CN109890500A - The adsorbent of odorous substance - Google Patents
The adsorbent of odorous substance Download PDFInfo
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- CN109890500A CN109890500A CN201780065808.XA CN201780065808A CN109890500A CN 109890500 A CN109890500 A CN 109890500A CN 201780065808 A CN201780065808 A CN 201780065808A CN 109890500 A CN109890500 A CN 109890500A
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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
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- 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
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Abstract
The present invention provides a kind of adsorbent of odorous substance, and containing sour hydrazide compound and silica, and the silanol group density on the surface of the silica is 5.0/nm2Below；Even if can also be improved storage-stable in the case where mixing hydrazine compound and silica.
Description
Technical field
The present invention relates to a kind of adsorbents of odorous substance.
Background technique
In recent years, demand of the consumer to smelly eliminating increasingly increases.Wherein, the aldehyde compounds such as formaldehyde, acetaldehyde are considered as disease
The reason of state synthetic building syndrome substance, be therefore the extra high object of demand to smelly eliminating for the difficult substance of adsorbent absorption
Matter.As the adsorbent of this odorous substance, such as it has been known that there is hydrazine compounds.
Wherein, adipic dihydrazide has good aldehyde absorption property.In addition, in the neutral region of adipic dihydrazide
Storage-stable is also high, it may have 200 DEG C or more of heat resistance (decomposition temperature in TG-DTA is 230~275 DEG C or so).
As described above, high absorption property can be obtained by using hydrazine compound, but absorption property is improved, adsorbed in turn
The demand that speed improves is still very high.For example, being assigned and being mixed hydrazine compound and silica in the prior art
Heat resistance improves absorption property.
But hydrazine compound storage-stable reduction under acidity or under alkalinity.Silica has as solid acid
Character, therefore, when being mixed hydrazine compound and silica, usual storage-stable is reduced, and therefore, will contain hydrazine
It is very difficult that the adsorbent of conjunction object and silica, which carries out commercialization,.Although in particular, storage-stable at room temperature sometimes
Property is not a problem, but in full summer at a high temperature of storage-stable seriously reduce sometimes, cannot fully adsorb aldehyde compound, cannot
Solve the problems, such as unhappy foul smell.In addition, it is also known that have the storage-stable of adjoint hydrazine compound reduce and the feelings that colour
Condition.For example, being recorded in patent document 1: although can imagine through inanimate matter powder (SiO2Deng) urging of having of pore surface
Dihydrazide compound is decomposed in agent effect, but details is not yet clear.In the patent document 1, by more with moisture quantitative change
Mode smelly eliminating composition is heated within specified temperatures and solves the technical problem, but can't inhibit hydrazine compound point
Solution will only be decomposed and be inhibited in minimum, and therefore, the improvement of storage-stable is insufficient.
Existing technical literature
Patent document
Patent document 1: International Publication No. 2013/118714
Summary of the invention
The technical problems to be solved by the invention
As described above, currently, hydrazine compound cannot be inhibited in the case where being mixed hydrazine compound and silica
Decomposition.It reduces and colours with the storage-stable of hydrazine compound.In order to avoid coloring, the storage of hydrazine compound is improved
Stability is necessary.
Therefore, the object of the present invention is to provide a kind of adsorbents of odorous substance (aldehyde compound etc.), even if will
In the case that hydrazine compound and silica are mixed, storage-stable can also be improved, it can also be to avoid coloring.
Technical teaching for solving the problem was
To achieve the goals above, further investigation has been repeated in the inventors of the present invention, as a result, it has been found that: by using surface
Silanol group density is 5.0/nm2Silica below, even if in the feelings for mixing hydrazine compound and silica
Under condition, storage-stable can also be improved, it can also be to avoid coloring.The present inventor is based on above-mentioned discovery, is further repeated
Research, completes the present invention.That is, the present invention includes content as shown below.
A kind of 1. adsorbents of odorous substance of item, containing sour hydrazide compound and silica, and
The silanol group density on the surface of the silica is 5.0/nm2Below.
The adsorbent of 2. odorous substances according to item 1 of item, wherein moisture is 5.0 mass % or less.
3. adsorbents according to item 1 or 2 of item, wherein the silica is selected from by wet silica, dry method dioxy
It is at least one kind of in the group that SiClx and vitreous silica are constituted.
4. adsorbents according to any one of item 1~3 of item, wherein the acid hydrazide compound is selected from by carbazide
(carbodihydrazide), acid dihydrazide, amber acid dihydrazide, adipic dihydrazide, sebacic dihydrazide, dodecane
It is at least one kind of in the group that dihydrazi and isophthalic dihydrazide are constituted.
5. adsorbents according to any one of item 1~4, wherein the specific surface area of the silica is 100~
1000m2/g。
6. adsorbents according to any one of item 1~5 of item, wherein the odorous substance is aldehyde compound.
