CN109890500B - Adsorbent for odorant - Google Patents
Adsorbent for odorant Download PDFInfo
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- CN109890500B CN109890500B CN201780065808.XA CN201780065808A CN109890500B CN 109890500 B CN109890500 B CN 109890500B CN 201780065808 A CN201780065808 A CN 201780065808A CN 109890500 B CN109890500 B CN 109890500B
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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
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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
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
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- 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
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
Abstract
The invention provides an adsorbent for odorous substances, which contains an acid hydrazide compound and silica, wherein the density of silanol groups on the surface of the silica is 5.0/nm2The following; even when a hydrazine compound and silica are mixed, the storage stability can be improved.
Description
Technical Field
The invention relates to an adsorbent for an odor substance.
Background
In recent years, consumer demand for deodorization has been increasing. Among them, aldehyde compounds such as formaldehyde and acetaldehyde are considered to be causative substances of sick building syndrome and are substances that are difficult to adsorb by an adsorbent, and therefore, the demand for deodorization is particularly high. As an adsorbent for such an odorant, for example, a hydrazine compound is known.
Among them, adipic acid dihydrazide has good aldehyde adsorption properties. Further, adipic acid dihydrazide has high storage stability in the neutral region and also has heat resistance of 200 ℃ or higher (decomposition temperature in TG-DTA is about 230 to 275 ℃).
As described above, the use of hydrazine compounds can provide high adsorption performance, but there is still a high demand for improvement in adsorption performance and improvement in adsorption rate. For example, in the prior art, a hydrazine compound and silica are mixed to impart heat resistance or to improve adsorption performance.
However, the storage stability of hydrazine compounds is lowered under acidic or basic conditions. Since silica has a property as a solid acid, when a hydrazine compound and silica are mixed, storage stability is generally lowered, and therefore, it is very difficult to commercialize an adsorbent containing the hydrazine compound and silica. In particular, although storage stability at room temperature is not a problem, storage stability at high temperatures in the midsummer is often severely reduced, aldehyde compounds cannot be sufficiently adsorbed, and the problem of unpleasant odor cannot be solved. In addition, it is also known that coloration occurs with a decrease in storage stability of the hydrazine compound. For example, patent document 1 describes: although it is conceivable to pass through inorganic powder (SiO)2Etc.) have a catalytic action to decompose the dihydrazide compound, but details thereof are not known. In patent document 1, this problem is solved by heating the deodorant composition at a specific temperature so as to increase the amount of water, but the decomposition of the hydrazine compound is not suppressed, but only suppressed to a minimum, and therefore the effect of improving the storage stability is insufficient.
Documents of the prior art
Patent document
Patent document 1 International publication No. 2013/118714
Disclosure of Invention
Technical problem to be solved by the invention
As described above, conventionally, in the case of mixing a hydrazine compound and silica, decomposition of the hydrazine compound cannot be suppressed. Coloration occurs with a decrease in storage stability of the hydrazine compound. In order to avoid coloring, it is necessary to improve the storage stability of the hydrazine compound.
Accordingly, an object of the present invention is to provide an adsorbent for an odorant (e.g., aldehyde compound) which can improve storage stability and prevent coloration even when a hydrazine compound and silica are mixed.
Means for solving the problems
The present inventors have made intensive studies to achieve the above object, and as a result, have found that: by using a density of silanol groups on the surface of 5.0 pieces/nm2The following silica can improve storage stability and avoid coloration even when a hydrazine compound and silica are mixed. The present inventors have further conducted extensive studies based on the above findings, and have completed the present invention. That is, the present invention includes the following.
Item 1. an adsorbent for odorous substances, which contains an acid hydrazide compound and silica, and
the density of silanol groups on the surface of the silica is 5.0 groups/nm2The following.
The adsorbent for an odorant according to item 1, wherein the water content is 5.0% by mass or less.
Item 3. the adsorbent according to item 1 or 2, wherein the silica is at least 1 selected from the group consisting of wet-process silica, dry-process silica, and fused silica.
The adsorbent according to any one of items 1 to 3, wherein the acid hydrazide compound is at least 1 selected from the group consisting of carbodihydrazide (carbodihydrazide), malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, and isophthalic acid dihydrazide.
The adsorbent according to any one of items 1 to 4, wherein the silica has a specific surface area of 100 to 1000m2/g。
The adsorbent according to any one of items 1 to 5, wherein the odorant is an aldehyde compound.
The method for producing the adsorbent according to any one of claims 1 to 6, wherein the method comprises (II) a step of mixing the acid hydrazide compound and the silica.
