WO2016031474A1

WO2016031474A1 - Adsorbent

Info

Publication number: WO2016031474A1
Application number: PCT/JP2015/071404
Authority: WO
Inventors: 将吾秋田; 田中　敦; 泰徳國本; 荒谷　渉
Original assignee: 大阪ガスケミカル株式会社
Priority date: 2014-08-27
Filing date: 2015-07-28
Publication date: 2016-03-03
Also published as: TW201609249A

Abstract

　The purpose of the present invention is to provide: a novel adsorbent in which the adsorption performance with respect to aldehyde-based malodorous substances and the aforementioned adsorption performance after a long period are excellent, any decrease in the adsorption performance due to regeneration is minimized, and excellent heat resistance is exhibited; a filter in which the adsorbent is used; a method for manufacturing the adsorbent; and a malodorous substance adsorption method in which the adsorbent is used. The above purpose is achieved by using an adsorbent in which imidazole and/or a derivative thereof is affixed to a porous carrier.

Description

Adsorbent

The present invention relates to an adsorbent.

In recent environmental society, interest in odor pollution countermeasures is increasing. Examples of odor pollution include pollution caused by exhaust gas. Odor substances contained in the exhaust gas include acidic odor substances, neutral odor substances, alkaline odor substances, and the like, and also odor substances such as aldehyde odor substances. Among them, aldehyde odor substances such as formaldehyde and acetaldehyde are considered as causative substances for sick house syndrome, and there is a high demand for removal and deodorization of the odor substances. Currently, in order to adsorb and remove various odorous substances, adsorbents attached with chemicals (chemical substances) corresponding to the respective odorous substances are used.

For example, for adsorption of aldehyde-based odorous substances having a high demand for the above-described removal and deodorization, (1) an adsorbent in which a saturated cyclic secondary amine (for example, morpholine) is supported (attached) to a porous carrier, ( 2) an adsorbent that also supports a non-volatile acid (for example, phosphoric acid) in addition to the saturated cyclic secondary amine on the porous carrier, and (3) an acid salt of p-aminobenzoic acid on the porous carrier. Also known are deodorizers (adsorbents) that carry inorganic acids (such as phosphoric acid) and bromides (alkali metal halides) (Patent Documents 1 to 3).

JP-A-4-358536 JP 2001-000524 A JP 2005-152726 A

However, when the chemical substance to be added is a saturated cyclic secondary amine, the adsorption performance of the aldehyde odor substance in the adsorbent is greatly reduced (deteriorated over time) after a long period of time (eg, 6 months). On the other hand, when a non-volatile acid is also carried in addition to the saturated cyclic secondary amine, although the above-described decrease in adsorption performance due to the passage of time is suppressed, there is room for improvement in (initial) adsorption performance, heat resistance, etc. There is. In addition, an adsorbent carrying an acid salt of p-aminobenzoic acid, an inorganic acid, and an alkali metal halide salt is obtained by such treatment when it is used once from the viewpoint of recycling and then regenerated (heat treatment, etc.). The metal component derived from the alkali metal halide salt remains on the porous carrier. Therefore, the adsorption performance of the adsorbent that uses (recycles) the porous carrier obtained by the regeneration treatment is deteriorated by the influence of the remaining metal component as compared with the adsorbent before the regeneration treatment.

Therefore, a novel adsorbent that is excellent in adsorption performance for odorous substances (particularly aldehyde-based odorous substances) and in the adsorption performance after a long period of time, and that suppresses a decrease in the adsorption performance due to regeneration treatment, and further has excellent heat resistance. It is desired.

The present invention is excellent in adsorption performance for odorous substances (particularly aldehyde odorous substances) and in the above-mentioned adsorption performance after a long period of time, and suppresses a decrease in the adsorption performance due to regeneration treatment, and further has excellent heat resistance. It is an object to provide an adsorbent, a filter using the adsorbent, a method for producing the adsorbent, and a method for adsorbing odorous substances using the adsorbent.

As a result of intensive studies, the present inventors have further added a non-volatile acid, an inorganic acid, an alkali metal halide salt or the like when a specific compound (component) is attached to the porous carrier. The present inventors have found that the above object can be achieved by solving the above problems. The present inventors have further researched and completed the present invention.

