CN108698017B - Volatile organic compound adsorbent and resin composition blended with volatile organic compound adsorbent - Google Patents
Volatile organic compound adsorbent and resin composition blended with volatile organic compound adsorbent Download PDFInfo
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- CN108698017B CN108698017B CN201780012226.5A CN201780012226A CN108698017B CN 108698017 B CN108698017 B CN 108698017B CN 201780012226 A CN201780012226 A CN 201780012226A CN 108698017 B CN108698017 B CN 108698017B
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
Abstract
A volatile organic compound adsorbent comprising SiO2/Al2O3(molar ratio) is 50 or more, and is characterized in that the zeolite has a (053) plane interplanar spacing (d value) in an X-ray diffraction spectrum of
Below, and a nitrogen partial pressure P of 0.005N2(P/P0) The lower nitrogen adsorption amount was 100 (cm)3(g) above.
Description
Technical Field
The present invention relates to a volatile organic compound adsorbent comprising an MFI-type zeolite.
Background
The zeolite having SiO in the zeolite framework2And Al2O3And the like, and further has regular channels (pores). In particular, MFI-type zeolites are rich in silica and are well known to contain 10 membersHole of ring structure (
And/or
)。
It is known that Al is present in the zeolite framework2O3Hydrophilicity is affected, and the more the amount of Al, the higher the hydrophilicity, and the less the amount of Al, the lower the hydrophilicity. The silica-rich MFI-type zeolite contains a small amount of Al and has low hydrophilicity; that is, the zeolite exhibits a high degree of adsorption to hydrophobic organic components. Further, since the silica-rich MFI-type zeolite has a pore diameter close to the size of low molecular weight hydrocarbons, it has been proposed to use it as an adsorbent for adsorbing organic compounds (see patent documents 1 to 3).
Further, the MFI-type zeolite has an action for reducing a peculiar smell generated by deterioration of a resin (hereinafter, referred to as a resin smell) (see patent document 4).
Here, it is known that volatile organic compounds (hereinafter, generally abbreviated as VOC) such as toluene, xylene, and ethyl acetate greatly affect the environment and become a cause of photochemical smog, for example. Therefore, the Air Pollution Control Law (Air Pollution Control Law) strictly controls the concentration of VOC discharged and scattered from a fixed generation source such as a factory. Therefore, it has been strongly demanded to provide an adsorbent capable of effectively removing volatile organic compounds from exhaust gas.
The above MFI-type zeolite shows high adsorptivity for various organic compounds and is therefore frequently used as a VOC adsorbent. However, since its adsorption capacity is small, it is necessary to use MFI-type zeolite in a large amount to obtain a desired effect. Therefore, it is desirable to improve the adsorption performance and capacity of MFI-type zeolites for VOCs. In particular, it is desirable to provide an adsorbent capable of adsorbing VOCs to a sufficient degree even when VOCs such as toluene are present in the atmosphere at a low concentration.
Documents of the prior art：
Patent document：
Patent document 1: JP-H01-171554
Patent document 2: JP-H09-253483
Patent document 3: JP-A-2003-126689
Patent document 4: JP-A-2002-069315
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide a volatile organic compound adsorbent exhibiting excellent adsorption even when a volatile organic compound is present at a low concentration.
It is another object of the present invention to provide an adsorbent which exhibits excellent adsorptivity particularly to toluene.
It is yet another object of the present invention to provide a resin composition blended with a volatile organic compound adsorbent.
Means for solving the problems
The present inventors have conducted many experiments on the adsorption properties of zeolites to volatile organic compounds. As a result, the present inventors have found the fact that MFI-type zeolite obtained by synthesis at low temperature shows excellent adsorption to VOC (toluene) present at low concentration in the atmosphere, and thus have completed the present invention.
According to the present invention, there is provided a volatile organic compound adsorbent comprising SiO2/Al2O3An MFI-type zeolite having a molar ratio of 50 or more and having an interplanar spacing (d value) in the (053) plane in an X-ray diffraction spectrum
Below, and a nitrogen partial pressure P of 0.005N2(P/P0) The lower nitrogen adsorption amount was 100 (cm)3(g) above.
For the volatile organic compound adsorbent of the present invention, it is desirable that:
(1)SiO2/Al2O3(molar ratio) is 90 or more;
(2) at a toluene partial pressure P of 0.01T(P/P0) The toluene adsorption amount is 8.2 mass% or more; and
(3) the content of alkali metal is suppressed to 0.1 mass% or less in terms of oxide of alkali metal.
Further, according to the present invention, there is provided a resin composition obtained by blending a resin with the above volatile organic compound adsorbent.
For the resin composition obtained by blending a resin with the adsorbent of the present invention, it is desirable that:
(1) the adsorbent is contained in an amount of 0.005 to 100 parts by mass relative to 100 parts by mass of the resin; and
(2) the resin is a thermoplastic resin.
ADVANTAGEOUS EFFECTS OF INVENTION
As shown in the examples described later, the volatile organic compound adsorbent of the present invention was used at a partial pressure P of tolueneT(P/P0) The toluene adsorption amount in an atmosphere of 0.01, i.e., an atmosphere containing a very small amount of toluene was 8.2 mass% or more, and in the highest case, 9.0 mass% or more. In such a low toluene concentration atmosphere, none of the conventional MFI-type zeolite adsorbents exhibits toluene adsorption of 8.2 mass% or more. Therefore, the volatile organic compound adsorbent of the present invention can be advantageously used in an apparatus for purifying the environment such as a chemical plant, for example, in such a manner that it is supported by a rotor for exhaust gas having a honeycomb structure.
