JP2022116822A - Adsorbent and method for producing the same - Google Patents

Abstract

To provide an adsorbent that has high aldehyde adsorptivity even when produced by dissolving an agent in water and spraying and/or dispersing the solution over a carrier without using deleterious substances or compounds prone to oxidization in the air.SOLUTION: An adsorbent includes activated carbon that has a salt of an aromatic amino sulfonic acid compound and an inorganic acid supported thereon.SELECTED DRAWING: None

Description

The present invention relates to an adsorbent and its manufacturing method.

Aldehyde compounds represented by formaldehyde, acetaldehyde and the like are all toxic gases with a peculiar irritating odor, and their harmfulness and odor have led to a demand for effective removal.

As a conventional adsorbent for aldehyde compounds, for example, an adsorbent in which a compound that reacts with an aldehyde compound is supported on a porous material such as activated carbon or zeolite has been used. For example, Patent Document 1 proposes an adsorbent in which a saturated cyclic secondary amine (such as piperidine) is supported on a porous carrier.

In addition, Patent Document 2 describes an adsorbent in which aniline is attached to activated carbon, and Patent Document 3 describes an activated carbon material (activated carbon fiber, etc.) with aminobenzenesulfonic acid and, if necessary, an aromatic An adsorbent impregnated with an amine (such as toluidine) is described, and Patent Document 4 describes a mixture of a basic substance of at least one of ammonium carbonate and ammonium hydrogencarbonate and aminobenzenesulfonic acid in a porous body. An adsorbent carrying a mixture is described, and Patent Document 5 discloses an adsorbent comprising a porous material carrying specific amines (such as aminobenzenesulfonic acid, but not salts) and acids. Have been described.

JP-A-4-358536 JP-A-56-053744 JP-A-7-136502 JP-A-2003-053181 WO2017/086177

However, since the saturated cyclic secondary amine described in Patent Document 1 is easily oxidized in the air, the aldehyde compound removal performance deteriorates significantly over time, and it is not suitable for long-term use. In applications such as deodorant filters for air cleaners and deodorant filters such as cabin air filters, which are in demand, the increased frequency of replacement makes them unsuitable for practical use.

Regarding aniline described in Patent Document 2 and aromatic amine described in Patent Document 3, aniline is a deleterious substance. However, it is difficult to use it for applications such as deodorizing filters, because of its adverse effects on the human body.

On the other hand, aminobenzenesulfonic acid is not a deleterious substance and is resistant to oxidation in the air, so it can withstand long-term use. shows good adsorption properties for aldehyde compounds. However, since aminobenzenesulfonic acid has extremely low solubility in water, it is difficult to attach it to a porous body by a spraying method, which is most commonly used as an attachment method.

Furthermore, since Patent Document 5 indicates that the adsorption amount decreases when aminobenzenesulfonic acid is dissolved or emulsified, dissolution or emulsification of aminobenzenesulfonic acid is assumed. not For this reason, even if aminobenzenesulfonic acid and an aromatic amine are reacted to form a salt of aminobenzenesulfonic acid for water solubility as in Patent Document 3, the aldehyde compound removal performance is dramatically reduced. to degrade. Furthermore, as in Patent Document 4, even when an aminosulfonic acid compound and at least one of ammonium carbonate and ammonium hydrogen carbonate are used in combination, the aldehyde compound is less than aminobenzenesulfonic acid alone. removal performance is deteriorated.

An object of the present invention is to solve the above-described problems by dissolving a drug in water and spraying and/or spraying it onto a carrier without using deleterious substances or compounds that are easily oxidized in the air. An object of the present invention is to provide an adsorbent having high aldehyde adsorption performance even when produced by

As a result of extensive research, the present inventors have found that activated carbon is supported by a combination of a salt of an aromatic aminosulfonic acid compound and an inorganic acid. is not used, and even when the drug is dissolved in water and sprayed and / or sprayed on the carrier, the aldehyde adsorption performance is high, so it was found that the above object can be achieved. The inventors of the present invention have further studied and completed the present invention. That is, the present invention includes the following configurations.

Section 1. An adsorbent comprising a salt of an aromatic aminosulfonic acid compound and an inorganic acid supported on activated carbon.

Section 2. Item 2. The adsorbent according to Item 1, wherein the aromatic aminosulfonic acid compound is aminobenzenesulfonic acid.

Item 3. Item 3. The adsorbent according to Item 1 or 2, wherein the salt is an alkali metal salt or an ammonium salt.

Section 4. Item 4. The adsorbent according to any one of Items 1 to 3, wherein the salt of the aromatic aminosulfonic acid compound is ammonium aminobenzenesulfonate.