Item 8 the production method according to item 7, wherein,
prior to the step (II) described above,
the production method comprises (I) a step of heating silica at 300 ℃ or higher.
Item 9. the production method according to item 7 or 8, wherein,
the production method does not include a step of heating after the step (II).
An industrial product comprising the adsorbent according to any one of items 1 to 6.
Item 11. a method for adsorbing an odorant on an adsorbent by contacting a gas containing an aldehyde compound with the adsorbent, wherein,
the adsorbent contains an acid hydrazide compound and silica, and the density of silanol groups on the surface of the silica is 5.0/nm2The following.
Effects of the invention
Since the adsorbent of the present invention contains an acid hydrazide compound and the density of silanol groups on the surface is 5.0 per nm2The following silica can improve storage stability and can prevent coloration.
Detailed Description
1. Adsorbent and process for producing the same
The adsorbent of the present invention contains an acid hydrazide compound and silica, and the density of silanol groups on the surface of the silica is 5.0 molecules/nm2The following adsorbents of odorants.
The density of silanol groups on the surface of the adsorbent adopted by the invention is 5.0/nm2The following silica, therefore, contains acid acyl groupsHydrazine compounds and silica, however, are excellent in storage stability and can be prevented from coloring.
(1-1) acid hydrazide Compound
The acid hydrazide compound is not particularly limited, and a compound known in the art can be used. For example, an acid monohydrazide compound having 1 hydrazide group in the molecule, a dihydrazide compound having 2 hydrazide groups in the molecule, an acid triachydrazide compound having 3 hydrazide groups in the molecule, and the like can be used. Among them, a dihydrazide compound or an acid triachydrazide compound is preferable from the viewpoints of adsorption performance of an odorant (an aldehyde compound, etc.), storage stability of an adsorbent, suppression of coloring, and the like. Among them, the acid dihydrazide compound is preferably a general-purpose compound. The acid hydrazide compound is a compound having an action of adsorbing an odorant (e.g., aldehyde compound).
The molecular weight of the acid hydrazide compound is, for example, preferably 30 or more, more preferably 60 or more, and further preferably 90 or more, from the viewpoint of adsorption performance and adsorption rate. The molecular weight of the acid hydrazide compound is, for example, preferably 300 or less, more preferably 280 or less, and further preferably 260 or less, from the viewpoint of adsorption performance and adsorption rate. In addition, as additional properties, the molecular weight of the acid hydrazide compound is, for example, preferably 100 or more, and more preferably 130 or more, from the viewpoint of heat resistance and storage stability. In addition, as additional properties, the molecular weight of the acid hydrazide compound is, for example, preferably 300 or less, more preferably 270 or less, from the viewpoint of heat resistance and storage stability.
Specific examples of such acid hydrazide compounds include: carbodihydrazide, malonic dihydrazide, succinic dihydrazide, adipic dihydrazide, sebacic dihydrazide, dodecanedioic dihydrazide, isophthalic dihydrazide, citric acid trihydrazide, pyromellitic acid trihydrazide, 1,2, 4-benzenetricarboxylic acid trihydrazide, nitrilotriacetic acid trihydrazide, 1,3, 5-cyclohexanetricarboxylic acid trihydrazide, and the like. Among them, adipic acid dihydrazide and succinic acid dihydrazide are preferable from the viewpoint of an excellent balance among safety, adsorption performance, adsorption rate, coloration inhibition, heat resistance and storage stability. These acid hydrazide compounds may be used alone, or 2 or more of them may be used in combination.
The content of the acid hydrazide compound is, for example, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more, per 100 parts by mass of silica described later, from the viewpoint of further improving the adsorption performance, adsorption rate, coloration inhibition, heat resistance, and storage stability. The content of the acid hydrazide compound is, for example, preferably 80 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 20 parts by mass or less, based on 100 parts by mass of silica described later, from the viewpoint of further improving the adsorption performance, adsorption rate, heat resistance, and storage stability.
The content of the acid hydrazide compound in the adsorbent of the present invention is not particularly limited, and is, for example, preferably 0.1 mass% or more, more preferably 1.0 mass% or more, and further preferably 3.0 mass% or more, when the total amount of the adsorbent is 100 mass%, from the viewpoint of further improving the adsorption performance, adsorption rate, coloration inhibition, heat resistance, and storage stability. The content of the acid hydrazide compound in the adsorbent of the present invention is not particularly limited, but is, for example, preferably 90.0 mass% or less, more preferably 50.0 mass% or less, and further preferably 20.0 mass% or less, when the total amount of the adsorbent is 100 mass%, from the viewpoint of further improving the adsorption performance, adsorption rate, heat resistance, and storage stability.