The manufacturing method of 7. adsorbents according to any one of item 1~6 of item, the manufacturing method have (II) for the acid
The process that hydrazide compound and the silica are mixed.
8. manufacturing methods according to item 7 of item, wherein
Before the process (II),
The manufacturing method has the process that (I) heats silica at 300 DEG C or more.
9. manufacturing methods according to item 7 or 8 of item, wherein
After the process (II), the manufacturing method does not include the process heated.
A kind of 10. industrial products of item, contain adsorbent described in any one of item 1~6.
A kind of sides for making odorous substance be adsorbed in adsorbent and making the gas containing aldehyde compound and adsorbent contacts of item 11.
Method, wherein
The adsorbent contains sour hydrazide compound and silica, and the silanol group density on the surface of the silica is
5.0/nm2Below.
Invention effect
Since the silanol group density that adsorbent of the invention contains sour hydrazide compound and surface is 5.0/nm2Below
Silica can also be to avoid coloring it is thus possible to improve storage-stable.
Specific embodiment
1. adsorbent
Adsorbent of the invention is the silanol group on the surface containing sour hydrazide compound and silica and the silica
Density is 5.0/nm2The adsorbent of odorous substance below.
Since adsorbent of the invention uses the silanol group density on surface for 5.0/nm2Silica below, because
This, although containing sour hydrazide compound and silica, excellent storage stability can also be to avoid coloring.
(1-1) acid hydrazide compound
It as sour hydrazide compound, is not particularly limited, compound commonly known in the art can be used.For example, can make
With the single hydrazide compound of acid in molecule with 1 hydrazide group, the acid dihydrazide compound in molecule with 2 hydrazide groups, point
With three hydrazide compound of acid etc. of 3 hydrazide groups in son.Wherein, from the absorption property of odorous substance (aldehyde compound etc.), suction
The viewpoints such as attached dose of storage-stable, coloring inhibition are set out, preferred acid dihydrazide compound or sour three hydrazide compounds.Wherein,
Acid dihydrazide compound preferred generic compound.The acid hydrazide compound is the work with absorption odorous substance (aldehyde compound etc.)
Compound.
The molecular weight of sour hydrazide compound is from the viewpoint of absorption property and adsorption rate, such as preferably 30 or more, more
It is preferred that 60 or more, further preferred 90 or more.In addition, sight of the molecular weight of sour hydrazide compound from absorption property and adsorption rate
Point sets out, such as preferably 300 hereinafter, more preferable 280 hereinafter, further preferred 260 or less.In addition, as additional performance,
In terms of heat resistance and the viewpoint of storage-stable, the molecular weight of sour hydrazide compound such as preferably 100 or more, more preferable 130 with
On.In addition, as additional performance, in terms of heat resistance and the viewpoint of storage-stable, the molecular weight of sour hydrazide compound
As preferably 300 hereinafter, more preferable 270 or less.
As this sour hydrazide compound, specifically, can enumerate: carbazide, acid dihydrazide, two acyl of succinic acid
Hydrazine, adipic dihydrazide, sebacic dihydrazide, two hydrazides of dodecanedioic acid, isophthalic dihydrazide, three hydrazides of citric acid,
Three hydrazides of Pyromellitic Acid, three hydrazides of 1,2,4 benzenetricarboxylic acid, three hydrazides of nitrilotriacetic acid, 1,3,5- cyclohexanetricarboxylic acid three
Hydrazides etc..Wherein, from the balancing good of safety, absorption property, adsorption rate, coloring inhibition, heat resistance and storage-stable
Viewpoint is set out, preferably adipic dihydrazide, amber acid dihydrazide.These sour hydrazide compounds can be used alone, can also group
It closes two or more and uses.
The content of sour hydrazide compound from further increase absorption property, adsorption rate, coloring inhibit, heat resistance and storage
From the perspective of stability, relative to aftermentioned 00 mass parts of silica 1, such as more than preferably 2 mass parts, more preferable 3 matter
Part or more is measured, more than further preferred 5 mass parts.In addition, the content of sour hydrazide compound is from further increasing absorption property, inhale
From the perspective of attached speed, heat resistance and storage-stable, relative to aftermentioned 00 mass parts of silica 1, such as preferably 80
Below the mass, more preferable 40 below the mass, and further preferred 20 below the mass.
The content of sour hydrazide compound in adsorbent of the invention is not particularly limited, from further increasing adsorptivity
Energy, adsorption rate, coloring inhibit, from the perspective of heat resistance and storage-stable, when the total amount of adsorbent is set as 100 matter
When measuring %, such as preferably 0.1 mass % or more, more preferable 1.0 mass % or more, further preferred 3.0 mass % or more.Separately
Outside, the content of the sour hydrazide compound in adsorbent of the invention is not particularly limited, from further increase absorption property, absorption
From the perspective of speed, heat resistance and storage-stable, when the total amount of adsorbent is set as 100 mass %, such as preferably
90.0 mass % hereinafter, more preferable 50.0 mass % hereinafter, further preferred 20.0 mass % or less.