Item 5. Item 5. The adsorbent according to any one of Items 1 to 4, wherein the inorganic acid is at least one selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid.

Item 6. Item 6. The adsorbent according to any one of Items 1 to 5, wherein the amount of the inorganic acid attached is 0.30 mol or more per 1 mol of the salt of the aromatic aminosulfonic acid compound.

Item 7. Item 7. The adsorbent according to any one of Items 1 to 6, wherein the salt of the aminosulfonic acid compound is supported via the inorganic acid on at least part of the surface of the activated carbon.

Item 8. Item 8. The adsorbent according to any one of Items 1 to 7, which is an aldehyde adsorbent.

Item 9. A method for producing the adsorbent according to any one of Items 1 to 8,
(1) a step of impregnating an inorganic acid on the surface of activated carbon; and (2) a step of impregnating a salt of an aromatic aminosulfonic acid compound on the surface of the inorganic acid-supporting activated carbon obtained in step (1). Method.

Item 10. The step (1) is
(1A) a step of spraying and/or spraying an aqueous solution containing the inorganic acid onto the activated carbon; and
The step (2) is
(2A) The production method according to item 9, which is a step of spraying and/or spraying an aqueous solution containing the salt of the aromatic aminosulfonic acid compound onto the inorganic acid-supporting activated carbon.

Item 11. An industrial product using the adsorbent according to any one of items 1 to 8.

Item 12. A deodorizing filter using the adsorbent according to any one of items 1 to 8.

Item 13. A method for adsorbing an aldehyde compound, comprising contacting an aldehyde compound with an adsorbent in which a salt of an aromatic aminosulfonic acid compound and an inorganic acid are supported on activated carbon.

Item 14. Item 14. The adsorption method according to Item 13, wherein the salt of the aromatic aminosulfonic acid compound is supported via the inorganic acid on at least part of the surface of the activated carbon.

Item 15. Item 15. The adsorption method according to Item 13 or 14, wherein the boiling point of the aldehyde compound is 100°C or lower.

Item 16. Use of an adsorbent in which a salt of an aromatic aminosulfonic acid compound and an inorganic acid are supported on activated carbon for adsorbing an aldehyde compound.

Item 17. Item 17. Use according to item 16, wherein the salt of the aromatic aminosulfonic acid compound is supported via the inorganic acid on at least part of the surface of the activated carbon.

Item 18. 18. Use according to Item 16 or 17, wherein the boiling point of the aldehyde compound is 100°C or lower.

According to the present invention, deleterious substances and compounds that are easily oxidized in the air are not used, and even when the drug is dissolved in water and manufactured by spraying and / or spraying it on the carrier, aldehyde adsorption Adsorbents with high performance can be provided.

It is a schematic diagram of the apparatus used for the acetaldehyde circulation test.

As used herein, the term "impregnation" refers to supporting a chemical such as a salt of an aromatic aminosulfonic acid compound or an inorganic acid on a porous carrier such as activated carbon.

In addition, in this specification, "contain" is a concept that includes all of "comprise", "consist essentially of", and "consist of". be.

Further, in this specification, when a numerical range is indicated by "A to B", it means from A to B.

1. Aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent)
The aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) of the present invention supports an aromatic aminosulfonic acid compound salt and an inorganic acid on the activated carbon.

With such a configuration, by using the aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) of the present invention, a drug can be absorbed without using deleterious substances or compounds that are easily oxidized in the air. Aldehyde adsorption performance can also be improved when it is produced by dissolving it in water and spraying and/or spraying it on a carrier.

The shape and average particle size of the aromatic aminosulfonic acid compound salt-supporting activated carbon (adsorbent) of the present invention are the same as the shape and average particle size of activated carbon described later.

Hereinafter, each component of the aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) of the present invention will be described.

(1-1) Activated Carbon The activated carbon carrying an aromatic aminosulfonic acid compound salt (adsorbent) of the present invention contains activated carbon. This activated carbon is a carrier for supporting (impregnating) a salt of an aromatic aminosulfonic acid compound and an inorganic acid, which will be described later.

Unlike inorganic porous carriers such as zeolite and alumina, activated carbon has a disordered pore structure. It has a site that can be adsorbed even if there is. In addition, since activated carbon does not have free-moving cations, there is no risk of cation exchange (base exchange) with salts of aromatic aminosulfonic acid compounds and inorganic acids, which are impregnation components.

