JP7395903B2 - Deodorants - Google Patents

Description

The present invention relates to a deodorant for asphalt.

Asphalt contains various hydrocarbon compounds and sulfur compounds, and it is known that these are denatured into aldehydes and hydrogen sulfide through heating processes and the like.

Aldehydes and hydrogen sulfide are the main odor substances generated during the asphalt manufacturing process. Aldehydes and hydrogen sulfide have a low odor threshold and are also toxic, so they may pose a health risk to residents near asphalt manufacturing plants. Therefore, it is required to remove these harmful substances.

As a method for reducing odor during asphalt production, a method using an amino acid metal chelate as a deodorant has been disclosed (see, for example, Patent Document 1).

However, although the conventional method shows a high deodorizing effect on hydrogen sulfide, there is a problem in that the deodorizing effect on aldehydes is insufficient.

Special table 2017-505866 publication

The present invention has been made in view of the above-mentioned background art, and an object of the present invention is to provide a deodorizing agent that quickly captures aldehydes and hydrogen sulfide derived from asphalt.

As a result of intensive studies to solve the above problems, the present inventors found that a deodorant containing a specific carboxyl group-containing O-substituted hydroxylamine or a chemically acceptable salt or heavy metal salt thereof It was discovered that aldehydes and hydrogen sulfide derived from asphalt can be rapidly captured, and the present invention was completed.

That is, the present invention has the following gist.

[1] A deodorant characterized by containing a carboxyl group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof, and a heavy metal salt.

[2] The deodorant according to [1], which contains one or more carboxy group-containing O-substituted monohydroxylamine represented by the following general formula (1) or a chemically acceptable salt thereof .

(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. n represents an integer of 1 to 6. (Plural R's may be the same or different.)
[3] In general formula (1), R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a benzyl group, a phenyl group. The deodorant according to [2], which is any one of the above.

[4] The deodorant according to [1] to [3], wherein the heavy metal salt is any one of a zinc salt, an iron salt, and a copper salt.

[5] The deodorant according to [1] to [4], wherein the heavy metal salt is zinc glycine.

[6] A method for removing aldehydes and hydrogen sulfide, which comprises using the deodorant described in [1] to [5].

The deodorant of the present invention quickly captures aldehydes and hydrogen sulfide. As a result, aldehydes and hydrogen sulfide harmful to the human body can be reduced, and the living environment of humans can be improved.

The deodorant of the present invention is characterized in that it contains a carboxyl group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof, and a heavy metal salt.

In the above general formula (1), R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. n represents an integer from 1 to 6. A plurality of R's may be the same or different.

The alkyl group having 1 to 18 carbon atoms may be a linear, branched, or cyclic alkyl group, and is not particularly limited, but includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group (cetyl group), heptadecyl group, octadecyl group (stearyl group), oleyl group, elaidyl group group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,1-dimethylpropyl group, 2-ethylhexyl group, cyclopropyl group, cyclobutyl group , cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, and the like.

The aryl group having 6 to 14 carbon atoms is not particularly limited, but includes, for example, phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, cumenyl group, vinylphenyl group, biphenylyl group, phenanthryl group, and the like.

The arylalkyl group having 7 to 15 carbon atoms is not particularly limited, but includes, for example, benzyl group, phenylethyl group, phenylpropyl group, naphthylmethyl group, anthrylmethyl group, tolylmethyl group, xylylmethyl group, cumenylmethyl group, vinylphenyl group. Examples include methyl group, biphenylylmethyl group, phenanthrylmethyl group, and the like.

Among these, in general formula (1), R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a benzyl group, a phenyl group. Particularly preferred are carboxy group-containing O-substituted monohydroxylamines.

Part or all of the hydroxylamino group of the above-mentioned carboxy group-containing O-substituted monohydroxylamine may be a chemically acceptable salt with an inorganic acid or an organic acid. The type of salt is not particularly limited, but includes, for example, hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, and phosphoric acid. Examples include inorganic acid salts such as salts, organic acid salts such as acetate, citrate, fumarate, maleate, trifluoromethanesulfonate, trifluoroacetate, benzoate, and tosylate, and are inexpensive. In this respect, inorganic acid salts are preferred, and hydrochlorides are more preferred.

