Scavenger

Abstract

To provide a scavenger capable of efficiently scavenging sulfur-based gases and aldehydes.SOLUTION: A scavenger is brought into contact with an odorant, where the scavenger comprises a carrier having an aminooxyalkyl group supported through chemical bonding, the carrier being an inorganic carrier containing at least one metal selected from the group consisting of zinc, copper, iron, manganese, cobalt, and nickel.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to scavengers for sulfur-based gases, aldehydes, and the like.

Background Art

[0002] Various deodorants are commercially available to remove unpleasant odor substances and provide comfortable air quality. Examples of odor substances include sulfur-based gases such as hydrogen sulfide and aldehydes such as acetaldehyde, and these odors are known to give people a strong sense of discomfort. Zinc compounds are known to be used as scavengers for sulfur-based gases such as hydrogen sulfide and mercaptans. For example, Patent Document 1 discloses a deodorant containing zinc oxide as a main component. However, although zinc compounds have a capturing effect on sulfur-based gases, they have a problem in that the capturing effect on aldehydes is small.

[0003] On the other hand, activated carbon is known as a deodorant that can capture sulfur-based gases and aldehydes simultaneously. However, activated carbon may re-release the odor molecules once captured. In addition, since activated carbon itself is colored, there is also a problem that its applications are limited.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Conventional scavengers have problems in that they cannot capture sulfur-based gases and aldehydes together as a single entity, or even if they can capture them, re-release occurs.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that a specific scavenger described below solves the above problems and have completed the present invention.

[0007] That is, the present disclosure includes the following embodiments.

[0008] [1] A scavenger for odor substances in which an aminooxyalkyl group is supported on an inorganic carrier containing at least one metal selected from the group consisting of zinc, copper, iron, manganese, cobalt, and nickel by a chemical bond.

[0009] [2] The scavenger according to [1] above, wherein the carrier having an aminooxyalkyl group supported thereon by a chemical bond is a carrier having any of the structures represented by the following general formula (1).

[0010] [Chemical formula]

[0011] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer of 0 to 2. m' represents 0 or 1. n represents an integer of 1 to 12. When m is 2, a plurality of Rs may be the same or different. When m is 0, a plurality of Xs may be the same or different.

[0012] [3] The scavenger according to [2] above, wherein R is a methyl group and X is at least one selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

[0013] [4] The scavenger according to [2] or [3] above, wherein n is 3.

[0014] [5] The scavenger according to [1] above, wherein the carrier having an aminooxyalkyl group supported thereon by a chemical bond is a carrier obtained by reacting a compound represented by the following general formula (2) with an inorganic carrier having a hydroxyl group on its surface.

[0015] [Chemical formula]

[0016] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer of 0 to 2, and n represents an integer of 1 to 12. When m is 0 or 1, a plurality of Xs may be the same or different. When m is 2, a plurality of Rs may be the same or different.) [6] The scavenger according to [5] above, wherein R is a methyl group and X is at least one selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

[0017] [7] The scavenger according to [5] or [6] above, wherein n is 3.

[0018] [8] The scavenger according to any one of [1] to [7] above, wherein the inorganic carrier is zinc oxide or zinc hydroxide.

[0019] [9] A method for removing aldehydes by contacting the scavenger according to any one of [1] to [8] above with aldehydes.

[0020]

[10] A method for removing hydrogen sulfide or mercaptans by contacting the scavenger according to any one of [1] to [8] above with hydrogen sulfide or mercaptans.

[0021]

[11] A method for removing odorous substances by contacting the scavenger according to any one of [1] to [8] above with at least one odorous substance selected from the group consisting of aldehydes, hydrogen sulfide, and mercaptans. [Advantages of the Invention]

[0022] The scavenger according to one aspect of the present disclosure can effectively capture sulfur-based gases and aldehydes by itself and efficiently remove unpleasant odorous substances. [Modes for Carrying Out the Invention]

[0023] Hereinafter, the present invention will be described in detail. In this specification, "~" means a numerical range including the numerical values at both ends thereof.

[0024] The scavenger according to one aspect of the present disclosure is a scavenger for odor substances in which an aminooxyalkyl group is supported by a chemical bond on an inorganic carrier containing at least one metal selected from the group consisting of zinc, copper, iron, manganese, cobalt, and nickel.

[0025] The carrier on which the aminooxyalkyl group is supported by a chemical bond is not particularly limited, and examples thereof include carriers having any of the structures represented by the above general formula (1).

