WO2016031474A1 - Adsorbent - Google Patents

Adsorbent Download PDF

Info

Publication number
WO2016031474A1
WO2016031474A1 PCT/JP2015/071404 JP2015071404W WO2016031474A1 WO 2016031474 A1 WO2016031474 A1 WO 2016031474A1 JP 2015071404 W JP2015071404 W JP 2015071404W WO 2016031474 A1 WO2016031474 A1 WO 2016031474A1
Authority
WO
WIPO (PCT)
Prior art keywords
adsorbent
imidazole
porous carrier
derivative
mass
Prior art date
Application number
PCT/JP2015/071404
Other languages
French (fr)
Japanese (ja)
Inventor
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 (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 大阪ガスケミカル株式会社 filed Critical 大阪ガスケミカル株式会社
Publication of WO2016031474A1 publication Critical patent/WO2016031474A1/en

Links

Images

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/01Deodorant compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/16Disinfection, sterilisation or deodorisation of air using physical phenomena
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/72Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating

Definitions

  • the present invention relates to an adsorbent.
  • 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.
  • 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.
  • adsorbents attached with chemicals (chemical substances) corresponding to the respective odorous substances are used.
  • 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.
  • deodorizers adsorbents
  • inorganic acids such as phosphoric acid
  • bromides alkali metal halides
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. 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.
  • Item 4. Item 4.
  • 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. 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.
  • 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.
  • 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.
  • 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.
  • attachment means that a chemical such as imidazole and / or a derivative thereof is supported on a porous carrier.
  • Adsorbent In the adsorbent of the present invention, imidazole and / or a derivative thereof are attached to a porous carrier.
  • a specific component such as imidazole and / or a derivative thereof is attached to the porous carrier.
  • 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
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • plant-based raw materials are preferably used, and coconut shells are more preferably used from the viewpoint that odorous substances (particularly aldehyde-based odor)
  • 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.
  • the temperature condition for activation is usually 750 to 1200 ° C., preferably 800 to 1100 ° C.
  • 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.
  • 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.
  • 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.
  • the adsorbent of the present invention 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.
  • the adsorbent eg, organic compound contained in the adsorbent is removed (desorbed) in a short time without deteriorating the porous carrier. , Or skip).
  • 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.
  • 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.
  • 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.
  • the said heat processing is also called modification
  • the heat treatment includes (i) surface oxides, surface functional groups, etc.
  • the shape of the porous carrier is not particularly limited.
  • 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 are attached to a porous carrier.
  • imidazole derivatives include water-soluble derivatives of imidazole.
  • 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.
  • imidazole and / or its derivatives Commercial products can be used for imidazole and / or its derivatives.
  • 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).
  • 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.
  • alkali metal halide salts potassium iodide, etc.
  • alkaline earth metal halide salts iii)
  • acids phosphoric acid, etc.
  • 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
  • Adsorbent production 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.
  • 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 method of spraying and / or spraying a liquid containing the imidazole and / or derivative thereof on a porous carrier a method of spraying and / or spraying a liquid containing the imidazole and / or derivative thereof on a porous carrier
  • a method of immersing a porous carrier in a liquid containing the imidazole and / or derivative thereof 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.
  • 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.
  • the solvent constituting the liquid containing imidazole and / or its derivative is preferably a solvent that dissolves imidazole and / or its derivative.
  • 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).
  • a liquid containing 1 to 40 parts by weight of imidazole and / or a derivative thereof is dried by 100 parts by weight.
  • 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.
  • the porous carrier 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.
  • Odor substance adsorption method using adsorbent 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.
  • 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.
  • aldehyde odor substances include, in particular, lower aldehyde odor substances (lower aldehydes).
  • lower aldehyde odor substances include formaldehyde, acetaldehyde, propionaldehyde, acrolein, n-butyraldehyde, isobutyraldehyde, 3-methyl-butyraldehyde, crotonaldehyde, and the like.
  • the adsorbent of the present invention is particularly effective for the adsorption of formaldehyde and / or acetaldehyde.
  • 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.
  • 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.
  • a gas containing an odor substance particularly an aldehyde odor substance
  • a filter especially a deodorizing filter
  • its shape is not particularly limited.
  • 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.
  • 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.
  • 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).
  • coconut shell activated carbon granular white birch WH2c20 / 48, manufactured by Nihon Enviro Chemicals Co., Ltd., porous carrier
  • Example 1 ⁇ 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.).
  • 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.
  • PET polyethylene terephthalate
  • 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. .
  • -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. .
  • -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.
  • morpholine manufactured by Wako Pure Chemical Industries, Ltd.
  • 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.
  • PET polyethylene terephthalate
  • 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
  • the SV space velocity
  • 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.
  • 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.
  • 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.
  • 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%.
  • 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.
  • the regenerated coconut shell activated carbon (or regenerated coal of Example 1A) is used.
  • regeneration coconut shell activated carbon (or regenerated coal) of the comparative example 3A Also called.
  • Example 1A 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).
  • Test Example 3 Adsorption performance evaluation for aldehyde odorous substance in adsorbent after 6 months (durability evaluation)
  • the adsorbents of Example 1 and Comparative Example 4 were prepared (these adsorbents are also referred to as initial products).
  • 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).
  • Example 1B 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).
  • Comparative Example 4B 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.
  • 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)
  • the adsorbents of Example 2 and Comparative Example 2 were prepared (these adsorbents are also referred to as initial products).
  • 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).
  • 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%).
  • 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.
  • 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.
  • a predetermined packaging material polyethylene bag
  • the adsorbent after storage at room temperature is also referred to as a 4-month-old product and an 8-month-old 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
  • 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