Furthermore, the carboxy group of the above-mentioned carboxy group-containing O-substituted monohydroxylamine may form an inner salt with a hydroxylamino group within the molecule. Further, a part of the carboxyl group may be a carboxylate salt, but since the deodorizing effect of the deodorant of the present invention decreases when it becomes alkaline, the carboxylate salt may be used within a range where the pH is 7 or less. It is preferable to form. The type of carboxylate salt is not particularly limited, but examples include alkali metal salts such as lithium salts, sodium salts, potassium salts, and cesium salts, ammonium salts, and the like.

The heavy metal salt is not particularly limited as long as it shows reactivity with hydrogen sulfide, and examples thereof include zinc salt, iron salt, and copper salt.

Examples of zinc salts include, but are not limited to, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc acetate, and zinc glycine.

Examples of iron salts include, but are not limited to, iron chloride, iron bromide, iron sulfate, iron acetate, and iron glycine.

Examples of copper salts include, but are not limited to, copper chloride, copper bromide, copper iodide, copper sulfate, copper acetate, and copper glycine.

Among these, zinc glycine is particularly preferred.

The deodorant of the present invention can be used in any form depending on the purpose and use. For example, a carboxy group-containing O-substituted monohydroxylamine or its chemically acceptable salt and heavy metal salt (hereinafter referred to as "carboxy group-containing O-substituted monohydroxylamine and heavy metal salt") is dissolved in an arbitrary solvent. It can be used as a liquid deodorant, or it can be used as a solid deodorant by supporting carboxy group-containing O-substituted monohydroxylamines and heavy metal salts or the liquid deodorant on any carrier. .

The amount of carboxy group-containing O-substituted monohydroxylamines and heavy metal salts dissolved in the solvent when preparing the liquid deodorant of the present invention can be arbitrarily adjusted depending on the purpose, and is not particularly limited. However, each amount is preferably in the range of 0.0001 to 10% by weight based on the liquid deodorant of the present invention.

When preparing the solid deodorant of the present invention, any carrier supporting the carboxyl group-containing O-substituted monohydroxylamine and the heavy metal salt can be used without particular limitation as long as it is insoluble in water. For example, as a polymer carrier, styrene polymers such as polystyrene and crosslinked polystyrene, polyolefins such as polyethylene and polypropylene, poly(halogenated olefins) such as polyvinyl chloride and polytetrafluoroethylene, nitrile polymers such as polyacrylonitrile, and Examples include (meth)acrylic polymers such as methyl methacrylate and polyethyl acrylate, and high molecular weight polysaccharides such as cellulose, agarose, and dextran.Inorganic carriers include activated carbon, silica gel, diatomaceous earth, hydroxyapatite, alumina, and titanium oxide. , magnesia, polysiloxane, etc.

Here, crosslinked polystyrene refers to monovinyl aromatic compounds such as styrene, vinyltoluene, vinylxylene, and vinylnaphthalene, and divinylbenzene, divinyltoluene, divinylxylene, divinylnaphthalene, trivinylbenzene, bisvinyldiphenyl, bisvinylphenylethane, etc. These copolymers are mainly composed of crosslinked copolymers with polyvinyl aromatic compounds, and methacrylic acid esters such as glycerol methacrylate and ethylene glycol dimethacrylate may be copolymerized with these copolymers.

The shape of the carrier used in the preparation of the solid deodorant of the present invention is not particularly limited, but includes, for example, spherical (e.g., spherical particles), granules, fibers, granules, monolith columns, Shapes commonly used as separation substrates such as hollow fibers and membranes (e.g., flat membranes) can be used; among these, spherical, membrane-shaped, granular, granular, or fibrous shapes are available. is preferred. Spherical, granular, or granular carriers are particularly preferably used when used in a column method or a batch method, since the volume to be used can be freely set. As for the particle size of the spherical, granular, or granular carrier, those having an average particle size in the range of 1 μm to 10 mm can be used, but the average particle size is preferably in the range of 2 μm to 1 mm.

The carrier used in the preparation of the solid deodorant of the present invention may be porous or non-porous. The average pore diameter of the porous carrier can generally be 1 nm to 1 μm, but is preferably in the range of 1 nm to 300 nm from the viewpoint of deodorizing speed.

