JP2020110765A - Gas adsorbent - Google Patents

Abstract

To provide a chemisorption-type adsorbent that excels in the adsorption effect for basic gases such as ammonia gas and also has excellent chemical resistance, and to provide an adsorptive finished article such as fiber and resin molding using the same.SOLUTION: The adsorbent of the present invention comprises a solid represented by the following formula (1). aM12O-bP2O5-SiO2-cM2O2-dH2O (1). (In the formula (1), M1 is an alkali metal element, M2 is Zr and/or Ti, a to d represents molar ratios, a is 0.005 to 0.2, b is 0.05 to 1.0, c is 0.05 to 1.0, and d is 0.05 to 2.).SELECTED DRAWING: None

Description

The present invention relates to a solid adsorbent having a specific component composition and a gas adsorbent processed product using the same.

Due to the demand for a comfortable environment and increasing health consciousness, interest in the air environment in daily life has been increasing in recent years. For example, in order to improve the air environment, a gas-adsorbed processed product such as an indoor deodorant or an air purifier that can reduce a bad smell or harmful gas has been commercialized. In addition, various processed products having a deodorizing effect added to wallpaper, curtains, carpets, mats, sofas, masks, clothes and the like have been commercialized. Since the target gas components are varied in these adsorptive processed products, adsorbents are used according to the type of gas.

Conventionally, activated carbon has been frequently used as an adsorbent, but there is a limit to general-purpose use of activated carbon due to its black color tone and physical adsorption. One of the drawbacks of physical adsorption is that it adsorbs any gas component, and in the open space, gas other than malodorous is constantly adsorbed, resulting in immediate saturation. Furthermore, because the adsorption amount of the physical adsorbent used approaches the saturation range or the environmental temperature rises, the once adsorbed gas is released to the environment, and the physical adsorbent itself becomes a source of malodor, There is also a problem that it can only be used for products that can be replaced as soon as the adsorption effect decreases.

Therefore, various white or light-colored chemical adsorbents have been developed and put into practical use. The chemical adsorbent does not release the once adsorbed gas component and does not become a source of a bad odor even if the adsorption effect is lowered, and therefore it can be used for a product which is not easily replaced. However, since the chemical adsorbent is adsorbed by reacting with the target gas component, the types of gas components that can be adsorbed are limited. Among the gas components, basic gases such as ammonia and trimethylamine, which are contained in rotten odor, excretion odor, sweat odor, age odor, cigarette odor, pet odor, fish odor, etc. are adsorbed by activated carbon as compared with acidic gas. Since it is a difficult gas, it is important to develop a chemical adsorbent that adsorbs basic gas.

As an adsorbent having a chemical adsorption property to a basic gas, for example, in Patent Document 1, SiO ₂ : 50 to 80 mol% and MO _n/2 : 5 to 65 mol in terms of a three-component composition ratio expressed as an oxide. %, Al ₂ O ₃ : 1 to 60 mol% (M is at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin and zirconium, and n is a valence of the metal. The deodorant composition containing an aluminosilicate corresponding to (4) and a porous material having a specific surface area of 500 m ² /g or more is disclosed. Patent Document 2 discloses an antibacterial agent having a deodorizing property, which is composed of an amorphous composite of an oxide of a metal having an antibacterial effect and silicon dioxide. Patent Document 3 discloses a deodorant/antibacterial fiber finishing agent in which a porous silicic acid-based powder made of a solid solution of silicic acid or a salt thereof and a metal oxide and a porous titanium oxide powder are dispersed in a binder resin material. Is disclosed. Patent Document 4 discloses an antibacterial deodorant composed of an antibacterial deodorant component and silica-based composite oxide particles, containing 0.1 to 25% by weight of silver ion as Ag ₂ O as an antibacterial deodorant component, and Al 1 or 2 or more selected from ₂ O ₃ , B ₂ O ₃ , ZrO ₂ , TiO ₂ , MgO, CaO, CeO ₂ , SnO ₂ , Sb ₂ O ₅ , ZnO, Fe ₂ O ₃ and P ₂ O ₅ . Disclosed is an antibacterial deodorant characterized in that the silica-based composite oxide particles containing the oxide of 1) contain 1 to 20% by weight of sodium ions as Na ₂ O in the particles. Patent Document 5 has a molar composition ratio represented by SiO ₂ ·xZnO (0<x<0.60) in oxide display, and the amount of hydroxyl groups measured by the di-n-butylamine titration method is Disclosed is an amorphous-silica zinc-based ammonia deodorant represented by SiO ₂ .xZnO having a specific molar composition of 200 to 900 meq/kg and a primary particle diameter of 7.0 to 20.0 nm. ing. Patent Document 6, xM are _{2 O · Al 2 O 3 ·} ySiO 2 · nH 2 O (M is an alkali metal, x is a number from 0.1 to 0.5, y is a number of 5-15 And n is a number from 0.3 to 15), and the deodorant composed of amorphous aluminum silicate can surely adsorb odors such as ammonia gas and is easy for fibers and resin molded products. It is disclosed that it can be processed into. Patent Document 7 discloses a mixture of metal oxide particles having an average primary particle diameter of 3 nm or more and 100 nm or less and made of zinc oxide and/or zirconium oxide, and porous silica particles, and the specific surface area of the mixture is 100 m ^2. /G or more and 900 m ² /g or less, the reduction rate of ammonia measured by a specific method is 75% or more, the reduction rate of acetic acid is 85% or more, and the reduction rate of isovaleric acid is 95% or more. Odorants are disclosed.

