JP2023057487A - Amine compound-carried activated carbon and method of producing the same - Google Patents

Abstract

To provide an adsorbent that has excellent weather resistance and heat resistance without excessively deteriorating the initial performance of aldehyde adsorption.SOLUTION: Provided is an amine compound-carried activated carbon in which an amine compound is carried on activated carbon, wherein the heat loss of the activated carbon after the amine compound is removed from the amine compound-carried activated carbon at 200 to 300°C is 0.60 mass% or more with the total activated carbon content as 100 mass%.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an amine compound-supported activated carbon and a method for producing the same.

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 a hydroxylamine and a polymer having a functional group that interacts with the amino group of the hydroxylamine are attached to a carrier (activated carbon, etc.). Document 3 describes a deodorant in which an aromatic amine or its sulfate and, if necessary, sulfuric acid are supported on activated carbon.

All of the known adsorbents described above deteriorate quickly in adsorbability over time and also have problems with heat resistance. Some means for solving this problem have also been reported. A gas adsorbent impregnated on a carrier (activated carbon, etc.) is described, and Patent Document 5 discloses that an activated carbon having a surface oxide formed by an oxidation treatment is added with a cyclic saturated secondary amine and, if necessary, an alkaline earth metal. Adsorbents for lower aldehydes supported with metal halides and/or antioxidants are described.

JP-A-4-358536 JP 2008-259955 A JP 2019-198542 A JP 2014-073439 A Japanese Patent Application Laid-Open No. 2000-084406

However, there are problems with the technology that is said to have solved the above problems of speed of deterioration over time and heat resistance. For adsorbents of lower aldehydes supported by saturated cyclic secondary amines and optionally alkaline earth metal halides and/or antioxidants, the saturated cyclic secondary amines are oxidized in air. Furthermore, the mere use of activated carbon on which surface oxides are generated by oxidation treatment is insufficient in terms of deterioration over time and heat resistance.

An object of the present invention is to solve the above-described problems, and to provide an adsorbent having excellent weather resistance and heat resistance without excessively deteriorating the initial performance of aldehyde adsorption.

As a result of extensive research, the present inventors have found that a material in which an amine compound is supported on activated carbon having a heat loss of 0.60% by mass or more with respect to the total amount of activated carbon as 100% by mass at 200 to 300 ° C. It has been found that the above object can be achieved because the adsorbent has excellent weather resistance and heat resistance without excessively deteriorating the initial performance of aldehyde adsorption. The adsorbent can also be produced by dissolving the drug in water and spraying and/or spraying it on the carrier, and can be produced easily. Based on such findings, the inventors have further studied and completed the present invention. That is, the present invention includes the following configurations.

Section 1. An amine compound-supported activated carbon in which an amine compound is supported with respect to activated carbon,
An amine compound-supported activated carbon having a heat loss at 200 to 300° C. after removing the amine compound from the amine compound-supported activated carbon is 0.60% by mass or more based on the total amount of activated carbon as 100% by mass.

Section 2. Item 2. The amine compound-supported activated carbon according to Item 1, wherein the metal component contained in the activated carbon is 0.05% by mass or less based on 100% by mass of the total amount of the activated carbon that does not support an amine compound.

Item 3. Item 3. The amine compound-supported activated carbon according to Item 1 or 2, wherein the amount of the amine compound supported is 1 to 50 parts by mass with respect to 100 parts by mass of the activated carbon.

Section 4. 4. The amine compound-supported activated carbon according to any one of Items 1 to 3, wherein the amine compound is a primary hydroxylamine compound.

Item 5. Item 5. The amine compound-supported activated carbon according to any one of Items 1 to 4, wherein the amine compound is trishydroxymethylaminomethane.

Item 6. An adsorbent containing the amine compound-supported activated carbon according to any one of Items 1 to 5.

Item 7. Item 7. The adsorbent according to Item 6, which is an aldehyde compound adsorbent.

Item 8. A method for producing the amine compound-supported activated carbon according to any one of Items 1 to 5 or the adsorbent according to Item 6 or 7,
(1) a step of contacting activated carbon with an oxidizing agent; and (2) a step of supporting an amine compound on the oxidized activated carbon obtained in step (1).

Item 9. Item 9. The production method according to Item 8, wherein the activated carbon used in the step (1) is a pickled activated carbon obtained by washing activated carbon with an acid.