(1-2) silica
The adsorbent of the present invention has silica having a density of silanol groups on the surface of 5.0 molecules/nm2The following.
Silanol group density means: 1nm per unit calculated from the specific surface area of the silica particles measured by the BET method using nitrogen gas and the number of silanol groups measured according to JIS K1150-19942The number of silanol groups on the surface area of the silica particles (2).
When the density of the silanol group is high, the acid hydrazide compound becomes unstable when mixed with the acid hydrazide compound, and therefore, the storage stability of the obtained adsorbent becomes insufficient and the obtained adsorbent tends to be colored. From this viewpoint, silicon on the surface of silicaThe density of the alkanol group is 5.0 pieces/nm2Hereinafter, the number of molecules is preferably 4.8/nm2Hereinafter, more preferably 4.5 molecules/nm2The following. On the other hand, the lower limit of the density of silanol groups on the silica surface is not particularly limited, but is usually 0.1 number/nm2Above, preferably 1.4/nm2Above, more preferably 2.6/nm2The above.
The silica used in the present invention has a loss on ignition at 1050 ℃ measured in accordance with JIS K1150-1994 of preferably 4.0% by mass or less, more preferably 3.7% by mass or less, and still more preferably 3.0% by mass or less, from the viewpoint of further improving the adsorption performance, adsorption rate, coloration inhibition, heat resistance and storage stability. The lower limit of the ignition loss at 1050 ℃ of the silica used in the present invention, measured in accordance with JIS K1150-1994, is not particularly limited, but is usually preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.8% by mass or more. The ignition loss at 1050 ℃ of silica was measured in accordance with JIS K1150-1994.
The silica used in the present invention preferably has a specific surface area of 1000m from the viewpoint of further improving adsorption performance, suppression of coloration, adsorption rate, heat resistance and storage stability2A value of less than or equal to g, more preferably 600m2A total of 570m or less2The ratio of the carbon atoms to the carbon atoms is less than g. The lower limit of the specific surface area of the silica used in the present invention is preferably 100m from the viewpoint of further improving the adsorption performance, suppression of coloration, adsorption rate, heat resistance and storage stability2A value of at least one of,/g, more preferably 200m2A total of 300m or more2More than g. The specific surface area of silica was measured by the BET method using nitrogen gas.
The silica used in the present invention has an average particle diameter of preferably 3.0 μm or more, more preferably 5.0 μm or more, from the viewpoint of further improving adsorption performance, suppression of coloration, adsorption rate, heat resistance and storage stability. The silica used in the present invention has an average particle diameter of preferably 20.0 μm or less, more preferably 15.0 μm or less, from the viewpoint of further improving adsorption performance, coloration suppression, adsorption rate, heat resistance and storage stability. In the present invention, D50 measured by a laser method is defined as the average particle size of silica.
Examples of such silica include: wet silica (precipitated silica, gel silica, etc.), dry silica, fused silica, and the like. In particular, wet-process silica (precipitated silica, gel silica, etc.) which is easy to control the density of silanol groups is preferably used. In particular, by heating these silicas under the conditions described later, the density of silanol groups can be further reduced, the hydrazine compound can be further stabilized, and coloring can be further suppressed.
The content of silica in the adsorbent of the present invention is not particularly limited, and from the viewpoint of further improving the adsorption performance, adsorption rate, coloration inhibition, heat resistance and storage stability, when the total amount of the adsorbent is 100 mass%, for example, it is preferably 10.0 mass% or more, more preferably 50.0 mass% or more, and further preferably 80.0 mass% or more. The content of silica in the adsorbent of the present invention is not particularly limited, and is, for example, preferably 99.9% by mass or less, more preferably 99.0% by mass or less, and still more preferably 97.0% by mass or less, when the total amount of the adsorbent is 100% by mass, from the viewpoint of further improving adsorption performance, adsorption rate, coloration inhibition, heat resistance, and storage stability.
(1-3) adsorbent Supported on Carrier
In the present invention, since the silica functions as a carrier for the acid hydrazide compound, the acid hydrazide compound may be supported (added and adhered) on the silica and used as an adsorbent (hereinafter, may be referred to as "supported adsorbent"). In addition, supports other than silica may also be used.
When a porous support other than silica is used, the porous support is not particularly limited, and generally known supports can be widely used, and examples thereof include: zeolites, alumina, ceramics, diatomaceous earth, activated carbon, clay, talc, calcium carbonate, and the like. These porous supports may be used alone, or 2 or more kinds thereof may be used in combination.