[0026] In the above general formula (1), the alkyl group having 1 to 4 carbon atoms represented by R is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a tert-butyl group, and the like.

[0027] Among these, as R, a methyl group is preferable in terms of the efficiency of the silane coupling reaction described later.

[0028] In the above general formula (1), the alkoxy group having 1 to 4 carbon atoms represented by X is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a 2-methylpropyloxy group, a 1-methylpropyloxy group, a tert-butoxy group, and the like.

[0029] Among these, as X, a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group is preferable in terms of the efficiency of the silane coupling reaction described later, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable.

[0030] In the general formula (1) above, m represents an integer from 0 to 2, and m' represents an integer of 0 or 1. However, in terms of the efficiency of the silane coupling reaction described later, it is preferably 0 or 1 respectively.

[0031] In the general formula (1) above, n represents an integer from 1 to 12. However, in terms of excellent aldehyde capture effect, an integer from 3 to 12 is preferable, and 3 is more preferable.

[0032] The carrier on which the aminooxyalkyl group is supported by a chemical bond is not particularly limited. For example, a compound represented by the general formula (2) above (hereinafter also referred to as "silane coupling agent") and an inorganic carrier having a hydroxyl group on its surface are reacted (hereinafter, the reaction is also referred to as "silane coupling reaction") and supported. It is preferably a carrier.

[0033] That is, the carrier on which the aminooxyalkyl group is supported by a chemical bond can be produced by reacting the above silane coupling agent with an inorganic carrier having a hydroxyl group on its surface.

[0034] In the above silane coupling agent, the definitions and preferred ranges of R, X, and n are synonymous with the definitions and preferred ranges of R, X, and n in the general formula (1) above.

[0035] In the above silane coupling agent, m represents an integer from 0 to 2. Regarding this m, it is preferably 0 or 1 in terms of the efficiency of the silane coupling reaction.

[0036] The above silane coupling agent may be purchased as a commercial product and used, but it can also be synthesized according to the methods described in Organic Preparations and Procedures International, vol.26, 1994, 111 - 113, JP-A-7-233132, Tetrahedron Letters, Vol.46(14), 2005, 7973 - 7975, etc.

[0037] As described above, the scavenger according to one aspect of the present disclosure is characterized by having an aminooxyalkyl group [a group represented by -(CH2)n-ONH2 in the above general formulas (1) and (2)]. Regarding the aminooxyalkyl group, part or all of it may be a chemically acceptable salt with an inorganic acid or an organic acid.

[0038] The type of the above salt is not particularly limited. For example, inorganic acid salts such as hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, phosphate, etc., and organic acid salts such as acetate, citrate, fumarate, maleate, trifluoromethanesulfonate, trifluoroacetate, benzoate, p-toluenesulfonate, etc. are included. Among these, inorganic acid salts are preferred as salts in terms of being inexpensive, and hydrochloride is more preferred.

[0039] The loading amount of the aminooxyalkyl group in the carrier on which the aminooxyalkyl group is supported by a chemical bond can be arbitrarily adjusted according to the purpose and is not particularly limited. However, based on the unit weight of the carrier on which the aminooxyalkyl group is supported by a chemical bond, a range of 0.01 to 10 mmol / g is preferred.

[0040] The inorganic carrier is not particularly limited, but those containing transition elements are preferred in terms of excellent sulfur-based gas scavenging effect. For example, those containing zinc, copper, iron, nickel, cobalt, manganese are included. In terms of efficient silane coupling reaction, those containing zinc are preferred, and zinc oxide, zinc hydroxide or zinc silicate are preferred, and zinc oxide or zinc hydroxide are more preferred.

[0041] The shape of the inorganic carrier described above is not particularly limited. For example, shapes generally used as separation substrates such as spherical (spherical particles, etc.), granular, fibrous, particulate, monolithic column, hollow fiber, and film-like (flat film, etc.) can be used. Among these, spherical, film-like, granular, particulate, or fibrous ones are preferred. Spherical, granular, or particulate carriers are particularly preferably used because their usage volume can be freely set when used in column methods or batch methods. As the particle size of the spherical, granular, or particulate carrier, those in the range of usually 0.1 μm to 10 mm in average particle diameter can be used, but those in the range of 1 μm to 100 μm are preferred in terms of good dispersibility in liquid.