JP-A-1-148340 JP-A-3-190805 JP, 9-217278, A JP, 2010-273698, A JP, 2005-29645, A Re-table 2016-167272 JP, 2007-63945, A

However, the adsorbents disclosed in Patent Documents 1 to 7 do not have a sufficient ammonia gas adsorption effect. The adsorption effect can be shown by the maximum gas capacity mL/g that can be adsorbed per 1 g of the adsorbent. Ammonia gas adsorption capacity is preferably as high as 30 mL/g or more in consideration of application to various resin processed products such as fibers and films. If less than 30 mL/g, a large amount of adsorbent must be used. A sufficient deodorizing effect cannot be expressed. The adsorbents disclosed in Patent Documents 1 to 5 have an ammonia gas adsorption capacity of 10 mL/g or less, and the adsorbents disclosed in Patent Documents 6 and 7 have an ammonia gas adsorption capacity of 46 mL/g at the maximum. .. Further, since the disclosed adsorbent is composed of a component having low acid resistance such as Al ₂ O ₃ and ZnO, the chemical resistance is poor and the effect persistence remains a problem.
Then, the subject of this invention is providing the chemical adsorption type adsorbent which is excellent in the adsorption effect with respect to basic gas, such as ammonia gas, and also excellent in chemical resistance. Another object is to provide an absorbent processed product such as a fiber or a resin molded product using the same.

The present inventor has found that a solid adsorbent having a specific composition exhibits extremely high chemical adsorption of ammonia gas and is also excellent in chemical resistance. It was also found that adsorptive processed products containing this adsorbent, such as paper, non-woven fabrics, fibers and plastic molded products, exhibit high deodorant performance.
That is, in the first aspect of the present invention, the following adsorbent is provided.
1. An adsorbent comprising a solid represented by the following formula (1).
aM ¹ ₂ O・bP ₂ O ₅・SiO ₂・cM ² O ₂・dH ₂ O (1)
(In the formula (1), M ¹ is an alkali metal element, M ² is Zr and/or Ti, a to d represent a molar ratio, a is 0.005 to 0.2, and b is 0. 05 to 1.0, c is 0.05 to 1.0, and d is 0.05 to 2.)
2. 2. The adsorbent according to 1 above, which is amorphous and has a basic gas adsorption ability.
3. 3. The adsorbent according to 1 or 2 above, which has a chemical adsorption capacity of ammonia gas of 30 mL/g or more.
In a second aspect of the present invention, there is provided a gas adsorptive processed product containing the adsorbent according to any one of 1 to 3 above.

The adsorbent of the present invention exhibits an excellent adsorption effect on basic gas, particularly ammonia gas, by chemisorption. The adsorbent is composed of a component having acid resistance and has excellent chemical resistance. In addition, the adsorbent of the present invention can be easily applied to paper, fiber, resin molded products, etc. such as coating and kneading, and is excellent in production processability of adsorptive processed products. By using the adsorbent according to the present invention, it is possible to provide an adsorptive processed product such as a paper, a fiber, or a resin molded product that exhibits excellent adsorption performance.

The embodiments of the present invention are described below, but the present invention is not limited thereto. Unless otherwise specified,% means mass %, and part means part by mass.