That is, this invention includes the adsorbent shown below, the filter using the said adsorbent, the manufacturing method of the said adsorbent, and the adsorption method of the odorous substance using the said adsorbent.
Item 1. An adsorbent in which imidazole and / or a derivative thereof are attached to a porous carrier.
Item 2. Item 2. The adsorbent according to Item 1, wherein the amount of the imidazole and / or derivative thereof is 1 to 40 parts by mass with respect to 100 parts by mass of the dry mass of the porous carrier.
Item 3. Item 3. The adsorbent according to Item 1 or 2, wherein the porous carrier is activated carbon.
Item 4. Item 4. The adsorbent according to any one of Items 1 to 3, which is an adsorbent for odorous substances.
Item 5. Item 5. The adsorbent according to Item 4, wherein the odor substance is an aldehyde odor substance.
Item 6. An industrial product using the adsorbent according to any one of Items 1 to 5.
Item 7. Item 7. The industrial product according to Item 6, which is a filter.
Item 8. Item 8. The industrial product according to Item 6 or 7, which is a deodorizing filter.
Item 9. A method for producing an adsorbent in which imidazole and / or a derivative thereof are attached to a porous carrier,
A method for producing an adsorbent, comprising a step of bringing a liquid containing the imidazole and / or a derivative thereof into contact with the porous carrier.
Item 10. A method for adsorbing an odor substance, wherein a gas containing an odor substance is brought into contact with an adsorbent in which imidazole and / or a derivative thereof are attached to a porous carrier.
Item 11. Item 11. The adsorption method according to Item 10, wherein the odor substance is an aldehyde odor substance.

In the adsorbent of the present invention, a specific component such as imidazole and / or a derivative thereof is attached to a porous carrier, so that adsorption performance for odorous substances (particularly aldehyde odorous substances) and odorous substances after a long period of time have passed. Adsorption performance with respect to (especially aldehyde-based odorous substances) is excellent. Further, a decrease in adsorption performance with respect to odorous substances (particularly aldehyde-based odorous substances) due to regeneration treatment is suppressed, and heat resistance is also excellent.

It is a graph which shows the formaldehyde breakthrough rate (%) for every time passage with respect to each adsorbent obtained in Example 1, Comparative Example 1 and Comparative Example 2. It is a graph which shows the formaldehyde breakthrough rate (%) for every time passage with respect to each adsorbent obtained in Examples 1 and 1A and Comparative Examples 3 and 3A. It is a graph which shows the formaldehyde breakthrough rate (%) for every time passage with respect to each adsorbent obtained in Examples 1 and 1B and Comparative Examples 4 and 4B. It is a graph which shows the formaldehyde breakthrough rate (%) for every time passage with respect to each adsorbent obtained in Examples 2 and 2C and Comparative Examples 2 and 2C. It is a graph which shows the formaldehyde removal rate (%) in each time at the time of using each deodorizing filter obtained in Example 3, 3D and 3E, and Comparative Examples 5, 5D and 5E.

Hereinafter, the adsorbent of the present invention, the filter using the adsorbent, the method for producing the adsorbent, and the method for adsorbing odorous substances using the adsorbent will be described. In the present specification, “attachment” means that a chemical such as imidazole and / or a derivative thereof is supported on a porous carrier.

≪1. Adsorbent≫
In the adsorbent of the present invention, imidazole and / or a derivative thereof are attached to a porous carrier.

In the adsorbent of the present invention, a specific component such as imidazole and / or a derivative thereof is attached to the porous carrier.
(1) Excellent adsorption performance for odorous substances (especially aldehyde odorous substances)
(2) Excellent adsorption performance for odorous substances (especially aldehyde odorous substances) after a long period of time (also said to have aged deterioration or stability over time),
(3) Even if the adsorbent is regenerated and the porous carrier obtained by the treatment is used again, the decrease in adsorption performance for odorous substances (especially aldehyde odorous substances) is suppressed (regeneration) It is also said that it is excellent in performance or recycling performance)
(4) Excellent heat resistance (Suppresses the decrease in adsorption performance for odorous substances (especially aldehyde odorous substances) even after the adsorbent is exposed to high temperatures of 200 ° C or lower (eg, 100-200 ° C). Is also said),
The effect is played.

The shape and average particle size of the adsorbent of the present invention are the same as the shape and average particle size of the porous carrier described later.

Hereinafter, each component of the adsorbent of the present invention will be described.

Porous carrier The adsorbent of the present invention comprises a porous carrier.

The porous carrier is not particularly limited, and generally known carriers can be widely used as the carrier. For example, activated carbon, activated clay, zeolite, silica, alumina (including activated alumina), ceramic, clay mineral, calcium carbonate and the like can be mentioned. A preferred porous carrier is activated carbon. The reason why activated carbon is preferable as the porous carrier is that the activated carbon has a cluttered pore structure unlike the pore structure of inorganic porous carriers such as zeolite and alumina. This is presumed to be adsorbed uniformly (uniformly). Further, since activated carbon does not have a freely moving cation, there is no possibility of cation exchange (base exchange) with imidazole and / or a derivative thereof as an attachment component. The porous carrier can be used alone or in combination of two or more.