Item 10. An industrial product using the amine compound-supported activated carbon according to any one of Items 1 to 5 or the adsorbent according to Item 6 or 7.

Item 11. A deodorizing filter using the amine compound-supporting activated carbon according to any one of Items 1 to 5 or the adsorbent according to Item 6 or 7.

Item 12. A method for adsorbing an aldehyde compound,
A step of contacting an aldehyde compound with an amine compound-supported activated carbon on which an amine compound is supported on activated carbon,
The adsorption method, wherein the activated carbon after removing the amine compound from the amine compound-supported activated carbon has a weight loss on heating at 200 to 300° C. of 0.60% by mass or more when the total amount of activated carbon is 100% by mass.

Item 13. Item 13. The adsorption method according to Item 12, wherein the boiling point of the aldehyde compound is 100°C or lower.

ADVANTAGE OF THE INVENTION According to this invention, the adsorbent excellent in weather resistance and heat resistance can be provided, without reducing the initial performance of aldehyde adsorption excessively.

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

As used herein, the term "impregnation" means supporting a chemical such as an amine compound 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.

Moreover, in this specification, "activated carbon" means activated carbon that does not support an amine compound.

Further, in this specification, "activated carbon supporting an amine compound" means activated carbon supporting an amine compound.

1. Amine compound-supported activated carbon (adsorbent)
The amine compound-supported activated carbon (adsorbent) of the present invention is an adsorbent in which an amine compound is supported with respect to the activated carbon, and is 200 to 300% of the activated carbon after the amine compound is removed from the amine compound-supported activated carbon. Heating loss at °C is 0.6% by mass or more, with the total amount of activated carbon being 100% by mass.

With such a configuration, the amine compound-supported activated carbon (adsorbent) of the present invention is excellent in weather resistance and heat resistance without excessively deteriorating the initial performance of aldehyde adsorption. In addition, the amine compound-supporting activated carbon (adsorbent) of the present invention can be easily produced by dissolving the drug in water and spraying and/or spraying it on the carrier.

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

Each component of the amine compound-supporting activated carbon (adsorbent) of the present invention is described below.

(1-1) Activated Carbon The activated carbon supporting amines (adsorbent) of the present invention contains activated carbon. This activated carbon (also referred to as "activated carbon not supporting (impregnating) an amine compound" or "base carbon") is a carrier for supporting (impregnating) an amine compound, 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 the amine compound, which is an impregnation component.

The activated carbon used in the present invention is such that the heat loss of the activated carbon after removing the amine compound from the amine compound-supported activated carbon of the present invention at 200 to 300 ° C. is the total amount of activated carbon (the amine compound is removed from the amine compound-supported activated carbon of the present invention Based on 100% by mass of the total amount of activated carbon after that, it is 0.60% by mass or more, preferably 0.70 to 0.90% by mass, and more preferably 0.80 to 0.85% by mass. It is known that the weight loss on heating at 200 to 300°C is due to the carboxyl groups on the surface of the activated carbon decomposing into carbon monoxide and carbon dioxide and leaving, and the weight loss on heating at 200 to 300°C is 0.60. If it is more than mass %, it is suggested that a considerable amount of carboxyl groups are present on the activated carbon surface. Amine compounds are unstable substances, and when they are stored on activated carbon and stored in the air, the amine compounds are deactivated due to the reaction between the amine compounds and oxygen in the air, and the ability to adsorb aldehyde compounds decreases over time. It is common to continue However, the amine compound-supported activated carbon of the present invention is excellent in weather resistance and heat resistance without excessively deteriorating the initial performance of aldehyde adsorption. The reason for this is thought to be that the amine compound exists in a more stable state on the surface of the activated carbon due to the aforementioned weak interaction between the carboxyl group and the amine compound. Another reason is that during the contact between the activated carbon and the oxidizing agent, which will be described later, radical species such as dehydrogenated σ-radicals, dehydrogenated π-radical cations, and neutral π-radicals that originally exist on the surface of the activated carbon are A possible reason for this is that the radical species that react with the oxidizing agent to form carboxyl groups and cause deactivation of the amine compound disappeared from the surface of the activated carbon. The above-mentioned radical species are extremely active and react with oxygen in the air to generate superoxide anion radicals, which attack the amine compounds and deactivate them. It is considered that the deactivation of the amine compound can be suppressed by eliminating the radical species that result from the surface of the activated carbon. In the present invention, the weight loss on heating of the activated carbon at 200 to 300° C. is determined by boiling the activated carbon supporting the amine compound of the present invention with hydrochloric acid and then boiling it with water to remove the amine compound. Measured with Thermo plus EVO TG8120 manufactured by Rigaku.