(1-2) silica
The silanol group density on its surface of silica that adsorbent of the invention has is 5.0/nm2Below.
Silanol group density means: by using nitrogen BET method measure silica dioxide granule specific surface area and according to
1nm that the silanol group quantity of JIS K 1150-1994 measurement calculates, every2Silica dioxide granule surface area on silanol
The number of base.
When the silanol group density is more, in the case where being mixed with sour hydrazide compound, sour hydrazide compound destabilization,
Therefore, the storage-stable of the adsorbent obtained becomes insufficient, becomes easy coloring.From this point of view, silicon dioxide meter
The silanol group density in face is 5.0/nm2Hereinafter, preferably 4.8/nm2Hereinafter, more preferably 4.5/nm2Below.It is another
Aspect is not particularly limited the lower limit value of the silanol group density of silica surface, usually 0.1/nm2More than,
Preferably 1.4/nm2More than, more preferably 2.6/nm2More than.
Silica used in the present invention from further increase absorption property, adsorption rate, coloring inhibit, heat resistance and
From the perspective of storage-stable, according to 1050 DEG C of loss on ignitions that JIS K 1150-1994 is measured be preferably 4.0 mass % with
Under, more preferably 3.7 mass % are hereinafter, further preferably 3.0 mass % or less.In addition, titanium dioxide used in the present invention
The lower limit value of 1050 DEG C of loss on ignitions according to JIS K 1150-1994 measurement of silicon is not particularly limited, it is often preferred that 0.2 matter
Measure % or more, more preferably 0.5 mass % or more, further preferably 0.8 mass % or more.1050 DEG C of burnings of silica are lost
Amount is measured according to JIS K 1150-1994.
Silica used in the present invention from further increase absorption property, coloring inhibition, adsorption rate, heat resistance and
From the perspective of storage-stable, preferably specific surface area is 1000m2/ g is hereinafter, more preferably 600m2/ g is hereinafter, further preferably
For 570m2/ g or less.In addition, the lower limit value of the specific surface area of silica used in the present invention is from further increasing adsorptivity
From the perspective of, colouring inhibition, adsorption rate, heat resistance and storage-stable, preferably 100m2/ g or more, more preferably
200m2/ g or more, further preferably 300m2/ g or more.The specific surface area of silica using the BET method of nitrogen by being surveyed
It is fixed.
Silica used in the present invention from further increase absorption property, coloring inhibition, adsorption rate, heat resistance and
From the perspective of storage-stable, preferably average grain diameter is 3.0 μm or more, more preferable 5.0 μm or more.In addition, making in the present invention
Silica goes out from the viewpoint for further increasing absorption property, coloring inhibition, adsorption rate, heat resistance and storage-stable
Hair, average grain diameter is preferably 20.0 μm hereinafter, more preferable 15.0 μm or less.In the present invention, the D50 of laser method measurement will be utilized
It is set as the average grain diameter of silica.
It as this silica, can enumerate for example: wet silica (precipitated silica, gel method titanium dioxide
Silicon etc.), dry silica, vitreous silica etc..Especially it is easy to control the wet silica (precipitation method of silanol group density
Silica, gel silica etc.) be it is preferable to use.Particularly, by by these silica in aftermentioned condition
Under heated, silanol group density can be further decreased, hydrazine compound is more stabilized, coloring is further suppressed.
The content of silica in adsorbent of the invention is not particularly limited, from further increase absorption property, inhale
Attached speed, coloring inhibit, from the perspective of heat resistance and storage-stable, when the total amount of adsorbent is set as 100 mass %,
Such as preferably 10.0 mass % or more, more preferable 50.0 mass % or more, further preferred 80.0 mass % or more.In addition, this
The content of silica in the adsorbent of invention is not particularly limited, from further increasing absorption property, adsorption rate, coloring
Inhibit, from the perspective of heat resistance and storage-stable, when the total amount of adsorbent is set as 100 mass %, such as preferably
99.9 mass % hereinafter, more preferable 99.0 mass % hereinafter, further preferred 97.0 mass % or less.
(1-3) supports the adsorbent in carrier
In the present invention, the carrier due to above-mentioned silica as above-mentioned sour hydrazide compound works, it can will be
It is supported on above-mentioned silica and (adds attachment) and be used as adsorbent after having above-mentioned sour hydrazide compound (hereinafter, sometimes referred to as " supporting
Adsorbent ").Alternatively, it is also possible to use the carrier other than silica.
It in the case where the porous carrier other than using silica, as porous carrier, is not particularly limited, makees
Well known carrier can generally be widely used for carrier, can enumerate for example: zeolite, ceramics, diatomite, active carbon, glues aluminium oxide
Soil, talcum, calcium carbonate etc..These porous carriers also can be used alone, and can also combine two or more and use.