The present invention provides an adsorbent characterized by comprising a solid represented by the following formula (1).
aM ¹ ₂ O・bP ₂ O ₅・SiO ₂・cM ² O ₂・dH ₂ O (1)
(In Formula (1), M ¹ is an alkali metal element, M ² is Zr and/or Ti, a to d represent a molar ratio, a is 0.005 to 0.2, and b is 0. 05 to 1.0, c is 0.05 to 1.0, and d is 0.05 to 2.)
The element M ¹ is preferably Na or K, and particularly preferably Na, from the viewpoint of adsorption of ammonia gas. The element M ² is Zr and/or Ti that has acid resistance, is a component that is also effective in adsorbing a basic gas, particularly ammonia gas, and is preferably Ti.
The preferable ranges of the molar ratios a to d are as follows.
The range of a is preferably 0.01 to 0.2, and more preferably 0.05 to 0.1. When a is less than 0.005, the chemical resistance of the adsorbent is lowered. On the other hand, when it is larger than 0.2, the chemical adsorption of ammonia gas is lowered and, when compounded with a resin, problems such as yellowing are likely to occur.
The range of b is preferably 0.1 to 0.8, more preferably 0.2 to 0.7. When b is less than 0.05 or exceeds 1.0, the productivity of the adsorbent and the chemisorption of ammonia gas are reduced.
The range of c is preferably 0.1 to 0.9, and more preferably 0.2 to 0.8. If c is less than 0.05 or exceeds 1.0, the productivity of the adsorbent and the chemisorption of ammonia gas are reduced.
The range of d is preferably 0.1 to 1.5, and more preferably 0.2 to 1.0. When the value of d is lower than 0.05, the productivity of the adsorbent is lowered. On the other hand, if it exceeds 2.0, the adsorption performance is deteriorated and, when compounded with the resin, problems such as foaming are likely to occur.

The adsorbent of the present invention is an amorphous solid powder, and in the powder X-ray diffraction measurement, there is no clear diffraction peak due to the crystal structure, or when there is a diffraction peak, the half-value width of the maximum peak is 1. It is less than 5 rad. Similar to an adsorbent having a physical adsorptivity, even an adsorbent having a chemical adsorptivity adsorbs a gas more efficiently as the contact area with the gas is larger. In that respect, the amorphous powder has a large contact area with the gas and is excellent in adsorptivity. Moreover, since the amorphous solid of the present invention is composed of a specific composition, many reactive groups having chemisorption are arranged on the inner and outer surfaces of the solid, and thus the chemisorption is excellent.

Although the adsorbent of the present invention is an amorphous solid powder, it is not glass obtained by heat-melting raw materials having the same component composition at a high temperature of 1000° C. or higher, or a pulverized product thereof. This is because glass has a low specific surface area and a small number of active adsorption sites, and thus has poor gas adsorption properties. BET specific surface area, from the viewpoint of adsorption of ammonia gas, preferably 50 m ² / g or more, more preferably 100~1000m ² / g, more preferably 200-700 ² / g.

The particle size of the adsorbent of the present invention may be selected according to the intended use. The particle size is preferably 0.5 to 20 μm, more preferably 2 to 10 μm, as measured by laser diffraction type particle size distribution. The maximum particle size of the adsorbent is preferably 50 μm or less, more preferably 30 μm or less. When the maximum particle diameter is 50 μm or less, the workability in manufacturing the adsorptive processed product is good, and the appearance of the adsorptive processed product such as a molded product does not occur.

The powder color of the adsorbent of the present invention is not particularly limited, but is generally white and can be represented by the Lab color space display. In the Lab color space display method, the adsorbent can be sandwiched between transparent films and measured with a colorimeter. The powder color of the adsorbent in the present invention is preferably L value 90 to 99, a value -2 to 3, and b value -2 to 3. When the Lab color space display is within the above range, the adsorbent can be used for a wide range of purposes.

The adsorbent of the present invention is excellent in adsorbing a basic gas among various gas components. The types of gas can be classified into basic gas, acidic gas, sulfur-based gas, aldehyde gas, and the like, and typical basic gases include ammonia, trimethylamine, pyridine, and the like.