The content of the metal component contained in the activated carbon used in the present invention is preferably 0.05% by mass or less, more preferably 0.04% by mass or less, based on 100% by mass of the total amount of activated carbon that does not support an amine compound. Preferably, 0.02% by mass or less is more preferable. By setting the content of the metal component within this range, the weather resistance can be more easily improved, the deterioration over time can be more easily suppressed, and the heat resistance can be more easily improved. In the present invention, the content of the metal component contained in the activated carbon is determined according to JIS K 1474:2014 7.13 iron analysis method, each metal Al, Ca, Fe, K, Mg, Na, Zn The component content is determined by inductively coupled plasma emission spectrometry (ICP emission spectrometry) and determined as the sum of them.

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.

As for the shape of the activated carbon, since it is easy for the amine compound to be supported thereon and it is difficult for the activated carbon to fall off when it is filtered, for example, it can be appropriately selected from granular, pellet, fibrous, honeycomb, and the like.

As the activated carbon, various activated carbons can be used as long as they satisfy the above conditions. 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.

(1-2) Method for producing activated carbon
(1) Oxidized activated carbon obtained by contacting activated carbon with an oxidizing agent can be used.

According to this method, the weight loss on heating at 200 to 300° C. can be 0.6% by mass or more with respect to 100% by mass of the total amount of activated carbon, without substantially affecting the pore structure of the activated carbon. In addition, when pickling activated carbon obtained by washing activated carbon with acid is used as the raw material activated carbon, the content of the metal component contained in the activated carbon is set to 0.5%, based on the total amount of activated carbon as 100% by mass. 05% by mass or less.

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.

When washing activated carbon with an acid, the acid used for washing the activated carbon does not easily impair the initial adsorption performance of aldehyde compounds, and it is easy to reduce the content of metal components in the activated carbon. A strong acid is preferable, and an inorganic strong acid is more preferable, and specifically, hydrochloric acid, sulfuric acid, etc., can be mentioned, and hydrochloric acid is preferable.

When the activated carbon is washed with an acid, the method of washing the activated carbon with the acid is not particularly limited as long as the entire surface of the activated carbon can be washed with the acid.

By washing the activated carbon with an acid, the content of metal components contained in the activated carbon can be reduced, and the total amount of activated carbon can be reduced to 0.05% by mass or less when 100% by mass. Therefore, compared with the case where the step of washing the activated carbon with an acid is not performed, it is easy to improve the weather resistance and suppress deterioration over time, and it is easy to improve the heat resistance.

Next, in step (1), activated carbon (preferably pickled activated carbon obtained by washing activated carbon with acid) is brought into contact with an oxidizing agent. At this time, as the oxidizing agent that can be used, it is easy to sufficiently improve the heat loss of activated carbon at 200 to 300 ° C., easy to improve weather resistance, easy to suppress deterioration over time, and easy to improve heat resistance. Examples include hydrogen peroxide, nitric acid, ozone, halogens (fluorine, chlorine, bromine, iodine, etc.), and hydrogen peroxide is preferred.

The method of bringing activated carbon (preferably pickled activated carbon obtained by washing activated carbon with acid) into contact with an oxidizing agent is not particularly limited, but for example, activated carbon (preferably pickled activated carbon obtained by washing activated carbon with acid) is conveniently immersed in an aqueous solution of the oxidizing agent. The concentration of the aqueous solution of the oxidizing agent that can be used at this time is not particularly limited, and can be adjusted as appropriate.

The time during which activated carbon (preferably pickled activated carbon obtained by washing activated carbon with acid) is brought into contact with the oxidizing agent (activated carbon (preferably pickled activated carbon obtained by washing activated carbon with acid) is immersed in the aqueous solution of the oxidizing agent. time) does not easily impair the initial adsorption performance of aldehyde compounds, sufficiently improves the heat loss of activated carbon at 200 to 300 ° C., easily improves weather resistance and further suppresses deterioration over time, and also has heat resistance. From the viewpoint of facilitating further improvement, it is preferably 10 to 360 minutes, more preferably 60 to 180 minutes.