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

吸着剤Adsorbent
 本発明は、吸着剤に関する。 The present invention relates to an adsorbent.
 近年の環境社会において、臭気公害対策への関心が高まっている。臭気公害としては、例えば排ガスによる公害が挙げられる。当該排ガスに含まれる臭気物質には、酸性臭気物質、中性臭気物質、アルカリ性臭気物質等が存在する他、アルデヒド系臭気物質等の臭気物質も存在する。なかでも、ホルムアルデヒド、アセトアルデヒド等のアルデヒド系臭気物質は、シックハウス症候群の原因物質とされており、当該臭気物質の除去及び消臭に対する要望が高い。現在、各種臭気物質を吸着除去するために、それぞれの臭気物質に対応する薬品(化学物質)が添着した吸着剤が用いられている。 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.
 例えば、上述の除去及び消臭に対する要望の高いアルデヒド系臭気物質の吸着には、(1)多孔質担体に対して飽和環状第二アミン(例えばモルホリン等)を担持(添着)した吸着剤、(2)多孔質担体に対して前記飽和環状第二アミンに加えて不揮発性酸(例えばリン酸等)をも担持した吸着剤、(3)多孔質担体に対してp-アミノ安息香酸の酸性塩と、無機酸(例えばリン酸等)と、臭化物(ハロゲン化アルカリ金属塩)とを担持した脱臭剤(吸着剤)等が知られている(特許文献1~3)。 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).
特開平4-358536号公報JP-A-4-358536 特開2001-000524号公報JP 2001-000524 A 特開2005-152726号公報JP 2005-152726 A
 しかしながら、添着させる化学物質が飽和環状第二アミンである場合、長期間(例:6ヶ月)経過すると吸着剤におけるアルデヒド系臭気物質の吸着性能が大きく低下する(経年劣化する)。一方、前記飽和環状第二アミンに加えて不揮発性酸をも担持させる場合、上述の長時間経過による吸着性能の低下は抑制されるものの、(初期の)吸着性能、耐熱性等に改善の余地がある。また、p-アミノ安息香酸の酸性塩と無機酸とハロゲン化アルカリ金属塩とを担持させた吸着剤は、リサイクルの観点から一旦使用した後に再生処理(熱処理等)した場合、当該処理によって得られる多孔質担体に前記ハロゲン化アルカリ金属塩由来の金属成分が残存してしまう。そのため、再生処理して得られた多孔質担体を使用(再利用)する吸着剤の吸着性能は、再生処理前の吸着剤と比べて、前記残存する金属成分の影響によって低下してしまう。 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.
 よって、臭気物質(特にアルデヒド系臭気物質)に対する吸着性能及び長期間経過後の前記吸着性能に優れ、且つ、再生処理による前記吸着性能の低下が抑制され、さらに耐熱性に優れた新規吸着剤が望まれている。 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.
 本発明は、臭気物質(特にアルデヒド系臭気物質)に対する吸着性能及び長期間経過後の前記吸着性能に優れ、且つ、再生処理による前記吸着性能の低下が抑制され、さらに耐熱性に優れた新規吸着剤、当該吸着剤を用いたフィルター、当該吸着剤の製造方法及び当該吸着剤を使用した臭気物質の吸着方法を提供することを目的とする。 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.
 本発明者らは、鋭意研究を重ねた結果、多孔質担体に対して特定の化合物(成分)を添着させる場合には、不揮発性酸、無機酸、ハロゲン化アルカリ金属塩等をさらに添着させることなく上記問題を解消して上記目的を達成できることを見出した。本発明者らは、さらに研究を重ね、本発明を完成するに至った。 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.
 すなわち、本発明は、以下に示す吸着剤、当該吸着剤を用いたフィルター、当該吸着剤の製造方法及び当該吸着剤を使用した臭気物質の吸着方法を包含する。
項1.イミダゾール及び/又はその誘導体が多孔質担体に添着している、吸着剤。
項2.前記イミダゾール及び/又はその誘導体の添着量が、前記多孔質担体の乾燥質量100質量部に対して、1~40質量部である、項1に記載の吸着剤。
項3.前記多孔質担体が、活性炭である、項1又は2に記載の吸着剤。
項4.臭気物質の吸着剤である、項1~3のいずれかに記載の吸着剤。
項5.前記臭気物質がアルデヒド系臭気物質である、項4に記載の吸着剤。
項6.項1~5のいずれかに記載の吸着剤を用いた工業製品。
項7.フィルターである、項6に記載の工業製品。
項8.消臭フィルターである、項6又は7に記載の工業製品。
項9.イミダゾール及び/又はその誘導体が多孔質担体に添着している吸着剤の製造方法であって、
前記イミダゾール及び/又はその誘導体を含む液を前記多孔質担体に接触させる工程を含む、吸着剤の製造方法。
項10.臭気物質を含有する気体を、イミダゾール及び/又はその誘導体が多孔質担体に添着している吸着剤と接触させる、臭気物質の吸着方法。
項11.前記臭気物質がアルデヒド系臭気物質である、項10に記載の吸着方法。
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.
 本発明の吸着剤は、多孔質担体にイミダゾール及び/又はその誘導体という特定の成分を添着させているため、臭気物質(特にアルデヒド系臭気物質)に対する吸着性能、及び長期間経過した後における臭気物質(特にアルデヒド系臭気物質)に対する吸着性能に優れており、さらに再生処理による臭気物質(特にアルデヒド系臭気物質)に対する吸着性能の低下が抑制されており、さらに耐熱性にも優れている。 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.
実施例1、比較例1及び比較例2で得られた各吸着剤に対する時間経過毎のホルムアルデヒド破過率(%)を示すグラフである。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. 実施例1及び1A、並びに比較例3及び3Aで得られた各吸着剤に対する時間経過毎のホルムアルデヒド破過率(%)を示すグラフである。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. 実施例1及び1B、並びに比較例4及び4Bで得られた各吸着剤に対する時間経過毎のホルムアルデヒド破過率(%)を示すグラフである。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. 実施例2及び2C、並びに比較例2及び2Cで得られた各吸着剤に対する時間経過毎のホルムアルデヒド破過率(%)を示すグラフである。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. 実施例3、3D及び3E、並びに比較例5、5D及び5Eで得られた各消臭フィルターを用いた際の各時間におけるホルムアルデヒド除去率(%)を示すグラフである。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.
 以下、本発明の吸着剤、吸着剤を用いたフィルター、吸着剤の製造方法及び当該吸着剤を使用した臭気物質の吸着方法について説明する。なお、本明細書において、「添着」とは、イミダゾール及び/又はその誘導体等の薬品を多孔質担体に担持することをいう。 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.吸着剤≫
 本発明の吸着剤は、イミダゾール及び/又はその誘導体が多孔質担体に添着している。
≪1. Adsorbent≫
In the adsorbent of the present invention, imidazole and / or a derivative thereof are attached to a porous carrier.
 本発明の吸着剤は、多孔質担体にイミダゾール及び/又はその誘導体という特定の成分を添着しているため、
(1)臭気物質(特にアルデヒド系臭気物質)に対する吸着性能に優れており、
(2)長期間経過した後における臭気物質(特にアルデヒド系臭気物質)に対する吸着性能に優れており(経年劣化が抑制されている、又は耐久性若しくは経時安定性に優れている、ともいう)、
(3)吸着剤に対して再生処理を行い、当該処理により得られた多孔質担体を再び使用したとしても、臭気物質(特にアルデヒド系臭気物質)に対する吸着性能の低下が抑制されており(再生性能又はリサイクル性能に優れている、ともいう)、
(4)耐熱性に優れている(吸着剤を200℃以下の高温下(例えば100~200℃)にさらされた後においても、臭気物質(特にアルデヒド系臭気物質)に対する吸着性能の低下が抑制されている、ともいう)、
という効果が奏される。