Adsorbent of the invention is from further increasing storage-stable, absorption property, adsorption rate and further suppress
From the perspective of color, preferably moisture is 5.0 mass % hereinafter, more preferably 4.4 mass % are hereinafter, further preferably 3.0 matter
Measure % or less.In addition, the lower limit value of the moisture of adsorbent of the invention is not particularly limited, it is often preferred that 0.1 mass % with
On, more preferably 0.2 mass % or more, further preferably 0.3 mass % or more.The moisture of adsorbent of the invention according to
Volatile matter after heating 2 hours at 105 DEG C is measured.
In order to manufacture the adsorbent of the invention for having above-mentioned condition, as described above, it is preferred to use the silanol group on surface
Density is 5.0/nm2Silica below.The hygroscopicity of this silica is controlled, and thus, it is possible to adjust (reduction)
The moisture of adsorbent of the invention.
(1-4) suspending agent adsorbent, powder adsorbent or particle (pellet) adsorbent
In the present invention, manufacture it is above-mentioned support adsorbent after, solvent can also be scattered in and form suspending agent, as
Adsorbent uses.It is used alternatively, it is also possible to be mixed with powder as pulvis.Alternatively, it is also possible to be used as particle.
It as above-mentioned solvent, can enumerate for example: water, lower alcohol, polyalcohol, ketone, ether, ester, aromatic solvent, halogenated hydrocarbons
Class solvent, polar organic solvent etc..
As lower alcohol, the alcohol of such as straight or branched alkyl with carbon atom number 1~4 can be enumerated.Specifically,
Methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol etc. can be enumerated.
It as polyalcohol, can enumerate for example: ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, poly- the third two
Alcohol, 1,3 butylene glycol, 1,4- butanediol, 1,5- pentanediol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, two
Glycol monoethyl ether, diethylene glycol monoethyl ether etc..
As ketone, can enumerate for example: acetone, methyl ethyl ketone, methylisobutylketone, propylene carbonate etc..
As ether, can enumerate such as dioxanes, tetrahydrofuran, diethyl ether.
It as ester, can enumerate for example: ethyl acetate, butyl acetate, isobutyl acetate, 3- methyl -3- methoxyacetic acid fourth
Ester, gamma-butyrolacton, dimethyl adipate, dimethyl glutarate, dimethyl succinate etc..
As aromatic solvent, can enumerate for example: benzene,toluene,xylene, methyl naphthalene, dimethylnaphthalene, isopropyl naphthalene,
Diisopropyl naphthalene, ethyl biphenyl, diethyl biphenyl, solvent naphtha etc..
As halogenated hydrocarbon solvent, can enumerate for example: carbon tetrachloride, chloroform, methylene chloride etc..
As polar organic solvent, can enumerate for example: dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, second
Nitrile, N-Methyl pyrrolidone etc..
In these, from the viewpoint of further increasing absorption property and adsorption rate, be preferably selected from by water, lower alcohol and
At least one kind of, the more preferable water in group that polyalcohol is constituted.These solvents also can be used alone, two or more can also be combined and
It uses.
In above-mentioned various adsorbents of the invention, according to its purpose, purposes etc., in the well known additive of cooperation, for example
Other than the acid of fixedness, chelating agent, antioxidant, light stabilizer etc. can also be cooperated extensively and conventionally used for formulation each
Kind additive.
The acid of preferred fixedness can enumerate succinic acid, fumaric acid, maleic acid, boric acid etc., can also use theirs
Salt.The acid of these fixednesies can also be used alone with a kind, two or more can also be applied in combination.It is above-mentioned non-volatile by cooperating
The acid of property, can further improve the storage-stable of adsorbent.
Using the acid of fixedness, content is not particularly limited, when the total amount of adsorbent is set as 100
When weight %, preferably 1~10 weight % or so.
As chelating agent, such as ethylenediamine tetra-acetic acid, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA), oxalic acid, citric acid can be enumerated
Deng their salt can also be used.These chelating agents also can be used singly or in combination of two or more.Pass through
Cooperate this chelating agent, can more improve the storage-stable of adsorbent.
In the case where using chelating agent, content is not particularly limited, when the total amount of adsorbent is set as 100 weight %
When, preferably 1~10 weight % or so.
As antioxidant, can enumerate such as phenol antioxidant, amine antioxidants.As phenol antioxidant,
Specifically, can enumerate: 2,6-Di-tert-butyl-4-methylphenol, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol)
Deng.In addition, as amine antioxidants, specifically, can enumerate: alkyl diphenyl base amine, N, N '-di-sec-butyl-p-phenylenediamine
Deng.These antioxidants also can be used singly or in combination of two or more.