The adsorbent of the present invention preferably contains 5.0% by mass or less of water, more preferably 4.4% by mass or less of water, and even more preferably 3.0% by mass or less of water, from the viewpoints of further improving storage stability, adsorption performance, adsorption rate, and further suppressing coloring. The lower limit of the moisture content of the adsorbent of the present invention is not particularly limited, but is usually preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more. The moisture of the adsorbent of the present invention was measured in terms of the volatile content after heating at 105 ℃ for 2 hours.
In order to produce the adsorbent of the present invention having the above-mentioned conditions, it is preferable to use an adsorbent having a density of silanol groups on the surface of 5.0 molecules/nm as described above2The following silicon dioxide. The moisture absorption of such silica is controlled, whereby the moisture of the adsorbent of the present invention can be adjusted (reduced).
(1-4) suspension adsorbent, powder adsorbent or pellet (pellet) adsorbent
In the present invention, after the above-mentioned supported adsorbent is produced, it may be dispersed in a solvent to form a suspension, and this may be used as an adsorbent. Further, the powder may be mixed with a powder and used as a powder. In addition, the particles may be used.
Examples of the solvent include: water, lower alcohols, polyhydric alcohols, ketones, ethers, esters, aromatic solvents, halogenated hydrocarbon solvents, polar organic solvents, and the like.
Examples of the lower alcohol include alcohols having a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, and n-butanol.
Examples of the polyhydric alcohol include: ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and the like.
Examples of the ketone include: acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene carbonate, and the like.
Examples of the ether include dioxane, tetrahydrofuran, and diethyl ether.
Examples of the ester include: ethyl acetate, butyl acetate, isobutyl acetate, 3-methyl-3-methoxybutyl acetate, gamma-butyrolactone, dimethyl adipate, dimethyl glutarate, dimethyl succinate, etc.
Examples of the aromatic solvent include: benzene, toluene, xylene, methylnaphthalene, dimethylnaphthalene, isopropylnaphthalene, diisopropylnaphthalene, ethylbiphenyl, diethylbiphenyl, solvent naphtha, and the like.
Examples of the halogenated hydrocarbon solvent include: carbon tetrachloride, chloroform, dichloromethane, and the like.
Examples of the polar organic solvent include: dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, N-methylpyrrolidone, and the like.
Of these, from the viewpoint of further improving the adsorption performance and the adsorption rate, at least 1 selected from the group consisting of water, a lower alcohol and a polyol is preferable, and water is more preferable. These solvents may be used alone, or 2 or more kinds may be used in combination.
In the above-mentioned adsorbents of the present invention, various additives widely and conventionally used for formulation, such as an antioxidant and a light stabilizer, may be blended in addition to known additives, for example, a nonvolatile acid and a chelating agent, depending on the purpose, use, and the like.
Preferred nonvolatile acids include succinic acid, fumaric acid, maleic acid, and boric acid, and salts thereof may also be used. These nonvolatile acids may be used alone in 1 kind, or in combination with 2 or more kinds. By blending the nonvolatile acid, the storage stability of the adsorbent can be further improved.
When a nonvolatile acid is used, the content thereof is not particularly limited, and is preferably about 1 to 10% by weight when the total amount of the adsorbent is 100% by weight.
Examples of the chelating agent include ethylenediaminetetraacetic acid, ethyleneglycoldiethylenediamine tetraacetic acid, oxalic acid, and citric acid, and salts thereof can also be used. These chelating agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds. By incorporating such a chelating agent, the storage stability of the adsorbent can be further improved.
When the chelating agent is used, the content thereof is not particularly limited, and is preferably about 1 to 10% by weight when the total amount of the adsorbent is 100% by weight.
Examples of the antioxidant include a phenol antioxidant, an amine antioxidant, and the like. Specific examples of the phenolic antioxidant include: 2, 6-di-tert-butyl-4-methylphenol, 2' -methylenebis (4-methyl-6-tert-butylphenol), and the like. In addition, specific examples of the amine-based antioxidant include: alkyldiphenylamines, N' -di-sec-butyl-p-phenylenediamine, and the like. These antioxidants may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
When an antioxidant is used, the content thereof is not particularly limited, and the total amount of the adsorbent is set to 100% by weight, preferably about 1 to 10% by weight.
Examples of the light stabilizer include: and hindered amine light stabilizers such as bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate. These light stabilizers may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
When the light stabilizer is used, the content thereof is not particularly limited, and is preferably about 1 to 10% by weight when the total amount of the adsorbent is 100% by weight.