The activated carbon raw material is not particularly limited as long as it is a carbon source that is normally used as an activated carbon raw material. For example, wood, wood flour, coconut shell, by-products during pulp production, bagasse, molasses, peat, lignite, lignite , Bituminous coal, anthracite, petroleum distillation residue components, petroleum pitch, coke, coal tar and other plant or fossil materials; phenol resin, vinyl chloride resin, vinyl acetate resin, melamine resin, urea resin, resorcinol resin, celluloid, epoxy Various synthetic resins such as resins, polyurethane resins, polyester resins, acrylic resins and polyamide resins; synthetic rubbers such as polybutylene, polybutadiene and polychloroprene; other synthetic woods; synthetic pulps and the like. Among these activated carbon raw materials, plant-based raw materials are preferably used, and coconut shells are more preferably used from the viewpoint that odorous substances (particularly aldehyde-based odorous substances) are easily adsorbed in the gas phase.

Examples of the carbonization or activation method for the activated carbon raw material include known activated carbon production methods such as a fixed bed method, a moving bed method, a fluidized bed method, and a rotary kiln method.

Carbonization of activated carbon raw materials includes nitrogen gas, carbon dioxide, helium, argon, xenon, neon, carbon monoxide, inactive gases such as combustion exhaust gas, and mixing with other gases mainly composed of these inert gases The method of baking using gas is mentioned. The temperature condition for carbonization is usually preferably 500 to 900 ° C, more preferably 600 to 800 ° C.

As a method for activating (or activating) the activated carbon raw material, a gas activation method using water vapor, carbon dioxide, carbon monoxide, oxygen, hydrogen chloride, ammonia, combustion gas, etc .; calcium chloride, calcium sulfide, phosphoric acid, sulfuric acid, chloride Examples include a chemical activation method for activating activated carbon raw materials in the presence of zinc or the like. Steam activation is preferable. The temperature condition for activation is usually 750 to 1200 ° C., preferably 800 to 1100 ° C.

After activating the activated carbon raw material, if necessary, the inorganic substance (ash content) in the carbon may be washed and deashed with dilute hydrochloric acid, an alkaline aqueous solution or the like, and further purified by repeated washing with water, followed by drying and sieving.

As the activated carbon (also referred to as “activated carbon before impregnating imidazole and / or a derivative thereof” or “original coal”), a commercially available product can be used. Examples of commercially available products include granular white birch WH2c20 / 48 (manufactured by Nippon Enviro Chemicals), coal granulated coal 6/8 mesh (BET specific surface area 1200 m ² / g), and the like.

When the adsorbent of the present invention is regenerated, the imidazole and / or its derivative, which is an adhering component, is released and becomes the porous carrier. The porous carrier obtained by the regeneration treatment (also simply referred to as “regeneration”) can be used (reused) again as the porous carrier in the adsorbent of the present invention (here, the regenerated porous material). The carrier is also referred to as “regenerated porous carrier”). Examples of the regeneration treatment include heat treatment (heat treatment).

The temperature during the heat treatment is preferably 850 to 950 ° C. By heat-treating the adsorbent of the present invention within the temperature range, the adsorbent (eg, organic compound) contained in the adsorbent is removed (desorbed) in a short time without deteriorating the porous carrier. , Or skip). As a result, a regenerated porous carrier is preferably obtained.

The time for the heat treatment is not particularly limited, and can be appropriately set depending on the amount of the adsorbent (or the porous carrier). The heat treatment time is preferably 30 minutes or more, more preferably 30 to 60 minutes. The pressure during the heat treatment is not particularly limited.

The atmosphere during the heat treatment is preferably an inert gas atmosphere. The atmosphere during the heat treatment is an inert gas, so that (i) surface oxides, surface functional groups, etc. present on the surface of the porous carrier, (ii) (diluted hydrochloric acid, alkaline aqueous solution, etc. after the activated carbon raw material is activated) The dilute hydrochloric acid, the alkaline aqueous solution and the like can be suitably and stably removed in the case of washing and decalcifying with the above. Therefore, the amount of imidazole and / or its derivative that contributes to the adsorption of odorous substances (particularly aldehyde odorous substances) among the imidazole and / or its derivatives attached can be increased. Excellent adsorption performance. Examples of the inert gas include nitrogen gas, helium, argon, xenon, neon, carbon monoxide, and combustion exhaust gas.

The apparatus for the heat treatment is not particularly limited, but heat treatment using a rotary kiln (cylindrical rotary furnace) is preferable.

In addition, when activated carbon is used as the porous carrier, the above-described heat treatment may be performed on the activated carbon before attaching imidazole and / or a derivative thereof. Each condition (temperature, time, atmosphere, apparatus, etc.) of the heat treatment is the same as each condition of the heat treatment in the regeneration process described above. In addition, when performing the above-mentioned heat processing with respect to activated carbon, the said heat processing is also called modification | reformation of activated carbon (or activated carbon surface). The heat treatment includes (i) surface oxides, surface functional groups, etc. present on the activated carbon surface, (ii) (when activated carbon raw materials are activated and washed and decalcified with dilute hydrochloric acid, alkaline aqueous solution, etc.) Since aqueous solution etc. are removed suitably, the adsorption | suction performance of the said odorous substance can be improved.

