added to 200 g of raw chicken manure and stirred with a glass rod until it became homogeneous to obtain a slurry of chicken manure. Set this chicken feces slurry in a centrifugal sedimentation machine,
Sedimentation was carried out at 000 rpra for 30 minutes, and only the aqueous layer was separated. This liquid was diluted 30 times with pure water and used as a chicken feces odor liquid.

[Preparation of tobacco odor liquid]

In order to absorb tobacco odor into water, the apparatus shown in Figure 1 was prepared. As shown in Figure 1, a Mild Seven (manufactured by Nippon Tobacco) was set and lit. The suction pressure of the aspirator attached to absorption bottle A was adjusted so that one cigarette would burn in 5 minutes. The inhaled smoke was absorbed into 100 m of pure water placed in absorption bottle A. The smoke generated from the tip of the burning cigarette was put into an absorption bottle B10.
It was absorbed into 0 d of pure water. The cigarette butts were placed in a petri dish containing 50 d of pure water and the fire was extinguished. This operation was performed for 40 Mild Seven bottles. Finally, the liquids in absorption bottles A and B and the butts in the Petri dish were mixed, and the mixture was left to stand for 30 minutes. The mixture was suction-filtered using a Buchner funnel, and pure water was added to the separated liquid.
I made it d. This liquid was diluted 400 times with pure water to obtain a tobacco odor liquid.

[Preparation of kimchi odor liquid]

200 g of Kimchi No Soichiya Co., Ltd. was placed in a centrifugal sedimentation machine and sedimented and separated at 3000 rpm for 30 minutes to separate only the aqueous layer. This liquid was diluted 50 times with pure water to obtain a kimchi odor liquid. Examples 1-4, Comparative Examples 1-17 Accurately weigh 300 mg of each of the above deodorants, put them in a scent bag, fill with 3 i of odorless air, and inject 1 of each odor solution with a syringe into 4 bags each. Prepared. After being left at room temperature for 30 minutes, four panelists judged the odor intensity while comparing each odor liquid with a reference odor. The results are shown in Tables 3-6. Table 5 Odor liquid: Tobacco odor liquid Table 6 Odor liquid: Kimchi odor liquid

[Brief explanation of drawings]

Figure 1 shows Preparation of tobacco odor liquid in Examples FIG.

Claims (3)

[Claims] (1) Zeolite with a SiO_2/Al_2O_3 molar ratio of 30 or more and a SiO_2/Al_2O_3 molar ratio of 2 to 20
of aluminosilicate, Mn, Fe, Co, Nl, Cu, Z
A deodorizing agent comprising a salt of one or more metals selected from n, Al, and Sn (hereinafter referred to as aluminosilicate metal salt). (2) Claim (1) wherein the aluminosilicate metal salt is amorphous.
) Deodorizer described. (3) Claim (1) wherein the aluminosilicate metal salt is crystalline.
) Deodorizer described.