The adsorbent of the present invention can be manufactured by applying a known technique to each component, and there is no restriction on the raw material, the manufacturing method, the equipment and the like. Generally speaking, it is obtained by blending a water-soluble compound in a predetermined component ratio and collecting the resulting solid matter.
The preferred method for producing the adsorbent is as follows.
A water-soluble alkali metal compound, a water-soluble silicic acid compound, a water-soluble phosphoric acid compound, a water-soluble titanium compound and/or a water-soluble zirconium compound is used as a starting material to prepare an aqueous mixed solution of these, and the mixture is left to stand to give a solid product. To get The component ratio of these compounds, when converted to each oxide, is a number of 0.05 to 0.2 for the alkali metal element when divided by the molar ratio of silicon oxide, and 0.05 for phosphorus pentoxide. The number of titanium oxide and/or zirconium oxide is 0.05 to 1.0. As the water-soluble alkali metal compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium sulfate, sodium nitrate or the like can be used. Water glass, colloidal silica, or the like can be used as the water-soluble silicate compound. As the water-soluble titanium compound, titanium sulfate, titanium oxysulfate, colloidal titanium or the like can be used. As the water-soluble zirconium compound, zirconium sulfate, zirconium oxychloride, zirconium nitrate, colloidal zircon, or the like can be used. After these mixed solutions are prepared, they are mixed or stored by standing for several minutes to 10 days. The obtained solid is filtered, washed, and then dried at 80°C to 300°C. Then, the adsorbent of the present invention can be produced by pulverizing to adjust the particle size to a required level.

For other purposes, the adsorbent of the present invention may contain a small amount of an alkaline earth metal element, a transition metal element, or the like in an amount that does not significantly change the physical properties of the adsorbent or the gas adsorption capacity. In order to contain these other metal elements, a water-soluble compound of the corresponding element may be added in the above manufacturing method.

The adsorption capacity of the adsorbent of the present invention is 30 mL or more, preferably 40 mL or more, and more preferably 50 mL or more in terms of the amount of adsorbed ammonia gas per 1 g of the adsorbent. If the adsorption capacity is 30 mL or less, a sufficient adsorption effect cannot be obtained unless a large amount of adsorbent is used. This adsorption capacity is the maximum amount of a specific gas component that can be absorbed or adsorbed by the adsorbent, and in practice, the adsorption capacities adsorbed by both physical adsorption and chemical adsorption mechanisms are often not distinguished. Since physical adsorption does not adsorb at high temperatures, the chemisorption capacity of the adsorbent can be measured by increasing the adsorption test temperature to 40° C. or higher. The specific method for measuring the chemical adsorption capacity is as follows.
The adsorbent is placed in a test bag made of vinyl alcohol-based polymer or polyester, which is a material that does not easily adsorb the target gas and is impermeable to air, and the bag is sealed. After the target gas is injected into the sealed test bag, 40°C Store in an incubator at ~60°C. The concentration of the target gas remaining in the test bag is measured immediately after the target gas is injected and after a certain time has elapsed. At this time, the point when the residual gas concentration after a certain period of time became equal to the decreasing rate of the gas concentration of the comparison test bag containing no adsorbent was defined as the point at which the adsorption performance was saturated, The value obtained by multiplying the residual gas concentration difference in the test bag by the gas volume in the test bag is taken as the amount of adsorbed gas absorbed by the adsorbent. The value obtained by dividing the amount of adsorbed gas by the weight of the adsorbent used in the test is the adsorption capacity mL/g.

The adsorbent of the present invention may be mixed or diluted with other adsorbents or non-adsorbents. Use of the adsorbent of the present invention in combination with another gas adsorbent such as an acidic gas, a fatty acid gas, a sulfur-based gas, an aldehyde gas, etc., as an adsorbent composition in order to efficiently remove the complex malodor Is also possible. Other adsorbents include activated carbon, aluminum silicate, sodium silicate, potassium silicate, hydrotalcite, zeolite, silica gel, copper-containing silica gel, hydrous zirconium oxide, zirconium phosphate, titanium phosphate, zinc oxide, aluminum oxide. , Sepiolite, dihydrazide compounds and the like.

Preparation of adsorptive material (processed product) It will be described that the adsorbent of the present invention is combined with other materials such as paper, fiber and resin to form an adsorptive processed product. As the processing method of the adsorptive processed product to which the adsorbent is added, there is a method of kneading into the raw material resin and the adsorbent is spread by post-processing by using a binder etc. on the surface of the molded product that has already become the shape of the processed product. There is a way to do it.