The shape of the porous carrier is not particularly limited. For example, it may be in the form of powder, crushed, or fiber, or may be granulated and formed into a columnar shape (pellet shape), a spherical shape, a honeycomb shape, or the like.

The average particle diameter of the porous carrier, the BET specific surface area, the pore volume, and the average pore diameter due to nitrogen adsorption under liquid nitrogen temperature conditions are not particularly limited, but the BET specific surface area is preferably 1000 m ² / g or more. The pore volume is preferably 0.4 mL / g or more, and the average pore diameter is preferably 1.7 nm or more.

Imidazole and / or its derivative In the adsorbent of the present invention, imidazole and / or its derivative are attached to a porous carrier.

Examples of imidazole derivatives include water-soluble derivatives of imidazole. Examples of water-soluble derivatives of imidazole include 1-methylimidazole and 2-methylimidazole.

The amount of imidazole and / or its derivative added is preferably 1 to 40 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass (based on the dry product) of the porous carrier. Because the amount of imidazole and / or its derivative is within the above range, it is difficult for imidazole and / or its derivative to fill the pores of the porous carrier, and the odorous substance easily reaches the reaction site in the adsorbent. It is possible to adsorb odorous substances (particularly aldehyde odorous substances) more efficiently.

Commercial products can be used for imidazole and / or its derivatives. In addition, imidazole and / or its derivative can be used 1 type or in combination of 2 or more types.

The adsorbent of the present invention has only imidazole and / or its derivative attached as a chemical (chemical substance). In other words, the adsorbent of the present invention has no components interposed between the porous carrier and imidazole and / or its derivative, and is attached (supported) so that the porous carrier and imidazole and / or its derivative are in direct contact. ) In addition to imidazole and / or its derivatives, (i) alkali metal halide salts (potassium iodide, etc.), (ii) alkaline earth metal halide salts, (iii) acids (phosphoric acid, etc.) ) And the like, the respective components are difficult to be detached from the porous carrier and are accumulated. As a result, an adsorbent using a regenerated porous carrier obtained by regenerating the adsorbent cannot obtain excellent adsorption performance. Therefore, in this invention, components other than imidazole and / or its derivative are not used as a chemical | medical agent.

≪2. Adsorbent production method≫
The method for producing an adsorbent of the present invention (also referred to as an attaching method) is a method for producing an adsorbent in which imidazole and / or a derivative thereof are attached to a porous carrier,
A method including a step of bringing a liquid containing the imidazole and / or a derivative thereof into contact with the porous carrier is preferable. According to the method,
(1) Excellent adsorption performance for odorous substances (especially aldehyde odorous substances)
(2) Excellent adsorption performance for odorous substances (especially aldehyde odorous substances) after a long period of time,
(3) Even if the adsorbent is regenerated and the porous carrier obtained by the treatment is used again, the decrease in adsorption performance for odorous substances (particularly aldehyde odorous substances) is suppressed,
(4) Excellent heat resistance,
Thus, an adsorbent exhibiting the effect can be suitably obtained.

As a method of contacting a porous carrier with a liquid containing imidazole and / or a derivative thereof (preferably a solution in which imidazole and / or a derivative thereof are dissolved in a solvent),
(a) a method of spraying and / or spraying a liquid containing the imidazole and / or derivative thereof on a porous carrier;
(b) a method of immersing a porous carrier in a liquid containing the imidazole and / or derivative thereof,
(c) A method of mixing a powdery porous carrier and a liquid containing the imidazole and / or derivative thereof, adding a binder as necessary, and granulating or molding may be mentioned. Among them, the method (a) or (b) is a preferable method because imidazole and / or a derivative thereof can be attached to the entire porous carrier without any bias. The temperature of the liquid containing imidazole and / or its derivative used is preferably 15 to 30 ° C., and the attachment time is preferably within 1 hour.

In the above methods (a) to (c), the solvent constituting the liquid containing imidazole and / or its derivative (hereinafter also simply referred to as “solvent”) is preferably a solvent that dissolves imidazole and / or its derivative. Examples of the solvent that dissolves imidazole and / or a derivative thereof include water.

The amount of imidazole and / or its derivative used is preferably set so that the amount of imidazole and / or its derivative added is 1 to 40 parts by mass with respect to 100 parts by mass (based on the dry product) of the porous carrier ( More preferably, it is 10 to 30 parts by mass). For example, when producing a porous carrier to which imidazole and / or a derivative thereof are attached by the method (a) described above, a liquid containing 1 to 40 parts by weight of imidazole and / or a derivative thereof is dried by 100 parts by weight. By spraying and / or spraying on the porous carrier, an adsorbent in which the amount of imidazole and / or its derivative is 1 to 40 parts by mass with respect to 100 parts by mass of the porous carrier (based on the dried product) can be obtained.