Various activated carbons can be used as the activated carbon. For example, wood, wood flour, coconut husks, by-products of pulp manufacturing, bagasse, blackstrap molasses, coal (peat, lignite, lignite, bituminous coal, etc.), anthracite, petroleum distillation residue components, petroleum pitch, coke, coal tar, etc. Plant-based raw materials or fossil-based raw materials; Phenolic resins, vinyl chloride resins, vinyl acetate resins, melamine resins, urea resins, resorcinol resins, celluloid, epoxy resins, polyurethane resins, polyester resins, acrylic resins, various synthetic resins such as polyamide resins; Synthetic rubbers such as polybutylene, polybutadiene and polychloroprene; other synthetic wood; activated carbon made from synthetic pulp and the like. Among these, coal activated carbon or coconut shell activated carbon is preferable, and coconut shell activated carbon is more preferable, from the viewpoint of easily adsorbing aldehyde compounds (formaldehyde, acetaldehyde, etc.) in the gas phase. These activated carbons can be used alone or in combination of two or more.

Activated carbon can be obtained by carbonizing or infusibilizing these raw materials as necessary, followed by activation treatment. The carbonization method, the infusibilization method, and the activation method are not particularly limited, and conventional methods can be used. For example, activation includes a gas activation method of heat-treating a carbon raw material (or its carbide or infusibilized substance) in an activating gas (steam, carbon dioxide, etc.) at about 500 to 1000 ° C., a carbon raw material (or its carbide or infusibilized substance). ) is mixed with an activator (phosphoric acid, zinc chloride, potassium hydroxide, sodium hydroxide, etc.) and heat-treated at about 300 to 800° C. for chemical activation.

A commercially available product can also be used as the activated carbon (also referred to as "activated carbon before carrying (impregnating) the salt of the aromatic aminosulfonic acid compound and the inorganic acid" or "original carbon").

As for the shape of the activated carbon, since it is easy to support the salt of the aromatic aminosulfonic acid compound and the inorganic acid, and it is difficult to drop off when filtered, for example, it is appropriately selected from granular, pellet, fibrous, honeycomb, and the like. be able to.

The BET specific surface area of the activated carbon is preferably 600-2200 m ² /g, more preferably 900-2000 m ² /g. By setting the BET specific surface area within this range, the aldehyde compound adsorption performance and hardness can be better balanced. The specific surface area of activated carbon is measured by the BET method.

(1-2) Aromatic aminosulfonic acid compound salt In the aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) of the present invention, an aromatic aminosulfonic acid compound salt is supported (attached) to the activated carbon.

The aromatic aminosulfonic acid compound in the salt of the aromatic aminosulfonic acid compound used in the present invention is not particularly limited, but 2-aminobenzenesulfonic acid (ortanic acid), 3-aminobenzenesulfonic acid (methanilic acid), 4-aminobenzenesulfonic acid (sulphanilic acid) and other aminobenzenesulfonic acids, as well as polycyclic aromatics such as 2-amino-1-naphthalenesulfonic acid and 4-amino-1-naphthalenesulfonic acid Aminosulfonic acid compounds and the like can be mentioned. Among them, aminobenzenesulfonic acid is preferable from the viewpoints of solubility in water, adsorption performance of odorants such as aldehyde compounds when combined with inorganic acids, and the like. These aromatic aminosulfonic acid compounds can be used alone or in combination of two or more.

When the salt of the aromatic aminosulfonic acid compound used in the present invention is used alone, the adsorption performance of odorants such as aldehyde compounds is remarkably deteriorated as compared with the aromatic aminosulfonic acid compound. However, when this salt of the aromatic aminosulfonic acid compound is used in combination with an inorganic acid, unexpectedly, the adsorption performance of odorants such as aldehyde compounds is improved compared to the aromatic aminosulfonic acid compound. is possible. Here, the salt in the salt of the aromatic aminosulfonic acid compound is not particularly limited. Alkali metal salts or ammonium salts are preferred, and ammonium salts are more preferred from the viewpoints of water solubility and production. The alkali metal salt is not particularly limited, and includes sodium salt, potassium salt and the like. That is, the salt of the aromatic aminosulfonic acid compound includes sodium aminobenzenesulfonate, potassium aminobenzenesulfonate, ammonium aminobenzenesulfonate, etc., and ammonium aminobenzenesulfonate is preferred. These salts of aromatic aminosulfonic acid compounds can be used alone or in combination of two or more. In addition, known or commercially available salts of these aromatic aminosulfonic acid compounds can be used.