The kneading process can be obtained by blending a melted or melted or heat-melted liquid resin with the adsorbent of the present invention, and molding the obtained adsorbent-containing resin composition with a molding machine. It is also possible to prepare a pellet-shaped resin called a masterbatch containing a high concentration of an adsorbent in advance, mix this with a main resin, and then mold the resin with a molding machine. In order to improve the physical properties, the adsorbent-containing resin composition may include a dispersant, a pigment, a dye, an antioxidant, a light stabilizer, an antistatic agent, an antibacterial agent, a foaming agent, and an impact strengthening agent, if necessary. Additives such as glass fiber, moisture-proofing agents and extenders can also be added. As a molding method for producing the above resin molded product, general spinning and resin molding methods such as dry spinning, wet spinning, melt spinning, injection molding, extrusion molding, inflation molding, vacuum molding, and foam molding are applied. be able to. The resin to be applied is not particularly limited, and known synthetic, semi-synthetic or natural resins can be used, and these resins may be homopolymers or copolymers. Preferred resins are polyester, polycarbonate, polyamide, acrylic, polypropylene, polyethylene, polyvinyl chloride, polyvinylidene, polyurethane, polystyrene, ABS, AS, cellulose and the like. The adsorbent content in the case of kneading is not particularly limited, but is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin. If the content of the adsorbent is increased, the adsorptivity can be strongly exerted and can be maintained for a long period of time.However, if the content is excessively large, the adsorption effect does not significantly change, and the strength of the molded product decreases. Problems may also occur.

The method of post-processing the adsorbent on the surface of the processed product is carried out by spraying, coating or coating a working liquid composed of an adsorbent-containing liquid composition consisting of an aqueous or organic solvent-based suspension containing the adsorbent and a binder resin. It can be obtained by spreading it on the surface of the processed product by a method such as dipping and removing the medium such as a solvent. The binder component used in producing the adsorbent-containing processing liquid is not particularly limited, and may be any of natural vegetable oil, natural resin, semi-synthetic resin and synthetic resin. Examples of fats and oils that can be used include linseed oil, sesame oil, dry oil or semi-dry oil such as soybean oil, rosin, nitrocellulose, ethyl cellulose, cellulose acetate butyrate, benzyl cellulose, novolac type or resol type. Examples thereof include phenol resin, alkyd resin, aminoalkyd resin, acrylic resin, vinyl chloride resin, silicone resin, fluororesin, epoxy resin, urethane resin, saturated polyester resin, melamine resin and polyvinylidene chloride resin. These adsorbent processing liquids may be of a type that cures by any mechanism, and when curing a coating film, an oxidation polymerization type, a moisture polymerization type, a heat curing type, a catalyst curing type, an ultraviolet curing type, a polyol curing type, etc. Can be

The ratio of the adsorbent of the present invention contained in the adsorbent processing liquid is not particularly limited. Generally, if the content of adsorbent is increased, the adsorbability can be strongly exerted and can be maintained for a long period of time, but even if it is contained above a certain level, there is no big difference in the adsorption effect, or spread The processed surface loses its luster or cracks. Therefore, the adsorbent content ratio in the spreading process is such that the adhering amount of 0.1 g to 10 g per 1 m ² of the processed surface area is appropriate, and the binder used in combination is 10 parts to 500 parts, preferably 100 parts to 100 parts of the adsorbent. An appropriate amount is 30 to 200 parts. Further, the pigment, the dispersant, and other additives to be mixed in the processing liquid are not particularly limited, except those which may cause a chemical reaction with the adsorbent of the present invention. This adsorbent-containing working fluid can be easily prepared, and specifically, for example, using a general mixing device such as a ball mill, a roll mill, a disper or a mixer, a raw material such as an adsorbent, a binder or a solvent. It suffices to sufficiently disperse and mix the components.

Useful absorbent products using the adsorbent of the present invention include deodorant fibers. The deodorant fiber may be processed by kneading an adsorbent into a resin as a raw material for fiber, or may be spread by post-processing using a binder or the like on a fiber, cotton, non-woven fabric, knitted or woven fabric processed product, etc. It is possible. The type of fiber to be post-processed may be not only synthetic fibers but also natural fibers such as cotton and wool. The deodorant fiber containing the adsorbent of the present invention is used for underwear, socks, tights, aprons, spinning, clothing such as sportswear, nursing clothes, duvets, cushions, blankets, carpets, sofas, air filters, duvet covers, Curtains, car seats, car mats, etc. are exemplified, and they can also be used for deodorant sheets described later.