Note that, as described above, when the porous carrier is activated carbon, the activated carbon may be modified before the imidazole and / or derivative thereof is attached. Each condition (temperature, time, atmosphere, apparatus, etc.) of the heat treatment in the reforming is as described above.

≪3. Odor substance adsorption method using adsorbent≫
The adsorption method of the present invention is characterized in that a gas containing an odor substance (particularly an aldehyde odor substance) is brought into contact with an adsorbent in which imidazole and / or a derivative thereof are attached to a porous carrier. According to the adsorption method, the adsorbent adsorbs odorous substances (particularly aldehyde odorous substances) efficiently, so that the odorous substances can be efficiently removed.

The mechanism for adsorbing the odorous substance (bad odorous substance) using the adsorbent of the present invention is such that the imidazole and / or derivative thereof in the adsorbent chemically reacts with the odorous substance, and the product is It is believed that the adsorbent adsorbs.

Odor Substance The adsorbent of the present invention can efficiently adsorb odor substances (particularly aldehyde odor substances). Note that the adsorbent of the present invention is also effective for the odorous substances in which one kind or two or more kinds are combined.

Examples of aldehyde odor substances (aldehydes) include, in particular, lower aldehyde odor substances (lower aldehydes). Specific examples include formaldehyde, acetaldehyde, propionaldehyde, acrolein, n-butyraldehyde, isobutyraldehyde, 3-methyl-butyraldehyde, crotonaldehyde, and the like. Among these, the adsorbent of the present invention is particularly effective for the adsorption of formaldehyde and / or acetaldehyde.

Application to industrial products The adsorbent of the present invention can be used by mixing with industrial products. The industrial product includes the present invention.

Industrial products refer to industrial products and raw materials that have been widely known. Specifically, paints, adhesives, inks, sealants, paper products, binders, resin emulsions, pulp, wood materials, wood products, plastic products, films, wallpaper, building materials (gypsum board, interior materials, ceiling materials, floors) Materials), textile products, filters (especially deodorizing filters, etc.) and the like. These composite materials are also included in industrial products. Examples of the composite material include a composite material of wood and plastic. In the adsorption method of the present invention, the above-mentioned industrial product containing the adsorbent of the present invention is brought into contact with a gas containing an odor substance (particularly an aldehyde odor substance), whereby the adsorbent and the odor substance are brought into contact with each other. As a result, the odorous substance can be efficiently adsorbed and removed.

When a filter (especially a deodorizing filter) is adopted as an industrial product, its shape is not particularly limited. For example, the present invention is applied to a finely divided storage box (for example, a void in a resin-made honeycomb core such as polyethylene or polypropylene). It is possible to employ a filter (particularly a deodorizing filter or the like) that is filled with an adsorbent and is covered with a net made of a resin (polyethylene terephthalate or the like) that is excellent in air permeability and hard to break.

The method of filling the adsorbent of the present invention into a finely divided storage box is not particularly limited, and can be performed according to a conventional method.

In addition, the above-mentioned odorous substances can be efficiently adsorbed and removed by filling an adsorbing device such as a fixed bed, moving bed, fluidized bed, etc., and subjecting this to a gas containing odorous substances (particularly aldehyde odorous substances). be able to.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the embodiments.

Example 1
10 parts by mass of imidazole (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 20 parts by mass of water to prepare an adhesion solution (liquid temperature 20 ° C.). Next, while rotating a small sugar-coating machine containing 100 parts by mass of coconut shell activated carbon (granular white birch WH2c20 / 48, manufactured by Nihon Enviro Chemicals Co., Ltd., porous carrier) having a particle size of 0.850 to 0.300 mm (20 / 48mesh) The adsorbent in which imidazole was attached to the coconut shell activated carbon was obtained by spraying the above prepreg solution uniformly on the coconut shell activated carbon (attachment time: 20 minutes).

<Adhesive component and amount in Example 1>
-Imidazole addition amount: 10 parts by mass with respect to 100 parts by mass of the porous carrier.

Example 2
An adsorbent in which imidazole was attached to coconut shell activated carbon was obtained in the same manner as in Example 1 except that 20 parts by weight of imidazole was dissolved in 20 parts by weight of water to prepare an impregnation solution (liquid temperature 20 ° C.).

<Adhesion component and amount in Example 2>
-Imidazole addition amount: 20 parts by mass with respect to 100 parts by mass of the porous carrier.

Example 3
60 x 60 x 10 mm of adsorbent 7 g of 10 g of imidazole dissolved in 20 parts of water and sprayed on 100 parts by mass of coal granulated coal 6/8 mesh (BET specific surface area 1200 m ² / g) The voids of the polyethylene honeycomb core were filled by a conventional method, and both sides were covered with a polyethylene terephthalate (PET) net to obtain a deodorizing filter.

Comparative Example 1
Coconut shell activated carbon having a particle size of 0.850 to 0.300 mm (20 / 48mesh) (granular white birch WH2c20 / 48, manufactured by Nippon Enviro Chemicals Co., Ltd.) was used as an adsorbent. That is, the adsorbent of Comparative Example 1 is non-attached activated carbon to which nothing is attached.