The supported amount (impregnated amount) of the salt of the aromatic aminosulfonic acid compound is not particularly limited, but is preferably 1 to 30 parts by mass, and 5 to 15 parts by mass with respect to 100 parts by mass of activated carbon (dry product basis). part is more preferred. When the supported amount (impregnated amount) of the salt of the aromatic aminosulfonic acid compound is within the above range, the salt of the aromatic aminosulfonic acid compound is less likely to fill the pores of the activated carbon, and the aldehyde compound (formaldehyde, acetaldehyde, etc.) is not present. It is easy to reach the reaction site in the aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) of the invention, and the synergistic adsorption performance of odorants such as aldehyde compounds (formaldehyde, acetaldehyde, etc.) by using it in combination with the inorganic acid described later. It is easy to get the effect.

(1-3) Inorganic Acid In the activated carbon (adsorbent) supporting an aromatic aminosulfonic acid compound salt of the present invention, an inorganic acid is supported (attached) to the activated carbon in addition to the salt of the aromatic aminosulfonic acid compound.

The inorganic acid alone does not have the ability to adsorb odorous substances such as aldehyde compounds (formaldehyde, acetaldehyde, etc.). It is possible to dramatically improve the adsorption performance of odorants such as aldehyde compounds (formaldehyde, acetaldehyde, etc.).

As such an inorganic acid, by combining with a salt of an aromatic aminosulfonic acid compound, the adsorption performance of odorous substances such as aldehyde compounds (formaldehyde, acetaldehyde, etc.) is dramatically improved, and the aromatic aminosulfonic acid Sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, and the like are preferred, and sulfuric acid, phosphoric acid, and the like are more preferred, from the viewpoints of easily obtaining a synergistic effect when used in combination with a salt of the compound and having excellent solubility in water. These inorganic acids can be used alone or in combination of two or more. In addition, known or commercially available products can be used as these inorganic acids.

The amount of inorganic acid supported (impregnated) is not particularly limited, but is preferably 1 to 15 parts by mass, more preferably 2 to 10 parts by mass, based on 100 parts by mass of activated carbon (dry product basis). When the supported amount (impregnated amount) of the inorganic acid is within the above range, the salt of the aromatic aminosulfonic acid compound is less likely to fill the pores of the activated carbon, and the aldehyde compound (formaldehyde, acetaldehyde, etc.) becomes the aromatic aminosulfone of the present invention. It is easy to reach the reaction site in the acid compound salt-supporting activated carbon, and a synergistic effect of adsorption performance of odorants such as aldehyde compounds (formaldehyde, acetaldehyde, etc.) can be obtained by using it in combination with the salt of the aromatic aminosulfonic acid compound. Cheap.

The supported amount (attached amount) of the inorganic acid is not particularly limited, but is preferably 0.30 mol or more, and 0.50 to 1.80 mol per 1 mol of the salt of the aromatic aminosulfonic acid compound. More preferably 0.70 to 1.10 mol. When the supported amount (impregnated amount) of the inorganic acid is within the above range, the salt of the aromatic aminosulfonic acid compound is less likely to fill the pores of the activated carbon, and the aldehyde compound (formaldehyde, acetaldehyde, etc.) becomes the aromatic aminosulfone of the present invention. It is easy to reach the reaction site in the acid compound salt-supporting activated carbon (adsorbent), and synergistic adsorption performance of odorous substances such as aldehyde compounds (formaldehyde, acetaldehyde, etc.) by using it together with the salt of the above aromatic aminosulfonic acid compound. It is easy to get the effect.

(1-4) Aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent)
In the aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) of the present invention, it is preferable that no other component is interposed between the activated carbon and the salt of the aromatic aminosulfonic acid compound and the inorganic acid. It is preferable that the salt of the group aminosulfonic acid compound and the inorganic acid are carried (attached) so as to be in direct contact with each other. However, as will be described later, from the viewpoint of easily obtaining a synergistic effect of adsorption performance of odorants such as aldehyde compounds (formaldehyde, acetaldehyde, etc.), for activated carbon, after impregnating an inorganic acid on the surface of activated carbon, Since it is preferable to impregnate a salt of an aromatic aminosulfonic acid compound, due to the structure of the activated carbon (adsorbent) supporting an aromatic aminosulfonic acid compound salt of the present invention, at least part of the surface of the activated carbon has the aminosulfonic acid compound. is preferably supported (attached) via the inorganic acid.

The aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) of the present invention as described above is particularly excellent in adsorption performance for odorous substances such as aldehyde compounds, and is therefore useful as an adsorbent (especially an aldehyde adsorbent). . From the viewpoint of adsorption performance, the aldehyde compound to be adsorbed is preferably an aldehyde compound having a boiling point of 100° C. or lower (especially −20 to 20° C.). 4, particularly aldehyde compounds having 1 to 2 carbon atoms are preferred.