[0042] The inorganic carrier described above may be porous or non-porous. As the average pore diameter of the porous carrier, those in the range of usually 1 nm to 1 μm can be used, but the range of 1 nm to 300 nm is preferred in terms of the capture rate.

[0043] As a method of using the capture agent according to one aspect of the present disclosure, the capture agent is brought into contact with a gas or liquid containing aldehydes or sulfur-based gas, and the aldehydes or sulfur-based gas in the gas or liquid is reacted with the capture agent, whereby the concentration of aldehydes or sulfur-based gas in the gas or liquid can be reduced.

[0044] The gas is not particularly limited, and examples thereof include air and nitrogen. The liquid is not particularly limited, and examples thereof include water and alcohol.

[0045] The aldehydes are not particularly limited, and examples thereof include formaldehyde, acetaldehyde, acrolein, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, 2-nonenal, benzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, and the like.

[0046] Although the sulfur-based gas mentioned above is not particularly limited, examples thereof include hydrogen sulfide gas, methyl mercaptan gas, ethyl mercaptan gas, and the like.

[0047] As another method of using the scavenger according to one aspect of the present disclosure, although not particularly limited, for example, a method of using the scavenger in a state of being attached to a substrate, and a method of using the scavenger in a state of being kneaded into a resin can be mentioned. The substrate to which the scavenger is attached and the resin in which the scavenger is kneaded are hereinafter referred to as "capturing structures".

[0048] The capturing structure can be produced by applying or spraying the scavenger onto the substrate. The scavenger can also be made into a capturing structure by mixing it with a binder resin and then applying or spraying it onto the substrate.

[0049] The binder resin is not particularly limited, and examples thereof include acrylic ester resin, silicone resin, urethane resin, polyester resin, melamine resin, polypropylene resin, and fluororesin.

[0050] The capturing structure can capture odor-causing substances (including aldehydes or sulfur-based gases) in the gas by being exposed to a gas containing odor-causing substances that cause bad odors, and can reduce the bad odor of the gas.

[0051] The substrate is not particularly limited, and examples thereof include fibers, sheets, wallpapers, sponges, beads, woods, plywoods, gypsum boards, and the like.

[0052] The materials for the fibers, sheets, wallpapers, or sponges described above are not particularly limited. Examples include polyester, polyamide, polyacrylonitrile, polypropylene, polyethylene, polyvinyl chloride, fluororesins, aramid resins, sulfone resins, rayon, acetate, cotton, wool, silk, hemp, glass, carbon, ceramics, silicone resins, polyimide resins, natural rubber, polyurethane, and the like.

[0053] The capture structures described above are not particularly limited. Examples include clothing, curtains, carpets, wall coverings, automotive interior materials, furniture, and the like.

[0054] The amount of the capture agent immobilized on the substrate can be arbitrarily adjusted according to the purpose and is not particularly limited. However, based on the unit area of the substrate, the capture agent is preferably in the range of 0.1 to 200 g / m 2 and more preferably in the range of 0.5 to 75 g / m 2 .

[0055] The capture structure can also be produced by dispersing and mixing a resin and the capture agent described above. The resin is not particularly limited, and examples include high-pressure low-density polyethylene, high-density polyethylene, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, polypropylene, propylene-ethylene copolymer, propylene-1-butene copolymer, poly-1-butene, poly-1-hexene, poly-4-methyl-1-pentene, and the like.

[0056] The above-mentioned dispersion and mixing can be carried out by a commonly used resin kneading device. Examples of the kneading device include a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a Banbury mixer, a pressure kneader, a rotating roll, or an internal mixer, and the like.

[0057] The mixing amount of the scavenger in the resin can be arbitrarily adjusted according to the purpose and is not particularly limited. However, based on the unit weight of the resin, a range of 0.01 to 50% by weight is preferred, and a range of 0.01 to 10% by weight is more preferred.

Examples

[0058] Hereinafter, the present invention will be described in more detail, but the present invention should not be construed as being limited in any way by these examples. Unless otherwise specified, commercially available reagents and the like were used. The analytical instruments and evaluation methods used in this example are listed below.

[0059] <Abbreviations> The following abbreviations were used for the compounds used in the examples.