Comparative Example 2
10 parts by mass of morpholine (manufactured by Wako Pure Chemical Industries, Ltd.), 2 parts by mass of potassium iodide (manufactured by Wako Pure Chemical Industries, Ltd.), and 4 parts by mass of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) are 30 parts by mass of water. The adsorbent in which the three components morpholine, potassium iodide and phosphoric acid were adhering to the coconut shell activated carbon was obtained in the same manner as in Example 1 except that the adsorbing solution (liquid temperature 20 ° C.) was prepared by dissolving in coconut shell. .

<Adhesive component and amount in Comparative Example 2>
-Morpholine adhesion amount: 10 parts by mass with respect to 100 parts by mass of the porous carrier,
-Potassium iodide loading: 2 parts by mass with respect to 100 parts by mass of the porous carrier,
-Phosphoric acid adhesion amount: 4 parts by mass with respect to 100 parts by mass of the porous carrier.

Comparative Example 3
10 parts by mass of imidazole (manufactured by Wako Pure Chemical Industries, Ltd.), 2 parts by mass of potassium iodide (manufactured by Wako Pure Chemical Industries, Ltd.), and 6 parts by mass of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.), 30 parts by mass of water The adsorbent in which the three components of imidazole, potassium iodide and phosphoric acid were adsorbed to coconut shell activated carbon was obtained in the same manner as in Example 1 except that the adsorbent solution (liquid temperature 20 ° C.) was prepared by dissolving in coconut shell. .

<Adhesive component and amount in Comparative Example 3>
-Imidazole adhesion amount: 10 parts by mass with respect to 100 parts by mass of the porous carrier,
-Potassium iodide loading: 2 parts by mass with respect to 100 parts by mass of the porous carrier,
-Phosphoric acid adhesion amount: 6 parts by mass with respect to 100 parts by mass of the porous carrier.

Comparative Example 4
Morpholine is attached to coconut shell activated carbon in the same manner as in Example 1 except that 10 parts by weight of morpholine (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in 20 parts by weight of water to prepare an attachment solution (liquid temperature 20 ° C.). An adsorbent was obtained.

<Adhesive component and amount in Comparative Example 4>
-Morpholine adhesion amount: 10 parts by mass with respect to 100 parts by mass of the porous carrier.

Comparative Example 5
60 x 60 x 10 mm of adsorbent 7 g, which is obtained by dissolving 10 parts by mass of morpholine in 20 parts by mass of water and spraying it with 100 parts by mass of coal granulated coal 6/8 mesh (BET specific surface area 1200 m ² / g) The voids of the polyethylene honeycomb core were filled by a conventional method, and both sides were covered with a polyethylene terephthalate (PET) net to obtain a deodorizing filter.

Test example 1: Adsorption performance evaluation of adsorbents for aldehyde odor substances (Adsorption performance evaluation)
An odor gas (formaldehyde-containing) prepared by filling 3.2 ml of each of the obtained adsorbents (Example 1, Comparative Example 1 and Comparative Example 2) into a glass column having an inner diameter of 20 mm and adjusting the temperature to 25 ° C., 10 ppm formaldehyde and 60% humidity. Gas) at a flow rate of 2 L / min. The LV (linear velocity) was 0.11 m / sec, and the SV (space velocity) was 37000 / hr. The formaldehyde concentration (ppm) at the inlet and outlet of the glass column was analyzed by gas chromatography every time a certain time passed, and the breakthrough rate (%) was calculated. Further, based on the measured formaldehyde concentration, the amount of adsorption per mass (mg / g) when the breakthrough rate was 5% and 80% was calculated. For measurement of formaldehyde concentration in gas chromatography, a GC-FID with a methanizer (GC-14B, manufactured by Shimadzu Corporation) and a separation column (diameter 3 mm × length 600 mm, Porapak TYPE T 50/80) were used. The breakthrough rate is calculated by the following formula:
Breakthrough rate (%) = C / C ₀ × 100
C ₀ : Formaldehyde concentration (ppm)
C: Outlet formaldehyde concentration (ppm)
Calculated by The test results are shown in FIG.

<Discussion>
As is clear from FIG. 1 and Table 1, the adsorbent of Example 1 to which imidazole (only) is attached is a non-attached formaldehyde adsorbed when the breakthrough rate is 5% and 80%. Compared with the adsorbent of Example 1 and the adsorbent of Comparative Example 2 to which morpholine, potassium iodide and phosphoric acid are attached, each shows a large value. That is, the adsorbent of Example 1 is superior in comparison with the adsorbent of Comparative Example 1 which is non-added and the adsorbent of Comparative Example 2 in which morpholine, potassium iodide and phosphoric acid are attached. System odor substance adsorption performance is shown.