2. Method for producing an aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) Method for producing an aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) of the present invention (carrying a salt of an aromatic aminosulfonic acid compound and an inorganic acid ( The impregnation method) is a method for producing an aromatic aminosulfonic acid compound salt-supported activated carbon in which the salt of the aromatic aminosulfonic acid compound and the inorganic acid are supported (impregnated) on the activated carbon,
(1) a step of impregnating the surface of the activated carbon with an inorganic acid; and (2) a step of impregnating the surface of the inorganic acid-supporting activated carbon obtained in step (1) with a salt of an aromatic aminosulfonic acid compound. preferable.

According to this method, it is possible to obtain an adsorbent (particularly an aldehyde adsorbent) having particularly excellent adsorption performance for odorants such as aldehyde compounds (formaldehyde, acetaldehyde, etc.).

In addition, the thus-obtained aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) of the present invention does not use a compound that is easily oxidized in the air, so it is a material that can withstand repeated use. .

In the step (1), as a method for supporting an inorganic acid on activated carbon,
(1A) a method of spraying and/or spraying an aqueous solution containing the inorganic acid onto activated carbon;
(1B) a method of immersing activated carbon in an aqueous solution containing the inorganic acid;
etc.

Further, in the step (2), as a method for supporting the salt of the aromatic aminosulfonic acid compound on the inorganic acid-supporting activated carbon,
(2A) a method of spraying and/or spraying an aqueous solution containing a salt of the aromatic aminosulfonic acid compound onto an inorganic acid-supporting activated carbon;
(2B) a method of immersing an inorganic acid-supported activated carbon in an aqueous solution containing the salt of the aromatic aminosulfonic acid compound;
etc.

In particular, from the viewpoint that drying after impregnation is unnecessary, treatment of the residual solution after impregnation is unnecessary, and impregnation can be performed in a short time, steps (1A) and (2A), that is, Application by spraying and/or scattering is preferred.

By these methods, the salt of the aromatic aminosulfonic acid compound and the inorganic acid can be supported (impregnated) on the entire activated carbon. In addition, as described above, the inorganic acid is first supported (impregnated) on the activated carbon, and then the salt of the aromatic aminosulfonic acid compound is supported (impregnated). An aromatic aminosulfonic acid compound salt-supported activated carbon in which a salt of an aminosulfonic acid compound is supported (impregnated) via the inorganic acid is easily obtained, and has an ability to adsorb odorants such as aldehyde compounds (formaldehyde, acetaldehyde, etc.). It is possible to obtain an adsorbent (especially an aldehyde adsorbent) that is particularly excellent in

In addition, the temperature of the aqueous solution containing the inorganic acid and the aqueous solution containing the salt of the aromatic aminosulfonic acid compound to be used is not particularly limited, but can usually be 15 to 30° C., and the supporting (attachment) time is Although there is no particular limitation, it can be from 20 minutes to 1 hour.

The amount of the salt of the aromatic aminosulfonic acid compound used is such that the supported (impregnated) amount of the salt of the aromatic aminosulfonic acid compound is 1 to 30 parts by mass, particularly 5 to 15 parts by mass, per 100 parts by mass (dry product basis) of the activated carbon. It is preferable to set so as to be parts by mass. In addition, the amount of the inorganic acid used can be set so that the supported (impregnated) amount of the inorganic acid is 1 to 15 parts by mass, particularly 2 to 10 parts by mass, with respect to 100 parts by mass (dry product basis) of the activated carbon. preferable. For example, in the method of steps (1A) and (2A) described above, when the salt of the aromatic aminosulfonic acid compound and the inorganic acid are supported (impregnated) on activated carbon, the solution containing the inorganic acid used and the aromatic aminosulfonic acid Since the content of the salt of the inorganic acid and the salt of the aromatic aminosulfonic acid compound in the solution containing the salt of the compound is the supported (impregnated) amount as it is, the solution containing 1 to 15 parts by mass of the inorganic acid and 1 to 30 parts by mass By spraying and/or spraying a solution containing the salt of the aromatic aminosulfonic acid compound in parts by mass onto 100 parts by mass of dry activated carbon, the amount of the salt of the aromatic aminosulfonic acid compound supported (impregnated) is 100 parts by mass of the activated carbon. 1 to 30 parts by mass per part (dry product basis), and the amount of supported (impregnated) inorganic acid is 1 to 15 parts by mass per 100 parts by weight (dry product basis) of activated carbon. A compound salt-supported activated carbon is obtained.