These additives may be used alone or in combination according to the purpose.
The preparation of the above adsorbents of the present invention can be carried out under any conditions of cooling, room temperature and heating, but is preferably carried out at 5 to 40 ℃.
(1-5) method for producing adsorbent
The adsorbent of the present invention described above can be produced, for example, by a method including (II) a step of mixing the acid hydrazide compound and the silica.
The mixing method may be a usual method, and for example, mixing may be performed by a ball mill, a rod mill, a bead mill, a nauta mixer, a ribbon mixer, a V-type mixer, a rocking mixer, a high-speed mixer, a henschel mixer, a super mixer, a jet mill, an atomizer, a hammer mill, a screw feeder, a stirrer, a dancing agitator (dancing agitator), a double cone mixer, or the like.
For this mixing, wet blend and dry blend can be used. In the production method using wet blend, even when silica having a silanol group density of 5.0 or less is used, the density of the silanol group may sometimes be 5.0 or more when the silica is brought into contact with water, and thus dry blend is particularly preferably used. In this case, the decrease in storage stability due to the influence of moisture can be further suppressed, and the storage stability can be further improved not only at normal temperature but also at high temperature, and the coloring can be further suppressed while maintaining the adsorption performance.
The production method of the present invention preferably includes (I) a step of heating silica at 300 ℃ or higher before the step (II). As a result, a density of silanol groups on the surface of 5.0 pieces/nm can be obtained more reliably2The following silicon dioxide.
By heating at 300 ℃ or higher, the density of silanol groups on the surface can be further reduced, and the loss on ignition at 1050 ℃ as measured in accordance with JIS K1150-1994 can be further reduced, thereby further reducing the weight of silanol groups. In addition, the moisture content of the obtained adsorbent can be further reduced. The heating temperature is preferably 350 ℃ or higher, more preferably 400 ℃ or higher, from the viewpoint of more appropriately adjusting the density of silanol groups on the surface of silica, the loss on ignition at 1050 ℃, the weight of silanol groups, the specific surface area, and the like, to further improve the storage stability of the adsorbent of the present invention, and to further improve the adsorption performance of odor substances (aldehyde compounds and the like). The upper limit of the heating temperature is not particularly limited, but is usually preferably 1000 ℃ or lower, more preferably 900 ℃ or lower, and still more preferably 800 ℃ or lower. The heating time is preferably a time that can sufficiently reduce the density of silanol groups on the surface, and is preferably 5 minutes or longer, for example. The heating method is not particularly limited, and may be carried out by a conventionally known method such as a static method or a flow method. In particular, from the viewpoint of productivity, continuous furnace heating by a flow method is preferable.
Examples of the silica used in the step of heating at 300 ℃ or higher include wet-process silica (e.g., precipitated silica and gel-process silica), dry-process silica, and fused silica, and the wet-process silica is preferable from the viewpoint that silica having a silanol group density and/or a specific surface area in the above-described range can be easily prepared.
The density of silanol groups as the obtained surface was 5.0 pieces/nm2The following method of silica may be a method of reacting a compound of a silane coupling agent with silanol groups on the surface of silica (chemical modification method), in addition to the above-described method of heating at 300 ℃ or higher. Examples of silica usable in the chemical modification method include wet silica (e.g., precipitated silica and gel silica), dry silica, and fused silica.
The density of silanol groups as the obtained surface was 5.0 pieces/nm2The following method of silica is preferably a method of heating at 300 ℃ or higher because the chemical modification method causes problems such as changes in the surface properties of silica and the like and the remaining of chemical substances used for modification.
(1-6) odorant
The adsorbent of the present invention can effectively and rapidly adsorb an odorant (particularly, an aldehyde compound). In particular, the adsorbent of the present invention has excellent storage stability, and therefore can maintain the adsorption performance of an odorant (particularly, an aldehyde compound) for a long period of time not only at normal temperature but also at high temperature. The adsorbent of the present invention is effective for a combination of 1 or 2 or more of the above odorants.
The adsorbent to be adsorbed by the adsorbent of the present invention is not particularly limited, and examples thereof include aldehyde odorants (aldehyde compounds), and specifically include: aldehyde odorants (aldehyde compounds) such as formaldehyde, acetaldehyde, propionaldehyde, acrolein, n-butyraldehyde, isobutyraldehyde, 3-methyl-butyraldehyde, and crotonaldehyde; alcohols such as pentanal, hexanal, heptanal, octanal, nonanal, decanal; formic acid, and the like. Among them, the adsorbent of the present invention is particularly effective for adsorption of formaldehyde and/or acetaldehyde.