For the use of the adsorbent of the present invention, a deodorant sheet and a deodorant film are also mentioned as preferable examples. The raw material sheet before processing is not particularly limited, and its material, fine structure, and the like can be adapted according to the application and the like. A preferable material for the raw material sheet is resin, an organic material such as paper, an inorganic material, or a composite thereof. Preferable specific examples include Japanese paper, synthetic paper, non-woven fabric, resin film and the like, and a particularly preferable raw material sheet is paper made of natural pulp and/or synthetic pulp. The deodorant sheet provided with the adsorbent of the present invention is, for example, medical wrapping paper, food wrapping paper, electrical equipment wrapping paper, nursing care paper product, freshness keeping paper, paper clothing, air purifying filter, wallpaper, tissue paper. It can be used as toilet paper.

The resin molded product or foam molded product containing the adsorbent of the present invention is used, for example, as a home appliance such as a cooler box, an air purifier, or a refrigerator, a general household item such as a trash box or a drainer, and a care product such as a portable toilet. be able to.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In addition, "%" is mass% unless otherwise indicated.

The method for analyzing the adsorbent, the method for evaluating the adsorbent, and the method for evaluating the deodorant cloth, which is an adsorbent processed product, are as follows.
(1) was quantified _{Na 2 O, P 2 O 5} , SiO 2, TiO 2 and ZrO ₂ content by the composition analysis adsorbent of the adsorbent X-ray fluorescence spectrometer. Further, the H ₂ O content was quantified from the loss on drying at 150° C. for 2 hours, and the molar ratio of Na ₂ O, P ₂ O ₅ , SiO ₂ , TiO ₂ , ZrO ₂ and H ₂ O was calculated.

(2) Crystallinity of the adsorbent powder The powder crystallinity was measured by Cu Kα ray using a powder X-ray diffractometer to obtain an X-ray diffraction image. If a clear diffraction peak was obtained, it was judged to be crystalline, and if not, it was judged to be amorphous.

(3) Average particle size of adsorbent powder (d50)
The adsorbent powder was measured with a laser diffraction particle size distribution analyzer, and the results were analyzed on a volume basis. The content% of the particle size distribution is the volume% of all particles according to this analysis method, but since the density of the measured powder is constant, it has the same meaning as mass %.

(4) Ammonia gas adsorption capacity of adsorbent 0.01 g of dried adsorbent powder was placed in a test bag made of vinyl alcohol polymer film, 3 L of ammonia gas was injected therein, and the test bag was stored at 45°C for 1 hour. The residual gas concentration of was measured with a gas detector tube for ammonia. The amount of the adsorbed gas in 0.01 g of the adsorbent powder is determined from the difference with the residual gas concentration in the test bag without the adsorbent. The ammonia adsorption capacity is indicated by the ammonia adsorption capacity mL/g per 1 g of the adsorbent powder.

(5) Deodorant performance of deodorant cloth 100 cm ² of deodorant cloth was put in a test bag made of vinyl alcohol-based polymer film, 3 L of air containing 100 ppm of ammonia was injected therein, and the test bag was stored at 45°C for 2 hours. The residual gas concentration was measured by a gas detector tube, and the deodorization rate was shown when the residual gas concentration in the blank test with only the test bag, which was similarly measured without the deodorant cloth, was 100%.

(6) Chemical resistance of adsorbent The deodorant cloth was immersed in a hydrochloric acid solution of pH 3 for 2 hours, rinsed well with water, and the deodorant performance of the dried deodorant cloth was measured. That is, chemical resistance is evaluated by acid resistance.

-Production, analysis and evaluation of adsorbent (Example 1)
70 g of 75% aqueous phosphoric acid solution, 80 g of No. 1 sodium silicate and 100 g of 30% aqueous titanium sulfate solution were mixed to form a white solid, and then heated at 80° C. for 2 hours while stirring. Then, the obtained solid-containing liquid was filtered, the solid was washed with water, and then dried at 150° C. for 24 hours to obtain a solid. Table 1 shows the results of various analyzes and measurements of the powdery adsorbent obtained by crushing the solid matter.