[0060] Acetaldehyde = AA 4-Nitrobenzaldehyde = NBA <AA Capture Test> After enclosing 20 mg of the scavenger in a 5 L Tedlar bag, 3 L of nitrogen gas with an AA concentration of about 350 ppm was added. After standing at room temperature for 24 hours, 0.1 L of the gas in the Tedlar bag was adsorbed onto a cartridge (manufactured by Fujifilm Wako Pure Chemical Corporation, Presep-C DNPH) loaded with 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the DNPH-aldehyde condensate was quantified using a liquid chromatograph (manufactured by Shimadzu Corporation, LC-2030C Plus), and the residual acetaldehyde concentration inside the Tedlar bag was calculated. The AA capture capacity [mg / g] was calculated from the difference between the added AA and the residual AA.

[0061] <Hydrogen Sulfide Capture Test> After enclosing 50 mg of the scavenger in a 5 L Tedlar bag, 3 L of nitrogen gas with a hydrogen sulfide concentration of about 10 ppm was added. After standing at room temperature for 24 hours, the hydrogen sulfide concentration in the Tedlar bag was measured using a detector tube (manufactured by Gastech). The hydrogen sulfide capture rate was calculated using the following formula.

[0062] Hydrogen sulfide capture rate (%) = [(Initial hydrogen sulfide concentration - Residual hydrogen sulfide concentration) ÷ Initial hydrogen sulfide concentration] × 100.

[0063] <NBA Capture Test> 60 mg of NBA (manufactured by Tokyo Chemical Industry) and 10 g of p-xylene (manufactured by FUJIFILM Wako Pure Chemical Corporation) were mixed in a glass container to form a solution. Subsequently, 0.1 g of the capture agent and 10 g of water were added to the glass container, and the mixture was stirred at 80 °C for 1 hour. After stopping the stirring, the mixture was allowed to stand for 15 minutes, and the supernatant organic layer was passed through a syringe filter with a pore size of 0.45 μm (manufactured by Advantec, DISMIC13HP) to obtain an NBA solution after filtration. The NBA solution after filtration was analyzed using a liquid chromatograph (LC2050 manufactured by Shimadzu Corporation), and the remaining amount of NBA [mg] was calculated. The NBA capture capacity [mg / g] was calculated using the following formula.

[0064] NBA capture capacity [mg / g] = (Amount of charged NBA [mg] - Remaining amount of NBA [mg]) ÷ Amount of charged capture agent [g] Synthesis Example 1 After mixing 3.08 g of silica gel (manufactured by Tosoh Silica, NIPGEL CX-400) and 9.24 g of toluene, 0.976 g of the silane coupling agent represented by chemical formula (1a’) and 0.451 g of water were added dropwise, and the mixture was stirred under a nitrogen stream and heating reflux for 4 hours. The obtained reaction solution was filtered, and the residue was washed with methanol. The residue was dried at 120 °C for 4 hours to obtain 3.32 g of a carrier having an aminooxyalkyl group supported by a chemical bond (hereinafter referred to as “aminooxy group-supported carrier”).

[0065]

Chemical formula

[0066] Synthesis Example 2 The same procedure as in Synthesis Example 1 was carried out except that 3.08 g of zinc oxide (manufactured by FUJIFILM Wako Pure Chemical Corporation) was used instead of silica gel (manufactured by Tosoh Silica, NIPGEL CX-400), and 3.33 g of an aminooxy group-supported carrier was obtained.

[0067] Synthesis Example 3 Instead of silica gel (manufactured by Tosoh Silica, NIPGEL CX-400), 3.08 g of zinc hydroxide (manufactured by Chikamoto Junyaku) was used, and the procedure was the same as in Synthesis Example 1 to obtain 3.10 g of an aminooxy group-bearing carrier.

[0068] Synthesis Example 4 Instead of silica gel (manufactured by Tosoh Silica, NIPGEL CX-400), 3.08 g of titanium oxide (manufactured by Fujifilm Wako Pure Chemical Corporation) was used, and the procedure was the same as in Synthesis Example 1 to obtain 3.29 g of an aminooxy group-bearing carrier.

[0069] Synthesis Example 5 Instead of silica gel (manufactured by Tosoh Silica, NIPGEL CX-400), 3.08 g of aluminum hydroxide (manufactured by Fujifilm Wako Pure Chemical Corporation) was used, and the procedure was the same as in Synthesis Example 1 to obtain 3.09 g of an aminooxy group-bearing carrier.

[0070] Example 1 For the aminooxy group-bearing carrier obtained in Synthesis Example 2, an AA capture test and a hydrogen sulfide capture test were conducted. The results are shown in Table 1.