In the case where using antioxidant, content is not particularly limited, and the total amount of adsorbent is set as 100 weight %,
It is preferred that 1~10 weight % or so.
It as light stabilizer, can enumerate for example: the amine system of being obstructed such as bis- (2,2,6,6- tetramethyl -4- piperidyl) sebacates
Light stabilizer etc..These light stabilizers also can be used singly or in combination of two or more.
Using light stabilizer, content is not particularly limited, when the total amount of adsorbent is set as 100 weights
When measuring %, preferably 1~10 weight % or so.
These additives also can be used alone, and can also be used in combination according to purpose.
Above-mentioned various adsorbents of the invention preparation can under cooling, at room temperature and heating under either condition under into
Row, but preferably carried out at 5~40 DEG C.
The manufacturing method of (1-5) adsorbent
The adsorbent of present invention mentioned above for example can be by having (II) for the sour hydrazide compound and the dioxy
The method of the process that SiClx is mixed manufactures.
Mixed method can use usual way, such as can use ball mill, rod mill, ball mill, Nuo Ta mixing
Machine, ribbon blender, V-Mixer, Rocking Mixer, high-speed mixer, Henschel mixer, super mixing machine, injection
Mill, atomizer, hammer-mill, screw feeder, blender, dancing blender (dancing agitator), double cone mixer
Etc. being mixed.
For should mixing, wet blend (wet mixed) and dry blend (dry type mixing) can be used.For
Using the manufacturing method of wet blend (wet mixed), even if the use of silanol group density being 5.0 silica below
In the case of, it also will appear the situation that the silanol group density if contacting with water can reach 5.0 or more sometimes, it is therefore, especially excellent
Choosing is using dry blend (dry type mixing).In this case, storage-stable caused by the influence of moisture can be further suppressed
The reduction of property, not only at normal temperature, but also also can be further improved storage-stable at high temperature, can maintain adsorptivity
Can, and can also further suppress coloring.
In addition, the manufacturing method of the present invention preferably have before the above-mentioned operation (II) (I) by silica 300 DEG C with
On the process that is heated.Thus, it is possible to which the silanol group density for more reliably obtaining surface is 5.0/nm2Dioxy below
SiClx.
By being heated at 300 DEG C or more, the silanol group density on surface can be further decreased, root is further decreased
According to 1050 DEG C of loss on ignitions that JIS K 1150-1994 is measured, silanol group weight is further decreased.Furthermore it is possible to further drop
The moisture of low obtained adsorbent.Heating temperature from more suitably adjust silica surface silanol group density, 1050 DEG C
Loss on ignition, silanol group weight, specific surface area etc. further increase the storage-stable of adsorbent of the invention, and further
From the perspective of the absorption property for improving odorous substance (aldehyde compound etc.), preferably 350 DEG C or more, more preferable 400 DEG C or more.Separately
Outside, the upper limit value of heating temperature is not particularly limited, it is often preferred that 1000 DEG C hereinafter, more preferable 900 DEG C hereinafter, further it is excellent
Select 800 DEG C or less.In addition, heating time is preferably set to fully reduce the time of the silanol group density on surface, such as
It is preferred that 5 minutes or more.In addition, heating means are not particularly limited, the conventionally known method such as settled process, flow method can use
It carries out.Particularly, it from the viewpoint of productivity, is heated preferably by the continous way kiln of flow method.
As the silica for the above-mentioned process heated at 300 DEG C or more, such as wet process titanium dioxide can be enumerated
Silicon (precipitated silica, gel silica etc.), dry silica, vitreous silica etc., from can easily prepare
From the perspective of the silica of silanol group density and/or specific surface area with above range, preferred wet silica.
It is 5.0/nm as the silanol group density for obtaining surface2The method of silica below, except above-mentioned 300
DEG C or more other than the method that is heated, the silanol group of the compound and silica surface that make silane coupling agent can also be enumerated
The method (chemic modified method) of reaction.As the silica that can be used in the chemic modified method, such as wet process two can be enumerated
Silica (precipitated silica, gel silica etc.), dry silica, vitreous silica etc..
It is 5.0/nm as the silanol group density for obtaining surface2The method of silica below, since chemistry changes
The problem of property method can bring the chemical residue for variation or the modification of silica surface physical property etc., therefore preferably exist
300 DEG C or more the methods heated.
(1-6) odorous substance
The adsorbent of aforementioned present invention can effectively and quickly adsorb odorous substance (especially aldehyde compound).Especially this hair
Bright adsorbent due to excellent storage stability, can also not only maintain foul smell for a long time at normal temperature but also at high temperature
The absorption property of substance (especially aldehyde compound).In addition, adsorbent of the invention have to combination it is one kind or two or more above-mentioned
Odorous substance is effective.