(Example 2)
A 75% phosphoric acid aqueous solution (80 g) and No. 3 sodium silicate (80 g) were mixed with a 30% titanium sulfate aqueous solution (150 g) to form a white solid, which was then heated at 80° C. for 2 hours while stirring. Then, the obtained solid-containing solution was filtered, washed with water, and then dried at 150° C. for 24 hours to obtain a solid. This solid was ground. Table 1 shows the results of various analyzes and measurements of the powdery adsorbent obtained by crushing the solid matter.

(Example 3)
A 75% phosphoric acid aqueous solution (70 g) and No. 1 sodium silicate (80 g) were mixed with a 30% titanium oxysulfate aqueous solution (150 g) to form a white solid, which was then stored at 20° C. for 2 hours while stirring. Then, the obtained solid-containing solution was filtered, washed with water, and then dried at 150° C. for 24 hours to obtain a solid. Table 1 shows the results of various analyzes and measurements of the powdery adsorbent obtained by crushing the solid matter.

(Example 4)
30 g of 75% phosphoric acid aqueous solution, 15 g of 48% caustic soda, 80 g of 30% colloidal silica and 130 g of 20% titanium oxysulfate aqueous solution were mixed to form a white solid, which was then left standing at 20° C. for 2 hours. Then, the obtained solid-containing solution was filtered, washed with water, and then dried at 150° C. for 24 hours to obtain a solid. Table 1 shows the results of various analyzes and measurements of the powdery adsorbent obtained by crushing the solid matter.

(Example 5)
80 g of 75% phosphoric acid aqueous solution, 20 g of 48% caustic soda, 80 g of No. 1 sodium silicate and 100 g of 30% zirconium oxychloride aqueous solution were mixed to form a white solid, which was then stored at 20° C. for 2 hours while stirring. Then, the obtained solid-containing solution was filtered, washed with water, and then dried at 150° C. for 24 hours to obtain a solid. This solid was ground. Table 1 shows the results of various analyzes and measurements of the powdery adsorbent obtained by crushing the solid matter.

(Comparative Example 1)
A 75% phosphoric acid aqueous solution (5 g) and No. 1 sodium silicate (80 g) were mixed with a 30% titanium sulfate aqueous solution (150 g) to form a white solid, which was then heated with stirring at 100° C. for 10 hours. Then, the obtained solid-containing solution was filtered, washed with water, and then dried at 150° C. for 24 hours to obtain a solid. Table 1 shows the results of various analyzes and measurements of the powdery adsorbent obtained by crushing the solid matter.

(Comparative example 2)
80 g of sodium silicate No. 1 and 150 g of a 30% titanium sulfate aqueous solution were mixed to form a white solid, which was then heated at 80° C. for 2 hours while stirring. Then, the obtained solid-containing solution was filtered, washed with water, and then dried at 150° C. for 24 hours to obtain a solid. Table 1 shows the results of various analyzes and measurements of the powdery adsorbent obtained by crushing the solid matter.

(Comparative example 3)
30 g of 48% sodium hydroxide and 100 g of No. 3 sodium silicate and 150 g of 30% sodium aluminate aqueous solution were mixed to form a white solid, which was then heated at 100° C. for 2 hours while stirring. Then, the obtained solid-containing solution was filtered, washed with water, and then dried at 150° C. for 24 hours to obtain a solid. Table 1 shows the results of various analyzes and measurements of the powdery adsorbent obtained by crushing the solid matter.

(Comparative Example 4)
180 g of 75% phosphoric acid aqueous solution, 20 g of 48% caustic soda, 80 g of No. 1 sodium silicate and 100 g of 30% zirconium oxychloride aqueous solution were mixed to form a white solid, and the obtained solid-containing solution was filtered. After washing with water, it was dried at 150° C. for 24 hours to obtain a solid. Table 1 shows the results of various analyzes and measurements of the powdery adsorbent obtained by crushing the solid matter.

(Comparative example 5)
80 g of 75% phosphoric acid aqueous solution, 20 g of 48% caustic soda, 80 g of No. 1 sodium silicate and 100 g of 30% aluminum chloride aqueous solution were mixed to form a white solid. The obtained solid-containing liquid was filtered, washed with water, and then dried at 150° C. for 24 hours to obtain a solid. Table 1 shows the results of various analyzes and measurements of the powdery adsorbent obtained by crushing the solid matter.