2. Industrial product containing adsorbent
The adsorbent of the present invention can be used in the form of being contained in (blended with) an industrial product. The industrial article comprises the present invention (industrial article of the present invention).
The industrial product refers to the widely known industrial products and industrial raw materials. Specifically, there may be mentioned: coating materials, adhesives, inks, sealants, paper products, adhesives, resin emulsions, pulp, wood materials, wood products, plastic products, films, wallpaper, building materials (interior materials, ceiling materials, flooring materials, etc.), fiber products, filters, and the like.
The content of the adsorbent of the present invention in the industrial product of the present invention is not particularly limited, and may be appropriately set according to the industrial product and the use thereof.
3. Method for adsorbing odorant using adsorbent
The method for adsorbing an odorant according to the present invention adsorbs an odorant by contacting a gas containing an aldehyde compound with the adsorbent according to the present invention. The adsorbent of the present invention efficiently and rapidly adsorbs an odorant (particularly, an aldehyde compound) by the adsorption method, and thus can efficiently and rapidly remove the odorant (particularly, the aldehyde compound). Further, the adsorbent of the present invention is excellent in storage stability not only at normal temperature but also at high temperature, and therefore can further maintain the adsorption performance of an odorant (e.g., an aldehyde compound). In the adsorption method of the present invention, the above-mentioned industrial product of the present invention containing the adsorbent of the present invention is brought into contact with a gas containing an odorous substance (particularly, an aldehyde compound), whereby the adsorbent is brought into contact with the above-mentioned odorous substance (particularly, an aldehyde compound), and as a result, the above-mentioned odorous substance can be efficiently adsorbed and removed.
Further, by filling the adsorbent in an adsorption apparatus such as a fixed bed, a moving bed or a fluidized bed, and subjecting a gas containing an odorous substance (particularly an aldehyde compound) to a treatment of introducing gas thereinto, the odorous substance can be adsorbed and removed efficiently and quickly for a long period of time.
Examples
The present invention will be specifically described below with reference to examples. However, it is obvious that the present invention is not limited to the embodiment described below.
The parameters of the silica used in the examples and comparative examples were measured by the following methods.
Number of silanol groups
The number of silanol groups in 1g of silica was calculated in accordance with JIS K1150-1994.
Specific surface area
The specific surface area of silica was measured by the BET method using nitrogen gas using TriStar3000 manufactured by Micromeritics.
Density of silanol group
The density of silanol groups (number of silanol groups/specific surface area) was calculated from the number of silanol groups and the specific surface area.
Loss on ignition at 1050 deg.C
The loss on ignition at 1050 ℃ of silica was measured in accordance with JIS K1150-1994.
Weight of silanol group
The weight (% by mass) of the silanol group was calculated from the loss on ignition at 1050 ℃ by the following equation.
(34/18) × (1050 ℃ loss on ignition)
Bulk density
The bulk density was measured according to JIS K6220-1: 20157.8.2.
Average particle diameter
Using a MalverMaster Sizer S manufactured by n corporation, and D was measured by a laser method50As the average particle diameter.
Comparative example 1
10 parts by mass of adipic acid dihydrazide and 100 parts by mass of silica (gel-process silica manufactured by Mizukasi K.K.; MIZUKASIL P-758C) were dry-mixed with a dancing stirrer to prepare an adsorbent of comparative example 1. The silica used was 8.9% by mass of the weight of silanol groups and had a specific surface area of 572m2Density of silanol groups/g 5.5/nm2A loss on ignition at 1050 ℃ of 4.7 mass% and a bulk density of 0.31g/cm3And an average particle diameter of 5.7. mu.m.
Comparative example 2
The adsorbent of comparative example 2 was obtained in the same manner as in comparative example 1 except that 50 parts by mass of a 20% aqueous solution of adipic acid dihydrazide (the content of adipic acid dihydrazide was 10 parts by mass) was used instead of the adipic acid dihydrazide and wet-mixed by a dancing stirrer.
Example 1
Silica (gel-process silica manufactured by Shuizuzuksil corporation; MIZUKASILP-758C) was heated at 400 ℃ for 1 hour in an atmospheric air. The adsorbent of example 1 was obtained in the same manner as in comparative example 1, except that the silica heated at 400 ℃. The silica used was 7.0 mass% in weight of silanol group and had a specific surface area of 570m2Density of silanol groups of 4.3 pieces/nm/g2A loss on ignition at 1050 ℃ of 3.7 mass% and a bulk density of 0.32g/cm3And an average particle diameter of 5.9. mu.m.