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.
 本発明の吸着剤の形状及び平均粒子径については、後述する多孔質担体の形状及び平均粒子径と、それぞれ同等である。 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.
 以下、本発明の吸着剤の各成分について説明する。 Hereinafter, each component of the adsorbent of the present invention will be described.
 多孔質担体
 本発明の吸着剤は、多孔質担体を含む。
Porous carrier The adsorbent of the present invention comprises a porous carrier.
 多孔質担体としては、特に限定されず、担体として一般に公知の担体を広く使用することができる。例えば、活性炭、活性白土、ゼオライト、シリカ、アルミナ(活性アルミナを含む)、セラミック、粘土鉱物、炭酸カルシウム等が挙げられる。好ましい多孔質担体は、活性炭である。多孔質担体として活性炭が好ましい理由は、活性炭は、ゼオライト、アルミナ等の無機系多孔質担体の細孔構造とは違って雑然とした細孔構造を有しているので、気体成分を非選択的に(一様に)吸着するためと推測される。また、活性炭は、自由に動く陽イオンを有していないため、添着成分であるイミダゾール及び/又はその誘導体との陽イオン交換(塩基交換)が発生する虞もない。なお、多孔質担体は、1種又は2種以上を組み合わせて使用することができる。 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.
 活性炭原料としては、通常活性炭原料として用いられる炭素源であれば特に限定されるものではなく、例えば、木材、木粉、ヤシ殻、パルプ製造時の副産物、バガス、廃糖蜜、泥炭、亜炭、褐炭、瀝青炭、無煙炭、石油蒸留残渣成分、石油ピッチ、コークス、コールタール等の植物系原料又は化石系原料;フェノール樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、メラミン樹脂、尿素樹脂、レゾルシノール樹脂、セルロイド、エポキシ樹脂、ポリウレタン樹脂、ポリエステル樹脂、アクリル樹脂、ポリアミド樹脂等の各種合成樹脂;ポリブチレン、ポリブタジエン、ポリクロロプレン等の合成ゴム;その他合成木材;合成パルプ等が挙げられる。これらの活性炭原料のなかでは、臭気物質(特にアルデヒド系臭気物質)を気相吸着しやすいという観点から、植物系原料が好適に使用され、ヤシ殻がより好適に使用される。 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.
 活性炭原料の炭化又は賦活化方法としては、例えば、固定床方式、移動床方式、流動床方式、ロータリーキルン方式等のこれまでに知られている活性炭の製造方式が挙げられる。 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.
 活性炭原料の炭化方法としては、窒素ガス、二酸化炭素、ヘリウム、アルゴン、キセノン、ネオン、一酸化炭素、燃焼排ガス等の不活性ガス及びこれらの不活性ガスを主成分とした他のガスとの混合ガスを使用して焼成する方法が挙げられる。炭化の温度条件としては、通常500~900℃が好ましく、600~800℃がより好ましい。 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.
 活性炭原料の賦活化(又は賦活)方法としては、水蒸気、二酸化炭素、一酸化炭素、酸素、塩化水素、アンモニア、燃焼ガス等を用いるガス賦活法;塩化カルシウム、硫化カルシウム、リン酸、硫酸、塩化亜鉛等の存在下に、活性炭原料を賦活する薬品賦活法等が挙げられる。好ましくは水蒸気賦活である。賦活の温度条件としては、通常750~1200℃、好ましくは800~1100℃である。 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.
 活性炭原料を賦活した後は、必要に応じて、炭素中の無機質(灰分)を希塩酸、アルカリ水溶液等で洗浄脱灰し、さらに水洗を繰り返して精製後、乾燥、篩い分けしてもよい。 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.
 活性炭(「イミダゾール及び/又はその誘導体を添着させる前の活性炭」又は「元炭」ともいう)は、市販品を使用することもできる。市販品としては、例えば、粒状白鷺WH2c20/48(日本エンバイロケミカルズ株式会社製)、石炭造粒炭6/8mesh(BET比表面積1200 m2/g)等が挙げられる。 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.
 本発明の吸着剤は、再生処理されると添着成分であるイミダゾール及び/又はその誘導体が脱離し、前記多孔質担体となる。前記再生処理(単に「再生」ともいう)して得られる多孔質担体は、再び本発明の吸着剤における多孔質担体として使用(再利用)することができる(ここで、再生処理された多孔質担体を「再生多孔質担体」ともいう)。前記再生処理としては、例えば、熱処理(加熱処理)が挙げられる。 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).
 熱処理の際の温度は、850~950℃が好ましい。当該温度範囲内で本発明の吸着剤を熱処理することにより、多孔質担体を劣化させることなく、且つ、吸着剤に含まれる吸着物質(例えば有機化合物等)を短時間で除去する(脱離させる、又は飛ばす、ともいう)ことができる。その結果、好適に、再生多孔質担体が得られる。 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.
 熱処理の際の時間は、特に限定されず、吸着剤(又は多孔質担体)の量により適宜設定することができる。前記熱処理の時間は、30分以上が好ましく、30~60分がより好ましい。熱処理の際の圧力は、特に限定されない。 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.
 熱処理の際の雰囲気は、不活性ガス雰囲気が好ましい。熱処理の際の雰囲気が不活性ガスであることにより、(i)多孔質担体表面に存在する表面酸化物、表面官能基等、(ii)(前述の活性炭原料を賦活した後に希塩酸、アルカリ水溶液等で洗浄脱灰した場合において)前記希塩酸、アルカリ水溶液等を好適かつ安定的に除去することができる。よって、添着されたイミダゾール及び/又はその誘導体のうち、臭気物質(特にアルデヒド系臭気物質)の吸着に寄与するイミダゾール及び/又はその誘導体の量を多くすることができるため、結果として前記臭気物質の吸着性能に特に優れる。不活性ガスとしては、窒素ガス、ヘリウム、アルゴン、キセノン、ネオン、一酸化炭素、燃焼排ガス等が挙げられる。 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.
 熱処理する際の装置は、特に限定されないが、ロータリーキルン(円筒状の回転炉)を用いた加熱処理が好ましい。 The apparatus for the heat treatment is not particularly limited, but heat treatment using a rotary kiln (cylindrical rotary furnace) is preferable.
 また、多孔質担体として活性炭を使用する場合、イミダゾール及び/又はその誘導体を添着させる前に、活性炭に対して前述の熱処理を行ってもよい。当該熱処理の各条件(温度、時間、雰囲気、装置等)は、それぞれ、前述した再生処理における熱処理の各条件と同様である。なお、活性炭に対して前述の熱処理を行う場合、前記熱処理は活性炭(又は活性炭表面)の改質ともいう。前記熱処理は、(i)活性炭表面に存在する表面酸化物、表面官能基等、(ii)(前述の活性炭原料を賦活した後に希塩酸、アルカリ水溶液等で洗浄脱灰した場合において)前記希塩酸、アルカリ水溶液等を好適に除去するので、前記臭気物質の吸着性能を向上させることができる。 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.
 多孔質担体の形状は、特に限定されない。例えば、粉末状、破砕状、繊維状であってもよく、あるいは円柱状(ペレット状)、球状、ハニカム状等に造粒成型されたものであってもよい。 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.
 多孔質担体の平均粒子径、液体窒素温度条件下の窒素吸着によるBET比表面積、細孔容積、平均細孔直径については、それぞれ、特に限定されないが、BET比表面積は1000m2/g以上が好ましく、細孔容積は0.4mL/g以上が好ましく、平均細孔直径は1.7nm以上が好ましい。 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.