Test Example 2: Adsorption performance evaluation for aldehyde odorous substances in the adsorbent obtained after regeneration treatment (regeneration performance evaluation)
First, the adsorbents of Example 1 and Comparative Example 3 were prepared. Next, the adsorbents of Example 1 and Comparative Example 3 were subjected to a heat treatment at 900 ° C. for 30 minutes in a rotary kiln under a nitrogen gas atmosphere, and then naturally cooled. By this operation, the adsorbents in Example 1 and Comparative Example 3 were regenerated coconut shell activated carbon. Here, in order to distinguish the coconut shell activated carbon obtained by subjecting the adsorbent of Example 1 to the heat treatment and natural cooling from the new coal described later, the regenerated coconut shell activated carbon (or regenerated coal of Example 1A) is used. ). Moreover, in order to distinguish the coconut shell activated carbon obtained by performing the said heat processing and natural cooling with respect to the adsorption agent of the comparative example 3, from the new coal mentioned later, the reproduction | regeneration coconut shell activated carbon (or regenerated coal) of the comparative example 3A Also called.

Next, in place of the coconut shell activated carbon (granular white birch WH2c20 / 48, Nihon Enviro Chemicals Co., Ltd., new coal coconut shell activated carbon), the same procedure as in Example 1 was used except that the regenerated coconut shell activated carbon of Example 1A was used. Thus, an adsorbent in which imidazole was attached to the regenerated coconut shell activated carbon of Example 1A was obtained (hereinafter, this adsorbent is referred to as the adsorbent of Example 1A). Moreover, it replaces with coconut shell activated carbon (granular white birch WH2c20 / 48, Nippon Enviro Chemicals Co., Ltd., new charcoal coconut shell activated carbon), and uses the regenerated coconut shell activated carbon of the said comparative example 3A similarly to the comparative example 3. Thus, an adsorbent in which the three components of imidazole, potassium iodide and phosphoric acid were attached to the regenerated coconut shell activated carbon of Comparative Example 3A was obtained (hereinafter, this adsorbent is referred to as the adsorbent of Comparative Example 3A).

Next, in place of the adsorbents of Example 1, Comparative Example 1, and Comparative Example 2, except that the adsorbents of Example 1, Example 1A, Comparative Example 3, and Comparative Example 3A were used, In the same manner as in Test Example 1, the breakthrough rate (%) for each passage of time and the amount of adsorption (mg / g) per mass when the breakthrough rate was 5% and 80% were measured or calculated. The test results are shown in FIG.

<Discussion>
As is apparent from FIG. 2 and Table 2, the adsorbent of Example 1A to which imidazole (only) is attached (adsorbent after regenerating the porous carrier) is attached to imidazole (only). Compared with Example 1, a decrease in the adsorption performance of formaldehyde is suppressed (the adsorption performance is almost equivalent). In contrast, the adsorbent of Comparative Example 3A in which imidazole, potassium iodide and phosphoric acid are adsorbed (adsorbent after regenerating the porous carrier) is adsorbed with imidazole, potassium iodide and phosphoric acid. Compared with the comparative example 3 which exists, the big fall of the adsorption | suction performance of formaldehyde is seen. This large decrease in the adsorption performance is considered to be due to the influence of the potassium metal component remaining after the adsorbent is regenerated. Thus, the adsorbent of Example 1 is excellent in regeneration performance.

Test Example 3: Adsorption performance evaluation for aldehyde odorous substance in adsorbent after 6 months (durability evaluation)
First, the adsorbents of Example 1 and Comparative Example 4 were prepared (these adsorbents are also referred to as initial products). Next, each adsorbent (initial product) of Example 1 and Comparative Example 4 was put in a plastic bag and stored at room temperature for 6 months (the adsorbent after storing at room temperature is also referred to as a product after 6 months, In order to distinguish from the initial product, it is also referred to as the adsorbent of Example 1B and Comparative Example 4B).

Next, in place of the adsorbents of Example 1, Comparative Example 1 and Comparative Example 2, except that the adsorbents of Example 1, Example 1B, Comparative Example 4 and Comparative Example 4B are used, In the same manner as in Test Example 1, the breakthrough rate (%) for each passage of time and the amount of adsorption (mg / g) per mass when the breakthrough rate was 5% and 80% were measured or calculated. The test results are shown in FIG.

<Discussion>
As apparent from FIG. 3 and Table 3, the adsorbent of Example 1B to which imidazole (only) is attached (six months old product) is Example 1 (initial product) to which imidazole (only) is attached. ), The decrease in formaldehyde adsorption performance is suppressed (adsorption performance is almost the same). In contrast, the adsorbent of Comparative Example 4B (six months old product) to which morpholine (only) is attached is more formaldehyde than Comparative Example 4 (initial product) to which morpholine (only) is attached. The adsorption performance is greatly reduced. Thus, the adsorbent of Example 1 is excellent in the adsorption performance of aldehyde odorous substances even after a long period of time, and is excellent in durability.