Example 2
Silica (gel method silica manufactured by zeo chemical corporation; MIZUKASILP-758C) was heated at 600 ℃ for 1 hour in an atmospheric air atmosphere. The adsorbent of example 2 was obtained in the same manner as in comparative example 1, except that the silica heated at 600 ℃. In addition, use twoThe silica content was 4.0% by mass based on the weight of silanol group and had a specific surface area of 555m2Density of silanol groups 2.5 per nm/g2A loss on ignition at 1050 ℃ of 2.1 mass% and a bulk density of 0.33g/cm3And an average particle size of 5.7. mu.m.
Example 3
Silica (gel-process silica manufactured by Shuizuzuksil corporation; MIZUKASILP-758C) was heated at 800 ℃ for 1 hour in an atmospheric air. An adsorbent of example 3 was obtained in the same manner as in comparative example 1, except that the silica heated at 800 ℃. The silica used was 1.9% by mass of the weight of silanol groups and had a specific surface area of 504m2Density of silanol groups/g 1.3/nm2A loss on ignition at 1050 ℃ of 1.0 mass% and a bulk density of 0.35g/cm3And an average particle diameter of 5.5. mu.m.
Comparative example 3
The same operation as in comparative example 1 was carried out except that MIZUKASIL P-758C was replaced with MIZUKASORB C-1, a gel process silica manufactured by Shuizhiki Kaisha, to obtain an adsorbent of comparative example 3. The silica used was 6.2% by mass of the weight of silanol groups and had a specific surface area of 370m2Density of silanol groups 6.0 pieces/nm2A loss on ignition at 1050 ℃ of 3.3 mass% and a bulk density of 0.22g/cm3The average particle diameter was 10.6. mu.m.
Example 4
Silica (gel-process silica manufactured by Shuizuzukorb C-1) was heated at 400 ℃ for 1 hour in an atmospheric atmosphere. An adsorbent of example 4 was obtained in the same manner as in comparative example 1, except that the silica heated at 400 ℃. The silica used was 4.3% by mass of the weight of silanol groups and had a specific surface area of 370m2Density of silanol groups/g and 4.2 groups/nm2A loss on ignition at 1050 ℃ of 2.3 mass% and a bulk density of 0.23g/cm3The average particle diameter was 10.6. mu.m.
Example 5
Silica (gel-process silica manufactured by Shuizuzukorb C-1) was heated at 600 ℃ for 1 hour in an atmospheric atmosphere. The same operation as in comparative example 1 was carried out except that the silica heated at 600 ℃ was used, thereby obtaining an adsorbent of example 5. The silica used was 2.5% by mass of the weight of silanol group and had a specific surface area of 377m2Density of silanol groups/g 2.3/nm2A loss on ignition at 1050 ℃ of 1.3 mass% and a bulk density of 0.24g/cm3The average particle diameter was 10.6. mu.m.
Example 6
Silica (gel-process silica manufactured by Mizukasorb C-1, manufactured by Mizu chemical Co., Ltd.) was heated (fired) at 800 ℃ for 1 hour in an atmospheric atmosphere. An adsorbent of example 6 was obtained in the same manner as in comparative example 1, except that the silica heated at 800 ℃. The silica used was 1.5% by mass of the weight of silanol groups and had a specific surface area of 350m2Density of silanol groups of 1.5 pieces/nm2A loss on ignition at 1050 ℃ of 0.8 mass% and a bulk density of 0.24g/cm3The average particle diameter was 10.2. mu.m.
Example 7
The adsorbent of example 7 was obtained in the same manner as in comparative example 1 except that MIZUKASIL P-758C was replaced with MIZUKASORB C-6, a gel process silica manufactured by Shuizhiki Kaisha. Further, the silica used was 3.2% by mass of the weight of silanol group and had a specific surface area of 366m2Density of silanol groups/g 3.1 pieces/nm2Loss on ignition at 1050 ℃ of 1.7 mass% and bulk density of 0.23g/cm3The average particle diameter was 10.5. mu.m.
Test example (moisture)
The volatile residue of the adsorbent heated at 105 ℃ for 2 hours was measured as water content.
Test example (storage stability (adipic acid dihydrazide survival rate))
The adsorbents obtained in examples 1 to 7 and comparative examples 1 to 3 were kept at 60 ℃ for 2 weeks. Thereafter, the residual level of adipic acid dihydrazide was determined by HPLC method for the adsorbent.