It as the adsorbent with adsorbent object of the invention, is not particularly limited, such as aldehydes can be enumerated
Odorous substance (aldehyde compound) etc., specifically, can enumerate: formaldehyde, acetaldehyde, propionic aldehyde, methacrylaldehyde, n-butanal, isobutylaldehyde, 3- first
The aldehyde odours such as base-butyraldehyde, crotonaldehyde substance (aldehyde compound)；The alcohol such as valeral, hexanal, enanthaldehyde, octanal, aldehyde C-9, capraldehyde；Formic acid
Deng.Wherein, the absorption of adsorbent PARA FORMALDEHYDE PRILLS(91,95) and/or acetaldehyde of the invention is particularly effective.
2. the industrial product containing adsorbent
Adsorbent of the invention can contain (cooperation) in industrial product and use.The industrial product includes (this hair of the invention
Bright industrial product).
The industrial product refers to widely known at present industrial product and the raw material of industry.Specifically, can enumerate: applying
Material, bonding agent, ink, sealant, paper products, adhesive, resin emulsion, paper pulp, wood materials, timber product, plastic products,
Film, wallpaper, construction material (built-in material, ceiling tile materials, flooring material etc.), fibre, filter etc..
In industrial product of the invention, the content of adsorbent of the invention is not particularly limited, can be according to industrial product
And its usage and suitably set.
3. the adsorption method of the odorous substance using adsorbent
The adsorption method of odorous substance of the invention is and contacting the gas containing aldehyde compound and adsorbent of the invention
Odorous substance is set to be adsorbed in adsorbent of the invention.By above-mentioned adsorption method, adsorbent of the invention effectively and quickly is inhaled
Attached odorous substance (especially aldehyde compound), therefore, can effectively and quickly removing above-mentioned odorous substance, (especially hydroformylation is closed
Object).In addition, not only excellent storage stability therefore can be into one at normal temperature but also at high temperature for adsorbent of the invention
Step maintains the absorption property of odorous substance (aldehyde compound etc.).In adsorption method of the invention, by making containing of the invention
The above-mentioned industrial product of the invention of adsorbent is contacted with the gas containing odorous substance (especially aldehyde compound), adsorbent
It is contacted with above-mentioned odorous substance (especially aldehyde compound), as a result, above-mentioned odorous substance can also be effectively adsorbed and removed.
In addition, odorous substance (especially aldehyde will be contained by being filled in the adsorbent equipments such as fixed bed, moving bed, fluidized bed
Compound) gas carry out ventilation treatment thereto, can also effectively and quickly and for a long time be adsorbed and removed above-mentioned foul smell
Substance.
Embodiment
Hereinafter, specifically describing the present invention by showing embodiment.It will, however, be evident that the present invention does not limit
In the mode of embodiment below.
Each parameter of silica used in Examples and Comparative Examples is measured with the following method.
Silanol group quantity
According to JIS K 1150-1994, the silanol group quantity in 1g silica is calculated.
Specific surface area
Using Micromeritics corporation TriStar3000, by the specific surface of the BET method measurement silica using nitrogen
Product.
Silanol group density
Silanol group density (silanol group quantity/specific surface area) is calculated by silanol group quantity and specific surface area.
1050 DEG C of loss on ignitions
According to JIS K 1150-1994,1050 DEG C of loss on ignitions of silica are measured.
Silanol group weight
By 1050 DEG C of loss on ignitions, silanol group weight (quality %) is calculated with following formula.
(34/18) × (1050 DEG C of loss on ignitions)
Bulk density
According to JIS K 6220-1:2015 7.8.2, bulk density is measured.
Average grain diameter
Using Malvern corporation Master Sizer S, D is measured using laser method50, as average grain diameter.
Comparative example 1
By silica (Suisawa Chemical Industry Co., Ltd.'s gel of the adipic dihydrazide of 10 mass parts and 100 mass parts
Method silica；MIZUKASIL P-758C) using dancing blender carry out dry type mixing, adsorbent as comparative example 1.Separately
Outside, the silica used is 8.9 mass % of silanol group weight, specific surface area 572m2/ g, silanol group density 5.5/
nm2, 1050 DEG C of 4.7 mass % of loss on ignition, bulk density 0.31g/cm3, 5.7 μm of average grain diameter.
Comparative example 2
Replace adipic dihydrazide, uses 20% aqueous solution, the 50 mass parts (content of adipic dihydrazide of adipic dihydrazide
For 10 mass parts), wet mixed, which is carried out, using dancing blender in addition to this operates in the same way, compared with comparative example 1
The adsorbent of example 2.
Embodiment 1
By silica (Suisawa Chemical Industry Co., Ltd.'s gel silica；MIZUKASILP-758C) in atmosphere gas
It is heated 1 hour under atmosphere, at 400 DEG C.In addition to using such silica heated at 400 DEG C that passes through as two
It except silica, is operated in the same way with comparative example 1, obtains the adsorbent of embodiment 1.In addition, the silica used is silane
7.0 mass % of alcohol radical weight, specific surface area 570m24.3/g, silanol group density/nm2, 1050 DEG C of 3.7 mass % of loss on ignition,
Bulk density 0.32g/cm3, 5.9 μm of average grain diameter.