Test Example 4: Adsorption performance evaluation for aldehyde odorous substance in adsorbent after heating (heat resistance evaluation)
First, the adsorbents of Example 2 and Comparative Example 2 were prepared (these adsorbents are also referred to as initial products). Next, each of the adsorbents of Example 2 and Comparative Example 2 was subjected to heat treatment at 150 ° C. for 3 hours in an electric drying furnace, and then naturally cooled (adsorption after the heat treatment and natural cooling). The agent is also referred to as a heat-treated product, and is also referred to as the adsorbent of Example 2C and Comparative Example 2C in order to distinguish it from the initial product).

Next, in place of the adsorbents of Example 1, Comparative Example 1 and Comparative Example 2, except that the adsorbents of Example 2, Example 2C, Comparative Example 2 and Comparative Example 2C were used, In the same manner as in Test Example 1, the breakthrough rate (%) for each passage of time and the amount of adsorption (mg / g) per mass when the breakthrough rate was 5% and 80% were measured or calculated. The test results are shown in FIG.

<Discussion>
As is apparent from FIG. 4 and Table 4, the adsorbent (heat-treated product) of Example 2C to which imidazole (only) is attached is Example 2 (initial product) to which imidazole (only) is attached. ), The decrease in the adsorption performance of formaldehyde is suppressed (the decrease in the adsorption performance is about 20%). On the other hand, the adsorbent (heat-treated product) of Comparative Example 2C to which morpholine (only) is attached is more formaldehyde than Comparative Example 2 (initial product) to which morpholine (only) is attached. The adsorption performance is completely lost. Thus, the adsorbent of Example 2 is excellent in the adsorption performance of the aldehyde odor substance even after being heated at 150 ° C., and is excellent in heat resistance.

Test Example 5 Performance Evaluation Test of Deodorant Filter An air cleaner equipped with each of the deodorant filters of Example 3 and Comparative Example 5 in a 1 m ³ box filled with 2 ppm formaldehyde at LV1.0 m / sec 60 It was run for minutes, and the formaldehyde removal rate was calculated from the formaldehyde concentration and the initial concentration at each time. Separately, each of the deodorizing filters of Example 3 and Comparative Example 5 was packed in a predetermined packaging material (polyethylene bag), and stored at room temperature, and opened at 4 months and 8 months, respectively. Tests were performed under the same conditions as above, and deterioration with time was confirmed. The adsorbent after storage at room temperature is also referred to as a 4-month-old product and an 8-month-old product. To distinguish it from the initial product, the 4-month-old product of Example 3 is used as the deodorizing filter of Example 3D. The 8-month-old product of Example 3 is the deodorizing filter of Example 3E, the 4-month-old product of Comparative Example 5 is the deodorizing filter of Comparative Example 5D, and the 8-month-old product of Comparative Example 5 is the deodorizing filter of Comparative Example 5E. Called. The test results are shown in FIG.

<Discussion>
As is clear from FIG. 5 and Table 5, the odor filters (Examples after 4 months and Products after 8 months) of Examples 3D and 3E to which imidazole (only) is attached are attached with imidazole (only). In comparison with Example 3 (new coal), the formaldehyde removal performance after 60 minutes is as high as 70% or more, but the deodorization of Comparative Examples 5D and 5E to which morpholine (only) is attached The filter (4 month and 8 month products) has a formaldehyde removal performance of about 30% after 60 minutes compared to Comparative Example 5 (new coal) to which morpholine (only) is attached. . That is, Example 3 shows that the filter medium for the air cleaner has sufficient durability at a practical level as compared with Comparative Example 5, and hardly deteriorates over time.

Claims

An adsorbent in which imidazole and / or a derivative thereof are attached to a porous carrier.
The adsorbent according to claim 1, wherein the amount of the imidazole and / or derivative thereof is 1 to 40 parts by mass with respect to 100 parts by mass of the dry mass of the porous carrier.
The adsorbent according to claim 1 or 2, wherein the porous carrier is activated carbon.
The adsorbent according to any one of claims 1 to 3, which is an adsorbent for an odor substance.
The adsorbent according to claim 4, wherein the odor substance is an aldehyde odor substance.
An industrial product using the adsorbent according to any one of claims 1 to 5.
The industrial product according to claim 6, which is a filter.
The industrial product according to claim 6 or 7, which is a deodorizing filter.
A method for producing an adsorbent in which imidazole and / or a derivative thereof are attached to a porous carrier,
A method for producing an adsorbent, comprising a step of bringing a liquid containing the imidazole and / or a derivative thereof into contact with the porous carrier.
A method for adsorbing an odor substance, wherein a gas containing an odor substance is brought into contact with an adsorbent in which imidazole and / or a derivative thereof are attached to a porous carrier.
The adsorption method according to claim 10, wherein the odor substance is an aldehyde odor substance.