The physical properties of the silica used in each example and comparative example, the mixing ratio of the silica and adipic acid dihydrazide, the water content of each adsorbent, and the residual ratio of adipic acid dihydrazide are shown in table 1. In table 1, ADH represents adipic acid dihydrazide.
[ Table 1]
Test example (coloring)
About 5g of the sample was charged into Uni-Pak D-8, a product of Nikkimeda, and the color tone (L, a, b) of the sample was measured using a color measurement system CM-3500D. The color difference E was obtained from the hue before the experiment was conducted and the hue after the experiment was conducted, which were maintained at 60 ℃ for 2 weeks. The results are shown in Table 2.
Test example (acetaldehyde adsorption Performance)
77mg of the adsorbent of sampling examples 1 to 3 and comparative example 1 was placed in an aluminum dish, and the aluminum dish was sealed in a 1L Tydlar gas sampling bag, and then 1L of 1000ppm aldehyde gas was added. The gas injection was started, and the gas concentrations after 0.5 hour, 1.0 hour, 2.0 hours, 6.0 hours, and 24.0 hours were measured with time. The results are shown in Table 3.
The results of the coloring test and the acetaldehyde adsorption performance test of each adsorbent are shown in tables 2 and 3. In tables 2 and 3, ADH represents adipic acid dihydrazide.
[ Table 2]
[ Table 3]
As described above, the density of silanol groups on the surface of use is greater than 5.0 groups/nm2In comparative examples 1 to 3 of silica (A), when the silica was held at 60 ℃ for 2 weeks, the residual content of adipic acid dihydrazide was poor. Therefore, it is suggested that the adsorbents of comparative examples 1 to 3 hardly remain adipic acid dihydrazide, which has adsorption performance of an odorant (e.g., an aldehyde compound), and thus it is difficult to maintain the adsorption performance of the odorant (e.g., an aldehyde compound) for a long period of time. Further, the adsorbent of comparative example 1 could not suppress coloring. On the other hand, the density of silanol groups on the used surface was 5.0 pieces/nm2In examples 1 to 7 of the following silica, 89% or more of adipic acid dihydrazide was retained even after the silica was retained at 60 ℃ for 2 weeks. Therefore, the adsorbents of examples 1 to 7 use silica which is considered to be likely to decompose adipic acid dihydrazide in the prior art, but adipic acid dihydrazide is likely to remain having adsorption performance of an odorant (aldehyde compound or the like), and thus it is suggested that adsorption performance of the odorant (aldehyde compound or the like) can be maintained for a long period of time. Furthermore, the adsorbents of examples 1 to 3 can also suppress coloring. Therefore, in the adsorbent of the present invention, it is difficult to decompose adipic acid dihydrazide, so that the adsorption performance of an odorant (aldehyde compound or the like) is maintained for a long period of time, and coloring can be suppressed, and at the same time, characteristics such as heat resistance, which are the purpose of using silica, can be further provided.
Claims (11)
1. An adsorbent for odorous substances, which comprises an acid hydrazide compound and silica, and
the density of silanol groups on the surface of the silica is 5.0 groups/nm2In the following, the following description is given,
the adsorbent is produced by a production method comprising (II) a step of dry-mixing the acid hydrazide compound and the silica.
2. The adsorbent for odorant according to claim 1, wherein,
the water content is 5.0 mass% or less.
3. The adsorbent according to claim 1 or 2,
the silica is at least 1 selected from the group consisting of wet silica, dry silica and fused silica.
4. The adsorbent according to claim 1 or 2,
the acid hydrazide compound is at least 1 selected from the group consisting of carbodihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecane acid dihydrazide, and isophthalic acid dihydrazide.
5. The adsorbent according to claim 1 or 2,
the specific surface area of the silicon dioxide is 100-1000 m2/g。
6. The adsorbent according to claim 1 or 2,
the odor substance is an aldehyde compound.
7. The method for producing the adsorbent according to any one of claims 1 to 6,
the manufacturing method comprises: (II) a step of dry-mixing the acid hydrazide compound and the silica.
8. The manufacturing method according to claim 7,
prior to the step (II), the manufacturing method includes: (I) heating the silica at 300 ℃ or higher.
9. The manufacturing method according to claim 7 or 8,
the production method does not include a step of heating after the step (II).
10. An industrial article comprising the adsorbent according to any one of claims 1 to 6.
11. A method for adsorbing an odorant on an adsorbent, wherein the adsorbent according to any one of claims 1 to 6 is contacted with a gas containing an aldehyde compound to adsorb the odorant on the adsorbent.
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