 イミダゾール及び/又はその誘導体
 本発明の吸着剤は、イミダゾール及び/又はその誘導体が多孔質担体に添着している。
Imidazole and / or its derivative In the adsorbent of the present invention, imidazole and / or its derivative are attached to a porous carrier.
 イミダゾールの誘導体としては、例えば、イミダゾールの水溶性誘導体が挙げられる。イミダゾールの水溶性誘導体としては、1-メチルイミダゾール、2-メチルイミダゾール等が挙げられる。 Examples of imidazole derivatives include water-soluble derivatives of imidazole. Examples of water-soluble derivatives of imidazole include 1-methylimidazole and 2-methylimidazole.
 イミダゾール及び/又はその誘導体の添着量は、多孔質担体100質量部(乾燥品基準)に対して1~40質量部であることが好ましく、10~30質量部であることがより好ましい。イミダゾール及び/又はその誘導体の添着量が上記範囲内であることによって、イミダゾール及び/又はその誘導体が多孔質担体の孔を埋めにくく、上記臭気物質が吸着剤中の反応サイトに到達しやすいために、より効率的に臭気物質(特にアルデヒド系臭気物質)を吸着することができる。 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.
 イミダゾール及び/又はその誘導体は、市販品を使用することができる。なお、イミダゾール及び/又はその誘導体は、1種又は2種以上を組み合わせて使用することができる。 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.
 本発明の吸着剤は、薬品(化学物質)として、イミダゾール及び/又はその誘導体のみが添着されている。言い換えれば、本発明の吸着剤は、多孔質担体とイミダゾール及び/又はその誘導体との間に介在する成分は存在せず、多孔質担体とイミダゾール及び/又はその誘導体が直接接するように添着(担持)されている。添着成分として、イミダゾール及び/又はその誘導体に加えて、さらに、(i)ハロゲン化アルカリ金属塩(ヨウ化カリウム等)、(ii)ハロゲン化アルカリ土類金属塩、(iii)酸(リン酸等)等を使用すると、前記各成分が多孔質担体から脱離しにくく残留蓄積してしまう。その結果、吸着剤に対して再生処理を行って得られる再生多孔質担体を使用する吸着剤は、優れた吸着性能が得られない。そのため、本発明では、薬品として、イミダゾール及び/又はその誘導体以外の成分を使用しない。 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.吸着剤の製造方法≫
 本発明の吸着剤の製造方法(添着方法ともいう)は、イミダゾール及び/又はその誘導体が多孔質担体に添着している吸着剤の製造方法であって、
前記イミダゾール及び/又はその誘導体を含む液を前記多孔質担体に接触させる工程を含む方法が好ましい。当該方法によれば、
(1)臭気物質(特にアルデヒド系臭気物質)に対する吸着性能に優れており、
(2)長期間経過した後における臭気物質(特にアルデヒド系臭気物質)に対する吸着性能に優れており、
(3)吸着剤に対して再生処理を行い、当該処理により得られた多孔質担体を再び使用したとしても、臭気物質(特にアルデヒド系臭気物質)に対する吸着性能の低下が抑制されており、
(4)耐熱性に優れている、
という効果が奏される吸着剤を好適に得ることができる。
≪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.
 多孔質担体に、イミダゾール及び/又はその誘導体を含む液(好ましくは、イミダゾール及び/又はその誘導体が溶媒に溶解している溶液)を接触させる方法としては、
(a) 前記イミダゾール及び/又はその誘導体を含む液を多孔質担体に噴霧及び/又は散布する方法、
(b) 前記イミダゾール及び/又はその誘導体を含む液中に、多孔質担体を浸漬する方法、
(c) 粉末状の多孔質担体と、前記イミダゾール及び/又はその誘導体を含む液を混合し、必要に応じてバインダーを添加して造粒、又は成型する方法
等が挙げられる。なかでも、(a)又は(b)の方法は、多孔質担体全体に偏りなくイミダゾール及び/又はその誘導体を添着させることができるので、好ましい方法である。また、使用するイミダゾール及び/又はその誘導体を含む液の温度は15~30℃が好ましく、添着時間は1時間以内が好ましい。
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.
 前記(a)~(c)の方法において、イミダゾール及び/又はその誘導体を含む液を構成する溶媒(以下、単に「溶媒」ともいう)は、イミダゾール及び/又はその誘導体を溶解する溶媒が好ましい。イミダゾール及び/又はその誘導体を溶解する溶媒としては、例えば水等が挙げられる。 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.
 イミダゾール及び/又はその誘導体の使用量は、イミダゾール及び/又はその誘導体の添着量が多孔質担体100質量部(乾燥品基準)に対して1~40質量部となるように設定することが好ましい(より好ましくは10~30質量部である)。例えば、上述の(a)の方法でイミダゾール及び/又はその誘導体が添着された多孔質担体を製造する場合、1~40質量部のイミダゾール及び/又はその誘導体を含む液を、100質量部の乾燥多孔質担体に噴霧及び/又は散布することにより、イミダゾール及び/又はその誘導体の添着量が多孔質担体100質量部(乾燥品基準)に対して1~40質量部である吸着剤が得られる。 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.
 なお、上述の通り、多孔質担体が活性炭である場合、前記イミダゾール及び/又はその誘導体を添着させる前に、前記活性炭を改質してもよい。前記改質における熱処理の各条件(温度、時間、雰囲気、装置等)については、上述の通りである。 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.吸着剤を使用した臭気物質の吸着方法≫
 本発明の吸着方法は、臭気物質(特にアルデヒド系臭気物質)を含有する気体を、イミダゾール及び/又はその誘導体が多孔質担体に添着している吸着剤と接触させることを特徴とする。上記吸着方法によれば、上記吸着剤が臭気物質(特にアルデヒド系臭気物質)を効率よく吸着するので、上記臭気物質を効率的に除去することができる。
≪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.
 本発明の吸着剤を用いた上記臭気物質(悪臭物質)を吸着するメカニズムは、上記吸着剤中のイミダゾール及び/又はその誘導体が有するアミノ基と前記臭気物質とが化学反応し、当該生成物を吸着剤が吸着するものと考えられている。 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.
 臭気物質
 本発明の吸着剤は、臭気物質(特にアルデヒド系臭気物質)を効率良く吸着することができる。なお、本発明の吸着剤は、1種又は2種以上を組み合わせた上記臭気物質に対しても有効である。
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.
 アルデヒド系臭気物質(アルデヒド類)としては、特に、低級アルデヒド系臭気物質(低級アルデヒド類)が挙げられる。具体的には、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、アクロレイン、n-ブチルアルデヒド、イソブチルアルデヒド、3-メチル-ブチルアルデヒド、クロトンアルデヒド等を挙げることができる。なかでも、本発明の吸着剤は、ホルムアルデヒド及び/又はアセトアルデヒドの吸着に特に有効である。 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.
 工業製品への適用
 本発明の吸着剤は、工業製品に配合して使用することができる。当該工業製品は、本発明を包含する。
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.
 工業製品とは、従来より広く知られている工業製品及び工業原料を指す。具体的には、塗料、接着剤、インキ、シーリング剤、紙製品、バインダー、樹脂エマルション、パルプ、木質材料、木質製品、プラスチック製品、フィルム、壁紙、建材(石膏ボード、内装材、天井材、床材等)、繊維製品、フィルター(特に消臭フィルター等)等が挙げられる。また、これらの複合材料も工業製品に含まれる。複合材料としては、例えば、木材とプラスチックとの複合材料等が挙げられる。本発明の吸着方法では、本発明の吸着剤が配合された上述の工業製品を、臭気物質(特にアルデヒド系臭気物質)を含有する気体と接触させることによって、吸着剤と上記臭気物質とが接触し、その結果上記臭気物質を効率よく吸着除去することができる。 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.
