WO2016031474A1 - Adsorbant - Google Patents

Adsorbant Download PDF

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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
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Prior art keywords
adsorbent
imidazole
porous carrier
derivative
mass
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PCT/JP2015/071404
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English (en)
Japanese (ja)
Inventor
将吾 秋田
田中　敦
泰徳 國本
荒谷　渉
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大阪ガスケミカル株式会社
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Publication of WO2016031474A1 publication Critical patent/WO2016031474A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes 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.

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  • General Chemical & Material Sciences (AREA)
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Abstract

　L'objectif de la présente invention est de fournir : un nouvel adsorbant dans lequel la performance d'adsorption vis-à-vis des substances malodorantes à base d'aldéhyde et la performance d'adsorption mentionnée ci-dessus après une longue période sont excellentes, toute diminution de la performance d'adsorption due à la régénération est réduite au minimum, et une excellente résistance à la chaleur est présentée ; un filtre dans lequel l'adsorbant est utilisé ; un procédé de fabrication de l'adsorbant ; et un procédé d'adsorption de substances malodorantes dans lequel l'adsorbant est utilisé. L'objectif ci-dessus est réalisé au moyen d'un adsorbant dans lequel de l'imidazole et/ou un dérivé de celui-ci est fixé à un support poreux.
PCT/JP2015/071404 2014-08-27 2015-07-28 Adsorbant WO2016031474A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6607422B1 (ja) * 2019-02-06 2019-11-20 孝章 下原 ホルムアルデヒド捕捉材
WO2020162091A1 (fr) * 2019-02-06 2020-08-13 孝章 下原 Capteur de formaldéhyde

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JP2000356022A (ja) * 1999-06-17 2000-12-26 Daiken Trade & Ind Co Ltd ホルムアルデヒド吸着内装材
JP2001096149A (ja) * 1999-10-01 2001-04-10 Kuraray Chem Corp 多孔質吸着剤及びフィルター
JP2001104778A (ja) * 1999-10-13 2001-04-17 Tosoh Corp 酸性ガス吸着剤
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CN102513063A (zh) * 2011-12-16 2012-06-27 福建农林大学 活性炭固定化咪唑类离子液体及其制备方法和应用
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JPH0380934A (ja) * 1989-08-25 1991-04-05 Takeda Chem Ind Ltd 低級アルデヒド類の吸着剤
JPH04200742A (ja) * 1990-11-30 1992-07-21 Kuraray Chem Corp 炭酸ガス吸着剤
JPH06254390A (ja) * 1992-03-13 1994-09-13 Hidefumi Hirai 新規な複合体およびその製造方法、ならびに該複合体よりなる酸素吸着剤
JP2000356022A (ja) * 1999-06-17 2000-12-26 Daiken Trade & Ind Co Ltd ホルムアルデヒド吸着内装材
JP2001096149A (ja) * 1999-10-01 2001-04-10 Kuraray Chem Corp 多孔質吸着剤及びフィルター
JP2001104778A (ja) * 1999-10-13 2001-04-17 Tosoh Corp 酸性ガス吸着剤
JP2011206671A (ja) * 2010-03-30 2011-10-20 Yamagata Promotional Organization For Industrial Technology 環状グアニジン化合物からなる二酸化炭素吸着剤及び環状グアニジン化合物の製造方法
CN102513063A (zh) * 2011-12-16 2012-06-27 福建农林大学 活性炭固定化咪唑类离子液体及其制备方法和应用
CN102631903A (zh) * 2012-05-08 2012-08-15 福建农林大学 负载离子液体活性炭的原位制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6607422B1 (ja) * 2019-02-06 2019-11-20 孝章 下原 ホルムアルデヒド捕捉材
WO2020162091A1 (fr) * 2019-02-06 2020-08-13 孝章 下原 Capteur de formaldéhyde

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