The activated carbon may be modified (heat treated) before the salt of the aromatic aminosulfonic acid compound and the inorganic acid are supported (impregnated). Each condition (temperature, time, atmosphere, apparatus, etc.) of the heat treatment in the reforming can be carried out according to a conventional method.

3. Method for adsorbing odorous substances (aldehyde compounds, etc.) using activated carbon (adsorbent) carrying aromatic aminosulfonic acid compound salt The adsorption method of the present invention comprises the activated carbon (adsorbent) carrying an aromatic aminosulfonic acid compound salt of the present invention. It is characterized in that it is brought into contact with an odorant (such as an aldehyde compound). According to the above adsorption method, the activated carbon (adsorbent) carrying an aromatic aminosulfonic acid compound salt of the present invention efficiently adsorbs odorous substances (aldehyde compounds, etc.), so that odorous substances (aldehyde compounds, etc.) are efficiently removed. can do.

4. Application to industrial products The aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) of the present invention can be used by blending in industrial products. The industrial product encompasses the present invention.

Industrial products refer to conventional industrial products and industrial raw materials that are widely known. Specifically, paints, adhesives, inks, sealants, paper products, binders, resin emulsions, pulp, wood materials, wood products, plastic products, films, wallpapers, building materials (gypsum boards, interior materials, ceiling materials, floors, etc.) materials, etc.), textile products, filters (especially deodorizing filters for air purifiers, cabin air filters, etc.), and the like. In addition, these composite materials are also included in industrial products. Composite materials include, for example, composite materials of wood and plastic. In the adsorption method of the present invention, the above industrial product containing the aromatic aminosulfonic acid compound salt-supported activated carbon (adsorbent) of the present invention is brought into contact with an odorant (such as an aldehyde compound) to obtain the aromatic of the present invention. The group aminosulfonic acid compound salt-carrying activated carbon (adsorbent) and odorous substances (aldehyde compounds, etc.) come into contact with each other, and as a result, the odorous substances (aldehyde compounds, etc.) can be efficiently adsorbed and removed.

When a filter (particularly a deodorizing filter) is employed as an industrial product, a conventionally known structure can be employed as its structure.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the embodiments.

Example 1
5.66 parts by mass of 98% sulfuric acid (containing 5.55 parts by mass of sulfuric acid; containing 1 mol per 1 mol of sodium 4-aminobenzenesulfonate) was dissolved in 15 parts by mass of water, and the resulting solution (liquid 25° C.) was spray-impregnated with 100 parts by mass of activated carbon (coconut shell activated carbon manufactured by Osaka Gas Chemicals Co., Ltd.) having a BET specific surface area of 1000 m ² /g (impregnation time: 30 minutes) to obtain a sulfuric acid-supporting activated carbon. After that, 10 parts by mass of sodium 4-aminobenzenesulfonate was dissolved in 15 parts by mass of water, and the resulting solution (liquid temperature: 25°C) was spray-impregnated onto the activated carbon supporting sulfuric acid (impregnation time: 30 minutes). - Activated carbon (adsorbent) carrying (impregnated with) both sodium aminobenzenesulfonate and sulfuric acid was obtained. In the obtained adsorbent, sodium 4-aminobenzenesulfonate is supported (impregnated) via sulfuric acid on at least part of the surface of the activated carbon.

Example 2
A solution obtained by dissolving 2.35 parts by mass of 85% phosphoric acid (containing 2 parts by mass of phosphoric acid; containing 0.35 mol per 1 mol of ammonium 4-aminobenzenesulfonate) in 15 parts by mass of water (Liquid temperature: 25°C) was spray impregnated onto 100 parts by mass of activated carbon (coconut shell activated carbon manufactured by Osaka Gas Chemicals Co., Ltd.) with a BET specific surface area of 1000 m ² /g (impregnation time: 30 minutes) to obtain phosphoric acid-supporting activated carbon. rice field. After that, 10 parts by mass of ammonium 4-aminobenzenesulfonate was dissolved in 15 parts by mass of water, and the resulting solution (liquid temperature: 25°C) was spray-impregnated onto the phosphoric acid-supporting activated carbon (impregnation time: 30 minutes), An activated carbon (adsorbent) carrying (attached to) both ammonium 4-aminobenzenesulfonate and phosphoric acid was obtained. In the obtained adsorbent, ammonium 4-aminobenzenesulfonate is supported (impregnated) via phosphoric acid on at least part of the surface of the activated carbon.