Embodiment 2
By silica (Suisawa Chemical Industry Co., Ltd.'s gel silica；MIZUKASILP-758C) in atmosphere gas
It is heated 1 hour under atmosphere, at 600 DEG C.In addition to using such silica heated at 600 DEG C as titanium dioxide
It except silicon, is operated in the same way with comparative example 1, obtains the adsorbent of embodiment 2.In addition, the silica used is silanol group
4.0 mass % of weight, specific surface area 555m22.5/g, silanol group density/nm2, 1050 DEG C of 2.1 mass % of loss on ignition, accumulation
Density 0.33g/cm3, 5.7 μm of average grain diameter.
Embodiment 3
By silica (Suisawa Chemical Industry Co., Ltd.'s gel silica；MIZUKASILP-758C) in atmosphere gas
It is heated 1 hour under atmosphere, at 800 DEG C.In addition to using such silica heated at 800 DEG C as titanium dioxide
It except silicon, is operated in the same way with comparative example 1, obtains the adsorbent of embodiment 3.In addition, the silica used is silanol group
1.9 mass % of weight, specific surface area 504m21.3/g, silanol group density/nm2, 1050 DEG C of 1.0 mass % of loss on ignition, accumulation
Density 0.35g/cm3, 5.5 μm of average grain diameter.
Comparative example 3
Suisawa Chemical Industry Co., Ltd.'s gel method titanium dioxide is used instead of MIZUKASIL P-758C as silica
In addition to this silicon MIZUKASORB C-1 is operated in the same way with comparative example 1, obtain the adsorbent of comparative example 3.In addition, use
Silica is 6.2 mass % of silanol group weight, specific surface area 370m26.0/g, silanol group density/nm2, 1050 DEG C burn
3.3 mass % of vector, bulk density 0.22g/cm3, 10.6 μm of average grain diameter.
Embodiment 4
By silica (Suisawa Chemical Industry Co., Ltd.'s gel silica；MIZUKASORB C-1) in air atmosphere
Under, heat 1 hour at 400 DEG C.In addition to using such silica heated at 400 DEG C as silica
Except, it is operated in the same way with comparative example 1, obtains the adsorbent of embodiment 4.In addition, the silica used is silanol base weight
Measure 4.3 mass %, specific surface area 370m24.2/g, silanol group density/nm2, 1050 DEG C of 2.3 mass % of loss on ignition, accumulation it is close
Spend 0.23g/cm3, 10.6 μm of average grain diameter.
Embodiment 5
By silica (Suisawa Chemical Industry Co., Ltd.'s gel silica；MIZUKASORB C-1) in air atmosphere
Under, heat 1 hour at 600 DEG C.Other than using such silica heated at 600 DEG C, compared with
Example 1 operates in the same way, and obtains the adsorbent of embodiment 5.In addition, the silica used be 2.5 mass % of silanol group weight,
Specific surface area 377m22.3/g, silanol group density/nm2, 1050 DEG C of 1.3 mass % of loss on ignition, bulk density 0.24g/cm3、
10.6 μm of average grain diameter.
Embodiment 6
By silica (Suisawa Chemical Industry Co., Ltd.'s gel silica；MIZUKASORB C-1) in air atmosphere
Under, at 800 DEG C heat (firing) 1 hour.In addition to using such silica heated at 800 DEG C as two
It except silica, is operated in the same way with comparative example 1, obtains the adsorbent of embodiment 6.In addition, the silica used is silane
1.5 mass % of alcohol radical weight, specific surface area 350m21.5/g, silanol group density/nm2, 1050 DEG C of 0.8 mass % of loss on ignition,
Bulk density 0.24g/cm3, 10.2 μm of average grain diameter.
Embodiment 7
Suisawa Chemical Industry Co., Ltd.'s gel method titanium dioxide is used instead of MIZUKASIL P-758C as silica
In addition to this silicon MIZUKASORB C-6 is operated in the same way with comparative example 1, obtain the adsorbent of embodiment 7.In addition, use
Silica is 3.2 mass % of silanol group weight, specific surface area 366m23.1/g, silanol group density/nm2, 1050 DEG C burn
1.7 mass % of vector, bulk density 0.23g/cm3, 10.5 μm of average grain diameter.
Test example (moisture)
Residual point of volatilization after heating adsorbent 2 hours at 105 DEG C is measured, as moisture.
Test example (storage-stable (adipic dihydrazide survival rate))
Adsorbent obtained in Examples 1 to 7 and comparative example 1~3 is kept for 2 weeks at 60 DEG C.Thereafter, it to adsorbent, utilizes
HPLC method finds out the remaining degree of adipic dihydrazide.