 工業製品としてフィルター(特に消臭フィルター)を採用する場合、その形状は特に制限されないが、例えば、細かく分割された収納箱(例えば、ポリエチレン、ポリプロピレン等の樹脂製のハニカムコアの空隙)に本発明の吸着剤を充填し、その両側面を通気性に優れた破れにくい樹脂(ポリエチレンテレフタレート等)製のネットで覆ったフィルター(特に消臭フィルター等)を採用することができる。 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.
 細かく分割された収納箱中に本発明の吸着剤を充填する方法としては、特に制限されず、常法にしたがって行うことができる。 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.
 また、固定床、移動床、流動床等の吸着装置に充填し、これに臭気物質(特にアルデヒド系臭気物質)を含有する気体を通気処理することによっても、上記臭気物質を効率良く吸着除去することができる。 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.
 以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例の態様に限定されない。 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.
 実施例1
 イミダゾール(和光純薬工業株式会社製)10質量部を水20質量部に溶解して、添着溶液(液温20℃)を調製した。次に、粒径が0.850~0.300mm(20/48mesh)のヤシ殻活性炭(粒状白鷺WH2c20/48、日本エンバイロケミカルズ株式会社製、多孔質担体)100質量部が入った小型糖衣機を回転させながら、上記添着溶液を上記ヤシ殻活性炭に対して均一に噴霧することにより(添着時間:20分)、イミダゾールがヤシ殻活性炭に添着している吸着剤を得た。
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).
 <実施例1における添着成分及び添着量>
 ・イミダゾール添着量:多孔質担体100質量部に対して10質量部。
<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.
 実施例2
 イミダゾール20質量部を水20質量部に溶解して添着溶液(液温20℃)を調製する以外は実施例1と同様にして、イミダゾールがヤシ殻活性炭に添着している吸着剤を得た。
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.).
 <実施例2における添着成分及び添着量>
 ・イミダゾール添着量:多孔質担体100質量部に対して20質量部。
<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.
 実施例3
 石炭造粒炭6/8mesh(BET比表面積1200 m2/g)100質量部に対して、イミダゾール10質量部を水20質量部に溶解させ噴霧して添着した吸着剤7gを60×60×10mmのポリエチレン製ハニカムコアの空隙に常法で充填し、その両側面をポリエチレンテレフタレート(PET)製のネットで覆って、消臭フィルターを得た。
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.
 比較例1
 粒径が0.850~0.300mm(20/48mesh)のヤシ殻活性炭(粒状白鷺WH2c20/48、日本エンバイロケミカルズ株式会社製)を吸着剤とした。即ち、比較例1の吸着剤は、何も添着されていない無添着の活性炭である。
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.
 比較例2
 モルホリン(和光純薬工業株式会社製)10質量部、ヨウ化カリウム(和光純薬工業株式会社製)2質量部、及びリン酸(和光純薬工業株式会社製)4質量部を水30質量部に溶解して添着溶液(液温20℃)を調製する以外は実施例1と同様にして、モルホリン、ヨウ化カリウム及びリン酸の三成分がヤシ殻活性炭に添着している吸着剤を得た。
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. .
 <比較例2における添着成分及び添着量>
 ・モルホリン添着量  :多孔質担体100質量部に対して10質量部、
 ・ヨウ化カリウム添着量:多孔質担体100質量部に対して2質量部、
 ・リン酸添着量    :多孔質担体100質量部に対して4質量部。
<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.
 比較例3
 イミダゾール(和光純薬工業株式会社製)10質量部、ヨウ化カリウム(和光純薬工業株式会社製)2質量部、及びリン酸(和光純薬工業株式会社製)6質量部を水30質量部に溶解して添着溶液(液温20℃)を調製する以外は実施例1と同様にして、イミダゾール、ヨウ化カリウム及びリン酸の三成分がヤシ殻活性炭に添着している吸着剤を得た。
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. .
 <比較例3における添着成分及び添着量>
 ・イミダゾール添着量 :多孔質担体100質量部に対して10質量部、
・ヨウ化カリウム添着量:多孔質担体100質量部に対して2質量部、
・リン酸添着量    :多孔質担体100質量部に対して6質量部。
<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.
 比較例4
 モルホリン(和光純薬工業株式会社製)10質量部を水20質量部に溶解して添着溶液(液温20℃)を調製する以外は実施例1と同様にして、モルホリンがヤシ殻活性炭に添着している吸着剤を得た。
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.
 <比較例4における添着成分及び添着量>
・モルホリン添着量:多孔質担体100質量部に対して10質量部。
<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.
 比較例5
 石炭造粒炭6/8mesh(BET比表面積1200 m2/g)100質量部に対して、モルホリン10質量部を水20質量部に溶解させ噴霧して添着した吸着剤7gを60×60×10mmのポリエチレン製ハニカムコアの空隙に常法で充填し、その両側面をポリエチレンテレフタレート(PET)製のネットで覆って、消臭フィルターを得た。
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.
 試験例1:吸着剤のアルデヒド系臭気物質に対する吸着性能評価(吸着性能評価)
 内径20mmのガラスカラムに、得られた上記各吸着剤(実施例1、比較例1、比較例2)3.2mlを充填し、25℃、ホルムアルデヒド10ppm、湿度60%に調製した臭気ガス(ホルムアルデヒド含有ガス)を2L/minの流量で通気した。なお、LV(線速度)は0.11m/secとし、SV(空間速度)は37000/hrとした。一定時間経過毎にガラスカラムの入口と出口のホルムアルデヒド濃度(ppm)をガスクロマトグラフィーによって分析し、破過率(%)を算出した。また、上記測定されたホルムアルデヒド濃度を基に、破過率が5%時及び80%時における質量当たりの吸着量(mg/g)を算出した。なお、ガスクロマトグラフィーにおけるホルムアルデヒド濃度測定は、メタナイザー付きGC-FID(GC-14B、(株)島津製作所製)及び分離カラム(直径3mm×長さ600mm, Porapak TYPE T 50/80)を使用した。また、上記破過率は、次式: 
破過率(%)=C/C0×100
 C0 :入口ホルムアルデヒド濃度(ppm)
 C :出口ホルムアルデヒド濃度(ppm)
により算出した。試験結果を図1及び表1に示す。
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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 <考察>
 図1及び表1から明らかなように、イミダゾール(のみ)が添着している実施例1の吸着剤は、破過率が5%時及び80%時におけるホルムアルデヒド吸着量に関して、無添着である比較例1の吸着剤、並びにモルホリン、ヨウ化カリウム及びリン酸が添着している比較例2の吸着剤と比較して、それぞれ大きい値を示す。即ち、上記実施例1の吸着剤は、無添着である比較例1の吸着剤、並びにモルホリン、ヨウ化カリウム及びリン酸が添着している比較例2の吸着剤と比較して、優れたアルデヒド系臭気物質吸着性能を示す。
<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.