When activated carbon (preferably pickled activated carbon obtained by washing activated carbon with acid) is immersed in an aqueous solution of an oxidizing agent, the heat loss of activated carbon at 200 to 300 ° C. is sufficiently improved, and the weather resistance is easily improved. From the standpoint of further suppressing aging deterioration and further improving heat resistance, activated carbon (preferably pickled activated carbon obtained by washing activated carbon with acid) is immersed in an aqueous solution of an oxidizing agent and stirred by a conventional method. may

As described above, the activated carbon (oxidized activated carbon) used in the present invention can be obtained, and by using this activated carbon (oxidized activated carbon), the weather resistance is improved, deterioration over time is suppressed, and Heat resistance can also be improved, but after this, drying may be performed by a conventional method in order to obtain activated carbon (oxidized activated carbon) in the form of powder.

(1-3) Amine compound In the amine compound-supported activated carbon (adsorbent) of the present invention, an amine compound is supported (attached) to the activated carbon.

The amine compound used in the present invention is not particularly limited, but any of primary amine compounds, secondary amine compounds and tertiary amine compounds can be used. It is easy to improve the solubility of aldehyde compounds, it is difficult to impair the initial adsorption performance of aldehyde compounds, it is easy to improve weather resistance, it is easy to further suppress deterioration over time, and it is easy to further improve heat resistance. preferable.

Specific examples of such amine compounds include trishydroxymethylaminomethane; 2-aminobenzenesulfonic acid (ortanilic acid), 3-aminobenzenesulfonic acid (methanilic acid), 4-aminobenzenesulfonic acid (sulfanilic acid ) and other hydroxyamine compounds such as aminobenzenesulfonic acid, polycyclic aromatic aminosulfonic acid compounds such as 2-amino-1-naphthalenesulfonic acid and 4-amino-1-naphthalenesulfonic acid; dimethylamine, diethylamine saturated cyclic secondary amine compounds such as piperidine, piperazine and morpholine; and aliphatic tertiary amine compounds such as trimethylamine and triethylamine. Among them, it is easy to improve the solubility in water, it is difficult to impair the initial adsorption performance of aldehyde compounds, it is easy to improve weather resistance, it is easy to further suppress deterioration over time, and it is easy to further improve heat resistance. compounds are preferred, aliphatic hydroxyamine compounds are more preferred, monovalent aliphatic hydroxyamine compounds are even more preferred, and trishydroxymethylaminomethane is particularly preferred. These amine compounds can be used alone or in combination of two or more.

A well-known or a commercial item can be used for the above-described amine compound.

The supported amount (impregnated amount) of the amine compound is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of activated carbon (dry product basis). ~15 parts by mass is more preferred. When the supported amount (impregnated amount) of the amine compound is within the above range, the amine compound is less likely to fill the pores of the activated carbon, less likely to impair the initial adsorption performance of the aldehyde compound, more easily improve weather resistance, and further suppress aging deterioration. It is easy to heat, and it is easy to further improve heat resistance.

(1-4) Amine compound-supported activated carbon (adsorbent)
The amine compound-supported activated carbon (adsorbent) of the present invention, which satisfies the above conditions, has particularly excellent adsorption performance for odorous substances such as aldehyde compounds, and is therefore useful as an adsorbent (especially an aldehyde compound 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 Amine Compound-Supported Activated Carbon (Adsorbent) The method for producing an amine compound-supported activated carbon (adsorbent) of the present invention (also referred to as a method for supporting (attaching) an amine compound) comprises:
A method comprising (1) the step of contacting activated carbon with an oxidizing agent and (2) the step of supporting the amine compound on the oxidized activated carbon obtained in step (1) is preferred.

Further, as described above, the raw material activated carbon is preferably pickled activated carbon obtained by washing activated carbon with an acid.

According to this method, it is difficult to impair the initial adsorption performance of odorants such as aldehyde compounds (formaldehyde, acetaldehyde, etc.), it is easy to improve weather resistance, it is easy to further suppress deterioration over time, and it is easy to further improve heat resistance. .