(Comparative example 6)
A 10% aluminum sulfate aqueous solution and No. 2 water glass were mixed to form a white solid, which was then heat aged at 96° C. for 4 hours with stirring. Then, the obtained solid-containing liquid was filtered, washed with water, and then dried at 105° C. for 24 hours to obtain a solid. A powder of amorphous aluminum silicate was produced by crushing this solid material. Various analyzes or measurements were performed using the obtained powder as an adsorbent. The analysis results and measurement results are shown in Table 1.

As is clear from Table 1, the adsorbents of Examples 1 to 5 and Comparative Example 6 have an ammonia gas adsorption capacity of 30 mL/g or more at 45° C., and it was found that the adsorption effect by chemisorption is excellent. On the other hand, the adsorbents of Comparative Examples 1 to 5 had a low ammonia gas adsorption capacity at 45°C and were poor in the chemical adsorption effect.
The adsorbent of Comparative Example 6 had an ammonia gas adsorption capacity of 42 mL/g, but did not contain Ti or Zr, which is a component excellent in acid resistance, and contained Al having poor acid resistance. Inferior in sex. (See Comparative Example 9 in Table 2)

○ Production and evaluation of deodorant cloth (Example 6)
An adsorbent-containing working liquid was prepared by mixing 5 g of the adsorbent produced in Example 1, 100 g of an acrylic emulsion binder having a solid content of 40%, and 500 g of water. This processing liquid was applied to a polyester fiber cloth so that the spread amount of the adsorbent was 0.5 g/m ² and dried to produce a deodorant cloth. The obtained deodorant cloth as it is and the deodorant cloth were immersed in an aqueous hydrochloric acid solution of pH 3 for 2 hours, rinsed with purified water, and the dried deodorant cloth was used to evaluate deodorant performance and chemical resistance. The results are shown in Table 2. It was

(Examples 7 and 8, and Comparative Examples 7-9)
In the same manner as in Example 6, except that the adsorbent produced in Example 2, Example 5, Comparative Example 2, Comparative Example 4 or Comparative Example 6 was used instead of the adsorbent produced in Example 1. Table 2 shows the results of the production of odor cloth and the evaluation of deodorant performance and chemical resistance.

As is clear from Table 2, the deodorizing rates of the deodorizing cloths of Examples 6 to 8 with respect to the ammonia gas were 95% or more both in the untreated and after the chemical resistance test, while the deodorizing ratios of Comparative Examples 7 to 9 were high. The deodorizing rate of the odorous cloth with respect to the ammonia gas is less than 70%, and decreases to less than 20% after the chemical resistance test. It is apparent that the adsorbent of the present invention and the deodorant cloth using the same have excellent deodorizing effect and chemical resistance.

The adsorbent in the present invention is excellent in adsorbability to basic gas, especially ammonia gas. Further, since this adsorbent has excellent chemical resistance, it can be applied to or kneaded into products such as paper and fibers, and various adsorbent processed products can be provided.

It should be noted that the disclosures of each of the above cited patent documents are incorporated herein by reference. Modifications and adjustments of the exemplary embodiments and examples are possible within the scope of the overall disclosure (including claims) of the present invention and based on the basic technical concept of the invention. Further, within the framework of the disclosure of the present invention, various combinations of various disclosed elements (including each element of each claim, each element of each embodiment or example, each element of each drawing, etc.), or selection (non- Selection is possible). That is, it goes without saying that the present invention includes various variations and modifications that can be made by those skilled in the art according to the entire disclosure including the claims and the technical idea. In particular, with regard to the numerical range described in this specification, any numerical value or small range included in the range should be construed as being specifically described even if not otherwise specified.

Claims (4)

An adsorbent comprising a solid represented by the following formula (1).
aM ¹ ₂ O・bP ₂ O ₅・SiO ₂・cM ² O ₂・dH ₂ O (1)
(In Formula (1), M ¹ is an alkali metal element, M ² is Zr and/or Ti, a to d represent a molar ratio, a is 0.005 to 0.2, and b is 0. 05 to 1.0, c is 0.05 to 1.0, and d is 0.05 to 2.) The adsorbent according to claim 1, which is amorphous and has a basic gas adsorption ability. The adsorbent according to claim 1 or 2, which has a chemical adsorption capacity of ammonia gas of 30 mL/g or more. A gas-adsorbing processed product, comprising the adsorbent according to claim 1.