[0071] Example 2 For the aminooxy group-bearing carrier obtained in Synthesis Example 3, an AA capture test and a hydrogen sulfide capture test were conducted. The results are shown in Table 1.

[0072] Comparative Example 1 For the aminooxy group-bearing carrier obtained in Synthesis Example 1, an AA capture test and a hydrogen sulfide capture test were conducted. The results are shown in Table 1.

[0073] Comparative Example 2 For zinc oxide (manufactured by Fujifilm Wako Pure Chemical Corporation), an AA capture test and a hydrogen sulfide capture test were conducted. The results are shown in Table 1.

[0074] Comparative Example 3 For zinc hydroxide (manufactured by Chikamoto Junyaku), an AA capture test and a hydrogen sulfide capture test were conducted. The results are shown in Table 1.

[0075] Reference Example 1 For the aminooxy group-bearing carrier obtained in Synthesis Example 4, an AA capture test and a hydrogen sulfide capture test were conducted. The results are shown in Table 1.

[0076] Reference Example 2 For titanium oxide (manufactured by Fujifilm Wako Pure Chemical Corporation), an AA capture test and a hydrogen sulfide capture test were conducted. The results are shown in Table 1.

[0077] Reference Example 3 For the aminooxy group-bearing carrier obtained in Synthesis Example 5, an AA capture test and a hydrogen sulfide capture test were conducted. The results are shown in Table 1.

[0078] Reference Example 4 For aluminum hydroxide (manufactured by Fujifilm Wako Pure Chemical Corporation), an AA capture test and a hydrogen sulfide capture test were conducted. The results are shown in Table 1.

[0079] As shown in Table 1, it was found that the scavenger of the present invention exhibits a high scavenging effect on both AA and hydrogen sulfide, while the conventionally known scavengers exhibit a high scavenging effect only on one of AA and hydrogen sulfide.

[0080] [Table 1]

[0081] Example 3 When an NBA capture test was conducted on the aminooxy group-bearing carrier obtained in Synthesis Example 2, the NBA capture capacity was 85 mg / g.

[0082] Comparative Example 4 When an NBA capture test was conducted on zinc oxide (manufactured by Fujifilm Wako Pure Chemical Corporation), the NBA capture capacity was 4 mg / g.

Industrial Applicability

[0083] The scavenger according to one aspect of the present disclosure is industrially useful in that it provides a scavenger capable of capturing sulfur-based gases and aldehydes at once.

Claims

1. An odorant capture agent comprising an inorganic carrier containing at least one metal selected from the group consisting of zinc, copper, iron, manganese, cobalt and nickel, and an aminooxyalkyl group supported thereon by chemical bonding.

2. 2. The capture agent according to claim 1, wherein the support having an aminooxyalkyl group supported thereon by a chemical bond is a support having any structure represented by the following general formula (2): 【Chemistry 1】 (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer of 0 to 2. m' represents 0 or 1. n represents an integer of 1 to 12. When m is 2, multiple R may be the same or different. When m is 0, multiple X may be the same or different.

3. 3. The scavenger according to claim 2, wherein R is a methyl group, and X is at least one selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

4. The capture agent of claim 2 , wherein n is 3.

5. 2. The capture agent according to claim 1, wherein the support having aminooxyalkyl groups supported by chemical bonding is an inorganic support having hydroxyl groups on its surface, which is supported by reacting a compound represented by the following general formula (1): 【Chemistry 2】 (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer of 0 to 2, and n represents an integer of 1 to 12. When m is 0 or 1, multiple Xs may be the same or different. When m is 2, multiple Rs may be the same or different.)

6. 6. The scavenger according to claim 5, wherein R is a methyl group, and X is at least one selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

7. The capture agent of claim 5 , wherein n is 3.

8. 2. The scavenger according to claim 1, wherein the inorganic carrier is zinc oxide or zinc hydroxide.

9. A method for removing aldehydes, comprising contacting the scavenger according to any one of claims 1 to 8 with aldehydes.

10. A method for removing hydrogen sulfide or mercaptans, comprising contacting the scavenger according to any one of claims 1 to 8 with hydrogen sulfide or mercaptans.

11. A method for removing odorous substances, comprising contacting the scavenger according to any one of claims 1 to 8 with at least one odorous substance selected from the group consisting of aldehydes, hydrogen sulfide and mercaptans.

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