In addition, the amine compound-supported activated carbon (adsorbent) of the present invention obtained in this manner does not use compounds that are easily oxidized in the air, so it is a material that can withstand repeated use.

In addition, the process (1) can be adopted as it is described above.

In step (2), the oxidation-treated activated carbon obtained in step (1) is supported with an amine compound by:
(2A) a method of spraying and/or spraying an aqueous solution containing an amine compound onto the oxidized activated carbon;
(2B) A method of immersing oxidized activated carbon in an aqueous solution containing an amine compound.

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

By these methods, the amine compound can be carried (impregnated) on the entire oxidized activated carbon.

The temperature of the aqueous solution containing the amine compound to be used is not particularly limited, but it can usually be 15 to 30°C. can do.

The amount of the amine compound used is such that the supported (impregnated) amount of the amine compound is 1 to 50 parts by mass, particularly 1 to 30 parts by mass, and further 5 to 15 parts by mass with respect to 100 parts by mass (dry product basis) of the activated carbon. It is preferable to set For example, when the amine compound is supported (attached) to the oxidation-treated activated carbon by the method of step (2A) described above, the content of the amine compound in the aqueous solution containing the amine compound used becomes the supported (attached) amount as it is. Therefore, by spraying and/or sprinkling an aqueous solution containing 1 to 50 parts by mass, particularly 1 to 30 parts by mass, further 5 to 15 parts by mass of an amine compound onto 100 parts by mass of (dry) oxidation-treated activated carbon, Amine compound-supported activated carbon (adsorption agent) is obtained.

3. Method for adsorbing odorous substances (aldehyde compounds, etc.) using amine compound-supported activated carbon (adsorbent) In the adsorption method of the present invention, the amine compound-supported activated carbon (adsorbent) of the present invention and odorous substances (aldehyde compounds, etc.) are brought into contact. It is characterized by According to the adsorption method, the amine compound-supported activated carbon (adsorbent) of the present invention efficiently adsorbs odorous substances (aldehyde compounds, etc.), so that odorous substances (aldehyde compounds, etc.) can be efficiently removed.

4. Application to Industrial Products The amine compound-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-described industrial product blended with the amine compound-supported activated carbon (adsorbent) of the present invention is brought into contact with an odorant (aldehyde compound, etc.), whereby the amine compound-supported activated carbon of the present invention (adsorption agent) and odorous substances (such as aldehyde compounds) come into contact with each other, and as a result, the odorous substances (such as aldehyde compounds) 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.

Each step was performed at room temperature (25° C.) unless otherwise specified.

Metal component content JIS K 1474: 2014 7.13 In accordance with the iron analysis method, the content of each metal component of Al, Ca, Fe, K, Mg, Na, and Zn was analyzed by inductively coupled plasma atomic emission spectrometry (ICP). The metal component content of the activated carbon was determined by summing them.

Heat loss of activated carbon at 200 to 300° C. After boiling 3 g of activated carbon supporting an amine compound in 100 mL of 7% hydrochloric acid for 10 minutes, the activated carbon was recovered by filtration, and then the whole amount of the recovered activated carbon was boiled in 100 mL of distilled water for 10 minutes. , The activated carbon was filtered and recovered, and the recovered activated carbon after boiling in distilled water was dried at 115 ° C. for 3 hours, and the heat loss of the dried activated carbon was measured with a Thermo plus EVO TG8120 manufactured by Rigaku Corporation.

Examples 1 and 2
Activated carbon (coconut shell activated carbon manufactured by Osaka Gas Chemicals Co., Ltd.) having a BET specific surface area of 1000 m ² /g and a particle size of 42/80 mesh measured according to JIS Z 8801 was washed with 0.5% by mass hydrochloric acid to remove metal components. A pickled activated carbon with a content of 0.02% by weight was obtained.

60 g of the resulting pickling activated carbon was immersed in 400 mL of 20 to 25% by mass hydrogen peroxide solution, stirred for 1 hour, and then dried to obtain oxidized activated carbon. In addition, in Example 1, 20 mass % hydrogen peroxide water was used, and in Example 2, 25 mass % hydrogen peroxide water was used. Both the oxidation-treated activated carbon obtained here and Examples 1 and 2 had a metal component content of 0.02% by mass.