By the mixed of silica used in each Examples and Comparative Examples and its physical property, silica and adipic dihydrazide
Composition and division in a proportion example, the amount of moisture of each adsorbent and adipic dihydrazide survival rate are shown in table 1.In addition, ADH indicates adipic acid two in table 1
Hydrazides.
[table 1]
Test example (coloring)
About 5g sample is packed into production Japan society Uni-Pak D-8, is surveyed with Konica Minolta society color measurement system CM-3500d
The tone (L*, a*, b*) of random sample product.After tone and experiment before being carried out by the experiment kept at 60 DEG C 2 weeks carry out
Tone finds out color difference E*.Show the result in table 2.
Test example (acetaldehyde absorption property)
The adsorbent 77mg of sampling Examples 1 to 3 and comparative example 1 is placed in aluminum dish, is enclosed in 1L Tedlar gas sampling
After bag, 1000ppm aldehyde gas 1L is added.It is set as initial when injecting a gas into, after timely measuring 0.5 hour, 1.0 hours
Afterwards, the gas concentration after 2.0 hours, after 6.0 hours and after 24.0 hours.Show the result in table 3.
The test result of the staining test of each adsorbent and acetaldehyde absorption property is shown in table 2 and 3.In addition, in table 2 and 3
In, ADH indicates adipic dihydrazide.
[table 2]
[table 3]
As described above, being greater than 5.0/nm using the silanol group density on surface2Silica comparative example 1~3
In, in the case where 2 weeks are kept at 60 DEG C, adipic dihydrazide survival rate is poor.Therefore, in the adsorbent of comparative example 1~3, tool
There is the adipic dihydrazide of the absorption property of odorous substance (aldehyde compound etc.) to be not easy remaining, therefore, implies comparative example 1~3
Adsorbent is difficult to maintain the absorption property of odorous substance (aldehyde compound etc.) for a long time.Moreover, the adsorbent of comparative example 1 is not yet
It can inhibit coloring.It on the other hand, is 5.0/nm in the silanol group density using surface2The embodiment of silica below
In 1~7, even if after keeping 2 weeks at 60 DEG C, still being able to keep 89% or more adipic dihydrazide.Therefore, Examples 1 to 7
Adsorbent although used and think to be easy the silica for making adipic dihydrazide decompose in the prior art, still, tool
There is the adipic dihydrazide of the absorption property of odorous substance (aldehyde compound etc.) to be easy remaining, therefore, implies that it can be tieed up for a long time
Hold the absorption property of odorous substance (aldehyde compound etc.).Moreover, the adsorbent of Examples 1 to 3 can also inhibit to colour.Therefore,
In adsorbent of the invention, become difficult the decomposition of adipic dihydrazide, to maintain odorous substance (aldehyde compound for a long time
Deng) absorption property, can also inhibit to colour, at the same time, can also further assign as the purpose for using silica
The characteristics such as heat resistance.
Claims (11)
1. a kind of adsorbent of odorous substance, containing sour hydrazide compound and silica, and
The silanol group density on the surface of the silica is 5.0/nm2Below.
2. the adsorbent of odorous substance according to claim 1, wherein
Moisture is 5.0 mass % or less.
3. adsorbent according to claim 1 or 2, wherein
The silica is at least 1 in the group being made of wet silica, dry silica and vitreous silica
Kind.
4. adsorbent described in any one of claim 1 to 3, wherein
It is described acid hydrazide compound be selected from by carbazide, acid dihydrazide, amber acid dihydrazide, adipic dihydrazide,
It is at least one kind of in the group of sebacic dihydrazide, two hydrazides of dodecanedioic acid and isophthalic dihydrazide composition.
5. adsorbent according to any one of claims 1 to 4, wherein
The specific surface area of the silica is 100~1000m2/g。
6. adsorbent according to any one of claims 1 to 5, wherein
The odorous substance is aldehyde compound.
7. the manufacturing method of adsorbent described according to claim 1~any one of 6, wherein
The manufacturing method has: the process that (II) mixes the sour hydrazide compound and the silica.
8. manufacturing method according to claim 7, wherein
Before the process (II), the manufacturing method has: the work that (I) heats silica at 300 DEG C or more
Sequence.
9. manufacturing method according to claim 7 or 8, wherein
After the process (II), the manufacturing method does not include the process heated.
10. a kind of industrial product contains adsorbent according to any one of claims 1 to 6.
11. a kind of side by making the gas containing aldehyde compound and adsorbent make odorous substance be adsorbed in adsorbent and contact
Method, wherein
The adsorbent contains sour hydrazide compound and silica, and the silanol group density on the surface of the silica is
5.0/nm2Below.
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| PCT/JP2017/038708 WO2018079656A1 (en) | 2016-10-27 | 2017-10-26 | Odorant adsorbent |
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