 試験例2:再生処理後に得られた吸着剤における、アルデヒド系臭気物質に対する吸着性能評価(再生性能評価)
 まず、実施例1及び比較例3の吸着剤を用意した。次に、前記実施例1及び比較例3の各吸着剤を、窒素ガス雰囲気下でロータリーキルンにて900℃で30分間の熱処理を行った後、次いで自然冷却した。この操作により、前記実施例1及び比較例3の各吸着剤は、それぞれ、再生処理されたヤシ殻活性炭となった。ここで、実施例1の吸着剤に対して前記熱処理及び自然冷却を行って得られたヤシ殻活性炭を、後述の新炭と区別するために、実施例1Aの再生ヤシ殻活性炭(又は再生炭)とも称する。また、比較例3の吸着剤に対して前記熱処理及び自然冷却を行って得られたヤシ殻活性炭を、後述の新炭と区別するために、比較例3Aの再生ヤシ殻活性炭(又は再生炭)とも称する。
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.
 次に、ヤシ殻活性炭(粒状白鷺WH2c20/48、日本エンバイロケミカルズ株式会社製、新炭ヤシ殻活性炭)に代えて、前記実施例1Aの再生ヤシ殻活性炭を使用する以外は実施例1と同様にして、イミダゾールが前記実施例1Aの再生ヤシ殻活性炭に添着している吸着剤を得た(以下、この吸着剤を、実施例1Aの吸着剤と称する)。また、ヤシ殻活性炭(粒状白鷺WH2c20/48、日本エンバイロケミカルズ株式会社製、新炭ヤシ殻活性炭)に代えて、前記比較例3Aの再生ヤシ殻活性炭を使用する以外は比較例3と同様にして、イミダゾール、ヨウ化カリウム及びリン酸の三成分が前記比較例3Aの再生ヤシ殻活性炭に添着している吸着剤を得た(以下、この吸着剤を、比較例3Aの吸着剤と称する)。 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).
 次に、実施例1、比較例1、及び比較例2の各吸着剤に代えて、前記実施例1、実施例1A、比較例3、及び比較例3Aの各吸着剤を使用する以外は、試験例1と同様にして、時間経過毎の破過率(%)、並びに破過率が5%時及び80%時における質量当たりの吸着量(mg/g)を測定又は算出した。試験結果を図2及び表2に示す。 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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 <考察>
 図2及び表2からも明らかなように、イミダゾール(のみ)が添着している実施例1Aの吸着剤(多孔質担体を再生した後の吸着剤)は、イミダゾール(のみ)が添着している実施例1と比較して、ホルムアルデヒドの吸着性能の低下が抑制されている(吸着性能はほぼ同等である)。これに対して、イミダゾール、ヨウ化カリウム及びリン酸が添着している比較例3Aの吸着剤(多孔質担体を再生した後の吸着剤)は、イミダゾール、ヨウ化カリウム及びリン酸が添着している比較例3と比較して、ホルムアルデヒドの吸着性能の大きな低下が見られる。この吸着性能の大きな低下は、吸着剤を再生処理した後に残存するカリウム金属成分の影響によるものと考えられる。このように、実施例1の吸着剤は、再生性能に優れている。
<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.
 試験例3:6ヶ月経過後の吸着剤における、アルデヒド系臭気物質に対する吸着性能評価(耐久性評価)
 まず、実施例1及び比較例4の吸着剤を用意した(これらの吸着剤を初期品ともいう)。次に、前記実施例1及び比較例4の各吸着剤(初期品)を、ポリ袋に入れて6ヶ月間常温保管した(前記常温保管した後の吸着剤を6ヶ月経過品ともいい、前記初期品と区別するために、実施例1B及び比較例4Bの吸着剤とも称する)。
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).
 次に、実施例1、比較例1、及び比較例2の各吸着剤に代えて、前記実施例1、実施例1B、比較例4、及び比較例4Bの各吸着剤を使用する以外は、試験例1と同様にして、時間経過毎の破過率(%)、並びに破過率が5%時及び80%時における質量当たりの吸着量(mg/g)を測定又は算出した。試験結果を図3及び表3に示す。 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.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 <考察>
 図3及び表3からも明らかなように、イミダゾール(のみ)が添着している実施例1Bの吸着剤(6ヶ月経過品)は、イミダゾール(のみ)が添着している実施例1(初期品)と比較して、ホルムアルデヒドの吸着性能の低下が抑制されている(吸着性能はほぼ同等である)。これに対して、モルホリン(のみ)が添着している比較例4Bの吸着剤(6ヶ月経過品)は、モルホリン(のみ)が添着している比較例4(初期品)と比較して、ホルムアルデヒドの吸着性能の大きな低下が見られる。このように、実施例1の吸着剤は、長期間経過後もアルデヒド系臭気物質の吸着性能に優れており、耐久性に優れている。
<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.
 試験例4:加熱後の吸着剤における、アルデヒド系臭気物質に対する吸着性能評価(耐熱性評価)
 まず、実施例2及び比較例2の吸着剤を用意した(これらの吸着剤を初期品ともいう)。次に、前記実施例2及び比較例2の各吸着剤を、電気乾燥炉にて150℃で3時間の加熱処理を行った後、次いで自然冷却した(前記加熱処理及び自然冷却した後の吸着剤を加熱処理済品ともいい、前記初期品と区別するために、実施例2C及び比較例2Cの吸着剤とも称する)。
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).
 次に、実施例1、比較例1、及び比較例2の各吸着剤に代えて、前記実施例2、実施例2C、比較例2、及び比較例2Cの各吸着剤を使用する以外は、試験例1と同様にして、時間経過毎の破過率(%)、並びに破過率が5%時及び80%時における質量当たりの吸着量(mg/g)を測定又は算出した。試験結果を図4及び表4に示す。 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.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 <考察>
 図4及び表4からも明らかなように、イミダゾール(のみ)が添着している実施例2Cの吸着剤(加熱処理済品)は、イミダゾール(のみ)が添着している実施例2(初期品)と比較して、ホルムアルデヒドの吸着性能の低下が抑制されている(吸着性能の低下は20%程度である)。これに対して、モルホリン(のみ)が添着している比較例2Cの吸着剤(加熱処理済品)は、モルホリン(のみ)が添着している比較例2(初期品)と比較して、ホルムアルデヒドの吸着性能が完全に消失している。このように、実施例2の吸着剤は、150℃で加熱した後においてもアルデヒド系臭気物質の吸着性能に優れており、耐熱性に優れている。
<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.
 試験例5:消臭フィルターの性能評価試験
 2ppmのホルムアルデヒドを充満させた1m3ボックス中で、実施例3及び比較例5の各消臭フィルターを搭載した空気清浄機をLV1.0m/secで 60分間運転し、各時間におけるホルムアルデヒド濃度と初期濃度からホルムアルデヒド除去率を算出した。これとは別に、実施例3及びと比較例5の各消臭フィルターを所定の包材(ポリエチレン袋)に梱包し、常温保管したものをそれぞれ4か月と8か月経過時に開封し、上記と同条件にて試験し、経時劣化を確認した。なお、前記常温保管した後の吸着剤を4ヶ月経過品及び8ヶ月経過品ともいい、前記初期品と区別するために、実施例3の4ヶ月経過品を実施例3Dの消臭フィルター、実施例3の8ヶ月経過品を実施例3Eの消臭フィルター、比較例5の4ヶ月経過品を比較例5Dの消臭フィルター、比較例5の8ヶ月経過品を比較例5Eの消臭フィルターとも称する。試験結果を図5及び表5に示す。
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.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
 <考察>
 図5及び表5からも明らかなように、イミダゾール(のみ)が添着している実施例3D及び3Eの消臭フィルター(4ヶ月経過品及び8ヶ月経過品)は、イミダゾール(のみ)が添着している実施例3(新炭)と比較して、60分経過時点におけるホルムアルデヒド除去性能は70%以上という高い数値を示すが、モルホリン(のみ)が添着している比較例5D及び5Eの消臭フィルター(4ヶ月経過品及び8ヶ月経過品)は、モルホリン(のみ)が添着している比較例5(新炭)と比較して、60分経過時点におけるホルムアルデヒド除去性能は30%程度まで低下する。即ち、実施例3は比較例5と比較して空気清浄機用の濾材でも実用レベルで十分な耐久性を有し、経年劣化しにくいことを示す。
 