50 g of the obtained oxidized activated carbon was put into a 1 L desktop mixer, and while stirring, an aqueous solution prepared by dissolving 5 g of trishydroxymethylaminomethane in 12.5 g of distilled water was sprayed for 10 minutes on the oxidized activated carbon. Adsorbents of Examples 1 and 2 supported by trishydroxymethylaminomethane were obtained.

The obtained oxidized activated carbon of Examples 1 and 2 was boiled with hydrochloric acid and distilled water according to the above "heating loss of activated carbon at 200 to 300 ° C." When the weight loss on heating at 300° C. was measured, it was 0.85% by mass for Example 1 and 0.92% by mass for Example 2.

Comparative example 1
Neither pickling treatment with hydrochloric acid nor oxidation treatment with aqueous hydrogen peroxide was performed. That is, for activated carbon with a BET specific surface area of 1000 m ² /g and a particle size of 42/80 mesh measured in accordance with JIS Z 8801 (coconut shell activated carbon manufactured by Osaka Gas Chemicals Co., Ltd.; metal component content: 0.99% by mass) An adsorbent of Comparative Example 1 was obtained by supporting trishydroxymethylaminomethane in the same manner as in Examples 1 and 2 without pretreatment.

From the obtained adsorbent of Comparative Example 1, according to the above "heating loss of activated carbon at 200 to 300 ° C.", it was boiled with hydrochloric acid and distilled water to remove trishydroxymethylaminomethane, and then When the weight loss on heating was measured, it was 0.54% by mass.

Comparative Examples 2-4
As an oxidizing agent, 4 to 8% by mass nitric acid was used instead of hydrogen peroxide water (4% by mass nitric acid was used in Comparative Example 2, 6% by mass nitric acid was used in Comparative Example 3, and 8% by mass nitric acid was used in Comparative Example 4. ). That is, after subjecting activated carbon (coconut shell activated carbon manufactured by Osaka Gas Chemicals Co., Ltd.) having a BET specific surface area of 1000 m ² /g and a particle size of 42/80 mesh measured in accordance with JIS Z 8801 to a pickling treatment with hydrochloric acid, Oxidation treatment with nitric acid was performed (the metal component content was 0.02 mass in all of Comparative Examples 2 to 4), trishydroxymethylaminomethane was supported in the same manner as in Examples 1 and 2, and Comparative Example 2 ~4 adsorbents were obtained.

From the obtained adsorbents of Comparative Examples 2 to 4, according to the above "heating loss of activated carbon at 200 to 300 ° C.", boil with hydrochloric acid and distilled water to remove trishydroxymethylaminomethane. When the weight loss on heating at °C was measured, it was 0.50% by mass in Comparative Example 2, 0.52% by mass in Comparative Example 3, and 0.55% by mass in Comparative Example 4.

Example 3
No pickling treatment with hydrochloric acid was applied. That is, activated carbon (coconut shell activated carbon manufactured by Osaka Gas Chemicals Co., Ltd.) having a BET specific surface area of 1000 m ² /g and a particle size of 42/80 mesh measured according to JIS Z 8801 is subjected to oxidation treatment with hydrogen peroxide solution. (The metal component content was 0.33 mass.) Trishydroxymethylaminomethane was loaded in the same manner as in Examples 1 and 2 to obtain the adsorbent of Example 3.

From the obtained adsorbent of Example 3, according to the above "heating loss of activated carbon at 200 to 300 ° C.", boiled with hydrochloric acid and distilled water to remove trishydroxymethylaminomethane, and then When the weight loss on heating was measured, it was 0.83% by mass.

Comparative example 5
Activated carbon with a BET specific surface area of 1000 m ² /g and a particle size of 42/80 mesh measured in accordance with JIS Z 8801 (coconut shell activated carbon manufactured by Osaka Gas Chemicals Co., Ltd.; metal component content: 0.99 mass%) was added to 1 L volume. of Comparative Example 5 in which morpholine and potassium iodide are supported on activated carbon. A sorbent was obtained.

From the obtained adsorbent of Comparative Example 5, according to the above "heating loss of activated carbon at 200 to 300 ° C.", boil with hydrochloric acid and distilled water to remove morpholine and potassium iodide. When the weight loss on heating was measured, it was 0.50% by mass.