Comparative example 1
100 parts by mass of activated carbon (coconut shell activated carbon manufactured by Osaka Gas Chemicals Co., Ltd.) with a BET specific surface area of 1000 m ² /g and 10 parts by mass of 4-aminobenzenesulfonic acid were added to 300 parts by mass of water (liquid temperature: 25°C), After stirring for 1 hour, filtration and drying were carried out to obtain activated carbon (adsorbent) carrying (impregnated with) 4-aminobenzenesulfonic acid. Since 4-aminobenzenesulfonic acid has low solubility in water, a large amount of water was used, and since it still did not dissolve, it was supported (attached) by immersion instead of spraying.

Comparative example 2
10 parts by mass of sodium ⁴ -aminobenzenesulfonate was dissolved in 15 parts by mass of water, and the resulting solution (liquid temperature: 25°C) was treated with activated carbon (a palm Shell activated carbon) was spray impregnated (impregnation time: 30 minutes) to obtain activated carbon (adsorbent) on which sodium 4-aminobenzenesulfonate was carried (impregnated).

Comparative example 3
10 parts by mass of 4-aminobenzenesulfonic acid and 4.56 parts by mass of ammonium hydrogencarbonate were mixed with 15 parts by mass of water, and the resulting liquid (liquid temperature: 25°C) was treated with activated carbon having a BET specific surface area of 1000 m ² /g ( Coconut shell activated carbon manufactured by Osaka Gas Chemicals Co., Ltd.) was sprayed and impregnated (impregnation time: 30 minutes) to obtain activated carbon (adsorbent) carrying (impregnated) 4-aminobenzenesulfonic acid and ammonium hydrogen carbonate.

Test Example 1: Acetaldehyde Flow Test The apparatus shown in FIG. 1 was placed in a constant temperature chamber kept at 25°C. Specifically, the adsorbent F (the adsorbents obtained in Examples 1 and 2 and Comparative Examples 1 and 3) was packed in a column G having an inner diameter of 20 mm to a height of 20 mm. In addition, air with a relative humidity of 60% obtained by supplying air to a water vapor generating bottle C filled with water by a compressor A while controlling the flow rate by a mass flow controller B, and acetaldehyde gas supplied from an acetaldehyde gas cylinder D. were mixed in mixing bottle E to form a 20 ppm test gas. This gas was circulated at a flow rate of 2 L/min for 24 hours (sufficient time to reach breakthrough for any adsorbent), the outlet gas concentration was measured with a gas chromatograph, and the acetaldehyde equilibrium adsorption was determined from the breakthrough curve. asked for capacity.

Table 1 shows the results.

From Examples 1 and 2 and Comparative Example 1, the adsorbent in which the salt of aromatic aminosulfonic acid and the inorganic acid are supported (attached) is higher than the adsorbent in which the aromatic aminosulfonic acid alone is supported (attached). It can be understood that the acetaldehyde adsorption performance is remarkably improved.

Moreover, from Example 1 and Comparative Example 2, it can be understood that the addition of the inorganic acid significantly improves the performance as compared with the single salt of the aromatic aminosulfonic acid.

In addition, from Examples 1 and 2 and Comparative Example 3, the acetaldehyde adsorption performance was remarkably improved compared to the previously reported adsorbent carrying (impregnated with) a mixture of aminobenzenesulfonic acid and ammonium hydrogen carbonate. It is understandable that

Example 3
A solution obtained by dissolving 2.35 parts by mass of 85% phosphoric acid (containing 2 parts by mass of phosphoric acid; containing 0.35 mol per 1 mol of ammonium 4-aminobenzenesulfonate) in 15 parts by mass of water (Liquid temperature: 25° C.) was spray-impregnated with 100 parts by mass of activated carbon (coconut shell activated carbon manufactured by Osaka Gas Chemicals Co., Ltd.) having a BET specific surface area of 1500 m ² /g (impregnation time: 30 minutes) to obtain phosphoric acid-supported activated carbon. rice field. After that, 10 parts by mass of ammonium 4-aminobenzenesulfonate was dissolved in 15 parts by mass of water, and the resulting solution (liquid temperature: 25°C) was spray-impregnated onto the phosphoric acid-supporting activated carbon (impregnation time: 30 minutes), An activated carbon (adsorbent) carrying (attached to) both ammonium 4-aminobenzenesulfonate and phosphoric acid was obtained. In the obtained adsorbent, ammonium 4-aminobenzenesulfonate is supported (impregnated) via phosphoric acid on at least part of the surface of the activated carbon.