<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 (11)

  1. イミダゾール及び/又はその誘導体が多孔質担体に添着している、吸着剤。 An adsorbent in which imidazole and / or a derivative thereof are attached to a porous carrier.
  2. 前記イミダゾール及び/又はその誘導体の添着量が、前記多孔質担体の乾燥質量100質量部に対して、1~40質量部である、請求項1に記載の吸着剤。 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.
  3. 前記多孔質担体が、活性炭である、請求項1又は2に記載の吸着剤。 The adsorbent according to claim 1 or 2, wherein the porous carrier is activated carbon.
  4. 臭気物質の吸着剤である、請求項1~3のいずれかに記載の吸着剤。 The adsorbent according to any one of claims 1 to 3, which is an adsorbent for an odor substance.
  5. 前記臭気物質がアルデヒド系臭気物質である、請求項4に記載の吸着剤。 The adsorbent according to claim 4, wherein the odor substance is an aldehyde odor substance.
  6. 請求項1~5のいずれかに記載の吸着剤を用いた工業製品。 An industrial product using the adsorbent according to any one of claims 1 to 5.
  7. フィルターである、請求項6に記載の工業製品。 The industrial product according to claim 6, which is a filter.
  8. 消臭フィルターである、請求項6又は7に記載の工業製品。 The industrial product according to claim 6 or 7, which is a deodorizing filter.
  9. イミダゾール及び/又はその誘導体が多孔質担体に添着している吸着剤の製造方法であって、
    前記イミダゾール及び/又はその誘導体を含む液を前記多孔質担体に接触させる工程を含む、吸着剤の製造方法。
    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.
  10. 臭気物質を含有する気体を、イミダゾール及び/又はその誘導体が多孔質担体に添着している吸着剤と接触させる、臭気物質の吸着方法。 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.
  11. 前記臭気物質がアルデヒド系臭気物質である、請求項10に記載の吸着方法。 The adsorption method according to claim 10, wherein the odor substance is an aldehyde odor substance.
PCT/JP2015/071404 2014-08-27 2015-07-28 Adsorbent WO2016031474A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-172863 2014-08-27
JP2014172863 2014-08-27