Test Example 1 Acetaldehyde Flow Test The apparatus shown in FIG. 1 was installed in a constant temperature chamber maintained at 25°C. Specifically, the adsorbent F (the adsorbent obtained in Examples and Comparative Examples) 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. This measurement was performed immediately after the adsorbent was manufactured (initial), after storage at 50°C for 7 days, and after storage at 50°C for 30 days.

Table 1 shows the results.

From Examples 1 and 2 and Comparative Example 1, activated carbon having a heat loss of 0.60% by mass or more at 200 to 300° C. impregnated with trishydroxymethylaminomethane, which is a primary amine compound, was initially It can be understood that the acetaldehyde equilibrium adsorption capacity of is sufficiently large and is a value that does not cause any practical problems, and that the performance retention rate is superior to that of Comparative Example 1 even after storage at a high temperature of 50 ° C.

From Examples 1 and 2 and Comparative Examples 2 to 4, the content of the metal component is 0.05% by mass or less, and even if oxidation treatment with nitric acid is performed, the weight loss on heating at 200 to 300 ° C. is 0. When it is less than 0.60% by mass, it can be understood that the performance retention rate of Examples 1 and 2 cannot be achieved.

From Examples 1 to 3 and Comparative Example 1, if the weight loss on heating at 200 to 300° C. is 0.60% by mass, even if the content of the metal component is greater than 0.05% by mass, a sufficient performance maintenance rate can be achieved. I can understand what you have. Furthermore, it can be understood that the performance retention rate can be further improved by setting the content of the metal component to 0.05% by mass or less.

From Examples 1 and 2 and Comparative Example 5, the adsorbent supporting morpholine and potassium iodide has a very large initial acetaldehyde equilibrium adsorption capacity, but the adsorption performance after storage at 50 ° C. for 30 days is extremely low, and deterioration is not observed. I understand that it is very easy to proceed. In Examples 1 and 2, although the initial equilibrium adsorption capacity of acetaldehyde is inferior to that of Comparative Example 5, it is sufficiently large and has no problem in practical use. is understandable.

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 (13)

An amine compound-supported activated carbon in which an amine compound is supported with respect to activated carbon,
An amine compound-supported activated carbon having a heat loss at 200 to 300° C. after removing the amine compound from the amine compound-supported activated carbon is 0.60% by mass or more based on the total amount of activated carbon as 100% by mass. The amine compound-supported activated carbon according to claim 1, wherein the metal component contained in the activated carbon is 0.05% by mass or less based on 100% by mass of the total amount of the activated carbon that does not support an amine compound. 3. The amine compound-supported activated carbon according to claim 1, wherein the amount of the amine compound supported is 1 to 50 parts by mass with respect to 100 parts by mass of the activated carbon. The amine compound-supported activated carbon according to any one of claims 1 to 3, wherein the amine compound is a primary hydroxylamine compound. The amine compound-supported activated carbon according to any one of claims 1 to 4, wherein the amine compound is trishydroxymethylaminomethane. An adsorbent containing the amine compound-supported activated carbon according to any one of claims 1 to 5. The adsorbent according to any one of claims 1 to 6, which is an aldehyde compound adsorbent. A method for producing the amine compound-supported activated carbon according to any one of claims 1 to 5 or the adsorbent according to claim 6 or 7,
(1) a step of contacting activated carbon with an oxidizing agent; and (2) a step of supporting the amine compound on the oxidized activated carbon obtained in step (1). 9. The production method according to claim 8, wherein the activated carbon used in step (1) is pickled activated carbon obtained by washing activated carbon with an acid. An industrial product using the amine compound-supported activated carbon according to any one of claims 1 to 5 or the adsorbent according to claim 6 or 7. A deodorizing filter using the amine compound-supporting activated carbon according to any one of claims 1 to 5 or the adsorbent according to claim 6 or 7. A method for adsorbing an aldehyde compound,
A step of contacting an aldehyde compound with an amine compound-supported activated carbon on which an amine compound is supported on activated carbon,
The adsorption method, wherein the activated carbon after removing the amine compound from the amine compound-supported activated carbon has a weight loss on heating at 200 to 300° C. of 0.60% by mass or more when the total amount of activated carbon is 100% by mass. The adsorption method according to claim 12, wherein the aldehyde compound has a boiling point of 100°C or lower.

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