Example 4
Example except that phosphoric acid was 4.71 parts by mass instead of 2.35 parts by mass (containing 4 parts by mass of phosphoric acid; containing 0.71 mol per 1 mol of ammonium 4-aminobenzenesulfonate) As in 3, an activated carbon (adsorbent) carrying (impregnated with) both ammonium 4-aminobenzenesulfonate and phosphoric acid was obtained. In the obtained adsorbent, ammonium 4-aminobenzenesulfonate is supported (impregnated) via phosphoric acid on at least part of the surface of the activated carbon.

Example 5
Example except that phosphoric acid was 7.06 parts by mass instead of 2.35 parts by mass (containing 6 parts by mass of phosphoric acid; containing 1.06 mol per 1 mol of ammonium 4-aminobenzenesulfonate) As in 3, an activated carbon (adsorbent) carrying (impregnated with) both ammonium 4-aminobenzenesulfonate and phosphoric acid was obtained. In the obtained adsorbent, ammonium 4-aminobenzenesulfonate is supported (impregnated) via phosphoric acid on at least part of the surface of the activated carbon.

Test Example 2: Acetaldehyde Flow Test The apparatus shown in FIG. 1 was placed in a constant temperature chamber kept at 25°C. Specifically, the adsorbent F (the adsorbents obtained in Examples 3 to 5 and Comparative Example 1) was packed in a column G having an inner diameter of 20 mm to a height of 20 mm. In addition, air with a relative humidity of 60% obtained by supplying air to a water vapor generating bottle C filled with water by a compressor A while controlling the flow rate by a mass flow controller B, and acetaldehyde gas supplied from an acetaldehyde gas cylinder D. were mixed in mixing bottle E to form a 20 ppm test gas. This gas was circulated at a flow rate of 2 L/min for 24 hours (sufficient time to reach breakthrough for any adsorbent), the outlet gas concentration was measured with a gas chromatograph, and the acetaldehyde equilibrium adsorption was determined from the breakthrough curve. asked for capacity.

Table 2 shows the results.

From Examples 3 to 5 and Comparative Example 1, when 0.30 mol or more of the inorganic acid is attached to 1 mol of the salt of the aromatic aminosulfonic acid, the aromatic aminosulfonic acid carrier is supported (attached) ) It can be understood that the acetaldehyde adsorption performance is significantly improved compared to the adsorbent.

A Compressor B Mass Flow Controller C Steam Generation Bottle D Acetaldehyde Gas Cylinder E Mixing Bottle F Adsorbent G Column H Float Meter

Claims (15)

An adsorbent comprising a salt of an aromatic aminosulfonic acid compound and an inorganic acid supported on activated carbon. The adsorbent according to claim 1, wherein said aromatic aminosulfonic acid compound is aminobenzenesulfonic acid. The adsorbent according to claim 1 or 2, wherein said salt is an alkali metal salt or an ammonium salt. The adsorbent according to any one of claims 1 to 3, wherein the salt of the aromatic aminosulfonic acid compound is ammonium aminobenzenesulfonate. The adsorbent according to any one of claims 1 to 4, wherein the inorganic acid is at least one selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid. The adsorbent according to any one of claims 1 to 5, wherein the amount of the inorganic acid attached is 0.30 mol or more per 1 mol of the salt of the aminosulfonic acid compound. The adsorbent according to any one of claims 1 to 6, wherein the salt of the aminosulfonic acid compound is supported via the inorganic acid on at least part of the surface of the activated carbon. The adsorbent according to any one of claims 1 to 7, which is an aldehyde adsorbent. A method for producing the adsorbent according to any one of claims 1 to 8,
(1) a step of impregnating an inorganic acid on the surface of activated carbon; and (2) a step of impregnating a salt of an aromatic aminosulfonic acid compound on the surface of the inorganic acid-supporting activated carbon obtained in step (1). Method. The step (1) is
(1A) a step of spraying and/or spraying an aqueous solution containing the inorganic acid onto the activated carbon; and
The step (2) is
(2A) The production method according to claim 9, which is a step of spraying and/or spraying an aqueous solution containing the salt of the aromatic aminosulfonic acid compound onto the inorganic acid-supporting activated carbon. Industrial products using the adsorbent according to any one of claims 1 to 8. A deodorizing filter using the adsorbent according to any one of claims 1 to 8. A method for adsorbing an aldehyde compound, comprising contacting an aldehyde compound with an adsorbent in which a salt of an aromatic aminosulfonic acid compound and an inorganic acid are supported on activated carbon. 14. The adsorption method according to claim 13, wherein the salt of the aromatic aminosulfonic acid compound is supported via the inorganic acid on at least part of the surface of the activated carbon. The adsorption method according to claim 13 or 14, wherein the aldehyde compound has a boiling point of 100°C or lower.

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