Publications (1)

Publication Number Publication Date
WO2016031474A1 true WO2016031474A1 (en) 2016-03-03

Family

ID=55399375

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/071404 WO2016031474A1 (en) 2014-08-27 2015-07-28 Adsorbent

Country Status (2)

Country Link
TW (1) TW201609249A (en)
WO (1) WO2016031474A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6607422B1 (en) * 2019-02-06 2019-11-20 孝章 下原 Formaldehyde scavenger
WO2020162091A1 (en) * 2019-02-06 2020-08-13 孝章 下原 Formaldehyde scavenger

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0380934A (en) * 1989-08-25 1991-04-05 Takeda Chem Ind Ltd Adsorbent of lower aldehydes
JPH04200742A (en) * 1990-11-30 1992-07-21 Kuraray Chem Corp Carbon dioxide adsorbent
JPH06254390A (en) * 1992-03-13 1994-09-13 Hidefumi Hirai Novel composite and its production and oxygen adsorbent consisting of this composite
JP2000356022A (en) * 1999-06-17 2000-12-26 Daiken Trade & Ind Co Ltd Formaldehyde adsorbing interior trim material
JP2001096149A (en) * 1999-10-01 2001-04-10 Kuraray Chem Corp Porous adsorbent and filter
JP2001104778A (en) * 1999-10-13 2001-04-17 Tosoh Corp Acidic gas adsorbent
JP2011206671A (en) * 2010-03-30 2011-10-20 Yamagata Promotional Organization For Industrial Technology Carbon dioxide adsorbent composed of cyclic guanidine compound, and method for producing cyclic guanidine compound
CN102513063A (en) * 2011-12-16 2012-06-27 福建农林大学 Active carbon immobilized imidazole ionic liquid, preparation method thereof and application thereof
CN102631903A (en) * 2012-05-08 2012-08-15 福建农林大学 In-situ preparation method of activated carbon loaded with ionic liquid

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0380934A (en) * 1989-08-25 1991-04-05 Takeda Chem Ind Ltd Adsorbent of lower aldehydes
JPH04200742A (en) * 1990-11-30 1992-07-21 Kuraray Chem Corp Carbon dioxide adsorbent
JPH06254390A (en) * 1992-03-13 1994-09-13 Hidefumi Hirai Novel composite and its production and oxygen adsorbent consisting of this composite
JP2000356022A (en) * 1999-06-17 2000-12-26 Daiken Trade & Ind Co Ltd Formaldehyde adsorbing interior trim material
JP2001096149A (en) * 1999-10-01 2001-04-10 Kuraray Chem Corp Porous adsorbent and filter
JP2001104778A (en) * 1999-10-13 2001-04-17 Tosoh Corp Acidic gas adsorbent
JP2011206671A (en) * 2010-03-30 2011-10-20 Yamagata Promotional Organization For Industrial Technology Carbon dioxide adsorbent composed of cyclic guanidine compound, and method for producing cyclic guanidine compound
CN102513063A (en) * 2011-12-16 2012-06-27 福建农林大学 Active carbon immobilized imidazole ionic liquid, preparation method thereof and application thereof
CN102631903A (en) * 2012-05-08 2012-08-15 福建农林大学 In-situ preparation method of activated carbon loaded with ionic liquid

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6607422B1 (en) * 2019-02-06 2019-11-20 孝章 下原 Formaldehyde scavenger
WO2020162091A1 (en) * 2019-02-06 2020-08-13 孝章 下原 Formaldehyde scavenger

Also Published As

Publication number Publication date
TW201609249A (en) 2016-03-16

Similar Documents

Publication Publication Date Title
Wang et al. Development of carbon-based “molecular basket” sorbent for CO2 capture
Adelodun et al. Isotherm, thermodynamic and kinetic studies of selective CO2 adsorption on chemically modified carbon surfaces
EP1749571B1 (en) Co-formed base-treated aluminas for water and co2 removal
Huang et al. Removal of typical industrial gaseous pollutants: From carbon, zeolite, and metal-organic frameworks to molecularly imprinted adsorbents
US20070000385A1 (en) Adsorbents for removing H2S, other odor causing compounds, and acid gases from gas streams and methods for producing and using these adsorbents
KR101823622B1 (en) Carbon dioxide absorbent with improved moisture stability and manufacturing method thereof
CN104841369A (en) Air filter element for cellular network active carbon filter and preparation method thereof
JP6851834B2 (en) Aldehyde adsorbent
FI111245B (en) A process for separating ammonia from a gas mixture and using an adsorbent composition for this separation
WO2016031474A1 (en) Adsorbent
JP2001000524A (en) Adsorbent of lower aldehydes
JP2009056449A (en) Lower aldehyde adsorbent
JP5420434B2 (en) Composite gas adsorbent, composite gas adsorbent composition, and adsorption filter using the same
JP2006272078A (en) Absorbent for aldehydes, its manufacturing method and method for removing aldehyde in gas using adsorbent
JP2007038106A (en) Deodorization method
JP2000084406A (en) Adsorbent for lower aldehydes
BR112021007686A2 (en) catalyst adsorbent filters, catalyst adsorbent composition and method of forming a catalyst adsorbent filter
JPH01236941A (en) Gaseous ammonia adsorbent
WO2015072263A1 (en) Adsorbent
JP2007014857A (en) Adsorbent and its production method
JP2950683B2 (en) Air purifier and air purifier
Labaki Palm wastes reuse for gaseous effluent treatment
KR20170031838A (en) Preparation method of filter for removing odor and volatile organic compounds
JPH0252043A (en) Air purifying agent
KR20160104284A (en) Ethylene gas absorbent with improved efficiency for removing ethylene gas and process for producing thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15835258

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 15835258

Country of ref document: EP

Kind code of ref document: A1