The method for preparing the solid deodorant of the present invention is not particularly limited, but for example, the liquid deodorant of the present invention or the O-substituted monohydroxylamine containing a carboxyl group and a heavy metal salt are physically One example is a method of adsorbing and immobilizing.

The method of physically adsorbing and immobilizing the carboxyl group-containing O-substituted monohydroxylamines and heavy metal salts is not particularly limited, but for example, the carboxyl group-containing O-substituted monohydroxylamines and heavy metal salts are mixed with water, etc. Examples include a method in which the carrier is dissolved in a solvent, then the carrier described above is added, the carrier is impregnated with the carboxyl group-containing O-substituted monohydroxylamine and the heavy metal salt, and the solvent is further distilled off.

The amount of carboxy group-containing O-substituted monohydroxylamines and heavy metal salts supported on the carrier can be arbitrarily adjusted depending on the purpose, and is not particularly limited, but the amount of each of the carboxy group-containing O-substituted monohydroxylamines and heavy metal salts supported on the carrier used in the present invention is 0. A range of .0001 to 10% by weight is preferred.

FIG. 3 is a diagram showing the capture rates of acetaldehyde and hydrogen sulfide in Examples 1 to 2 and Comparative Examples 1 to 3.

The present invention will be specifically explained below, but the present invention should not be construed as being limited to these Examples.

Reference example 1 (adjustment of test gas)
400 g of asphalt was placed in a 4 L pressure container and heated at 175° C. for 6 hours, and then the generated gas was diluted 10 times with nitrogen to prepare a test gas. This gas contained 9.1 ppm acetaldehyde and 0.8 ppm hydrogen sulfide.

Examples 1-2 (deodorization of asphalt-derived gas)
A deodorant was prepared by dissolving aminooxyacetic acid and zinc glycine in water in the proportions shown in Table 1. 0.1 mL of this deodorant was injected into a Tedlar bag containing 1 L of the test gas prepared in Reference Example 1. After heating at 65° C. for 10 minutes, the gas in the Tedlar bag was adsorbed onto a cartridge supporting 2,4-dinitrophenylhydrazine (DNPH) (product name: Presep-C DNPH, manufactured by Wako Pure Chemical Industries, Ltd.). The DNPH-aldehyde condensate is eluted from this cartridge (eluent = acetonitrile), and the DNPH-aldehyde condensate in the eluate is quantified using a liquid chromatograph (device name: Agilent 1220 Infinity LC, manufactured by Agilent Technologies) to determine whether it remains. The aldehyde concentration was calculated. On the other hand, the residual hydrogen sulfide concentration was determined using a detection tube (manufactured by Gastech). Furthermore, the capture rate of aldehyde and hydrogen sulfide was calculated from the following formula.

Capture rate [%] = {(initial concentration - residual concentration) ÷ initial concentration} x 100.

Comparative examples 1 to 3
The same procedure as in Examples 1 and 2 was carried out except that a deodorant containing only one of aminooxyacetic acid and zinc glycine was used.

The results of Examples 1 and 2 and Comparative Examples 1 and 3 are shown in Table 1 and FIG. 1. As is clear from Table 1 and FIG. 1, the deodorant of the present invention exhibited higher deodorizing performance against acetaldehyde and hydrogen sulfide than existing deodorants.

The deodorizer of the present invention quickly captures aldehydes and hydrogen sulfide derived from asphalt. As a result, aldehydes and hydrogen sulfide harmful to the human body can be reduced, and the living environment of humans can be improved.

Claims (4)

An aldehyde and hydrogen sulfide scavenger comprising a carboxyl group-containing O-substituted monohydroxylamine represented by the following general formula (1) or a chemically acceptable salt thereof, and zinc glycine .
(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. n represents an integer of 1 to 6. (Plural R's may be the same or different.) In general formula (1), R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a benzyl group, or a phenyl group. The aldehyde and hydrogen sulfide scavenger according to claim 1 , characterized in that: Claim 1, wherein the carboxyl group-containing O-substituted monohydroxylamine represented by general formula (1) or a chemically acceptable salt thereof is aminooxyacetic acid or a chemically acceptable salt thereof. Aldehyde and hydrogen sulfide scavenger. A method for removing aldehydes and hydrogen sulfide, which comprises using the aldehyde and hydrogen sulfide scavenger according to any one of claims 1 to 3 .