Drawings
Fig. 1 is a graph of an X-ray diffraction image of the volatile organic compound adsorbent including MFI-type zeolite obtained in example 2.
FIG. 2 is a graph of X-ray diffraction images of (053) planes of example 3 and comparative examples 2 and 3.
Fig. 3 is a graph of nitrogen adsorption isotherms measured in example 2 and comparative examples 1, 2 and 3.
FIG. 4 is a graph of toluene adsorption isotherms measured in example 2 and comparative examples 2 and 3.
Fig. 5 is a scanning electron micrograph of the volatile organic compound adsorbent comprising MFI-type zeolite obtained in example 1.
Fig. 6 is a scanning electron micrograph of the volatile organic compound adsorbent comprising MFI-type zeolite obtained in example 6.
Detailed Description
The adsorbent comprising an MFI-type zeolite of the present invention is used for adsorbing or removing volatile organic compounds. Volatile organic compounds represent organic compounds having a boiling point in the range of 50 to 260 ℃ at atmospheric pressure. Examples thereof include toluene, xylene, ethyl acetate, ethanol, benzene, methyl ethyl ketone, dichloroethane, trichloroethane and the like, and particularly, toluene.
< MFI type zeolite >
The MFI-type zeolite is used as an adsorbent, and pores of a 10-membered ring form peculiar to the zeolite are formed, and thus, X-ray diffraction peaks as shown in fig. 1 are shown. For example, it shows narrow diffraction peaks ascribed to a (011) plane near 2 θ of 7.9 °, a (200) plane near 2 θ of 8.9 °, and a (051) plane near 2 θ of 23.1 °.
The above zeolite is rich in silica, and has SiO of 50 or more, preferably 90 or more, more preferably 100 or more, and most preferably 5,000 or more2/Al2O3(molar ratio), therefore, has low hydrophilicity, i.e., exhibits excellent adsorption to an organic compound having high hydrophobicity. On the other hand, zeolites containing a large amount of aluminum (the above molar ratio is less than 50) have high hydrophilicity and excellent adsorption of VOCs cannot be obtained.
The MFI-type zeolite used in the present invention is produced by reaction at a low temperature (80 to 130 ℃). As a result, the interplanar spacing (d value) of the (053) plane in the X-ray diffraction spectrum of the MFI-type zeolite was found to be
Below, and a nitrogen partial pressure P of 0.005N2(P/P0) The lower nitrogen adsorption amount was 100 (cm)3/g) or more, and preferably 103 (cm)3(g) above. The reason why the above d value and nitrogen adsorption amount can be obtained by the reaction at low temperature will be described later.
The above d value represents the spacing between specific planes that the pores in the zeolite have. A small d-value means that the zeolite is unstrained and the pores are uniformly distributed therein and have a large pore volume.
In connection with the above-mentioned small d-value, the MFI-type zeolite contains the above-mentioned micro-sized pores densely and uniformly distributed therein. As a result, the MFI type zeolite exhibits a nitrogen partial pressure P even when it is used as described aboveN2(P/P0) In an atmosphere as low as 0.005, a large nitrogen adsorption amount is also exhibited. In other words, the above-mentioned nitrogen adsorption amount means that the above-mentioned micro-sized pores are densely distributed in the MFI-type zeolite, and therefore, the zeolite shows very excellent adsorption to volatile organic compounds, and particularly to toluene.
Further, it is desirable that the MFI-type zeolite contains an alkali metal (hereinafter, alkali) in an amount suppressed to 1.70% by mass or less, preferably 1.25% by mass or less, and particularly 0.1% by mass or less in terms of an oxide thereof. That is, alkali components (e.g., Na and K) are mixed into zeolite as inevitable impurities. However, if the amount of the alkali component is large, the zeolite has increased hydrophilicity and greatly reduces its adsorbability to organic components. However, according to the present invention, the amount of such a base component has been suppressed to be very small to effectively avoid a decrease in the adsorbability of the organic compound. As a result, the MFI-type zeolite ensures high adsorption of VOCs. For example, as shown in the examples described later, the MFI-type zeolite used in the present invention is subjected to partial pressure P of tolueneT(P/P0) The toluene adsorption amount in an atmosphere of 0.01 was 8.2 mass% or more. If the amount of alkali in the zeolite in terms of the oxide of the alkali is suppressed to 0.1 mass% or less, the toluene adsorption amount of the MFI-type zeolite is 9 mass% or more, and in particular, close to 10 mass%.
< production of MFI-type zeolite >
The above MFI-type zeolite is produced by: in the mixed gel containing the silica source and the alumina source, the silica source and the alumina source are reacted (crystallized) by heating them in the presence of a template (template) and a seed crystal, and preferably, further in the presence of an alkali metal hydroxide for preparing a raw material to be described later.
The silica source is desirably one from which, e.g., Na has been removed2O and Al2O3High purity SiO with equal impurities to a certain degree2Such as tetraethyl orthosilicate, colloidal silica, silica gel dry powder, and silica hydrogel. These silica sources, once dissolved in aqueous solution during the reaction, are reconstituted into MFI-type zeolites. Here, if a small amount of impurities or non-reactive components unnecessary for the reaction are contained, the kind of the silica source does not greatly affect the crystallization of the MFI-type zeolite.
However, from the aspect of cost, it is desirable to use silica gel dry powder or silica hydrogel, and particularly, silica hydrogel, because MFI-type zeolite can be produced from them by a relatively simple method. Silica hydrogels can be readily obtained by: an alkali silicate such as sodium silicate is gradually dropped into an inorganic acid such as sulfuric acid, the final pH is adjusted to about 3.0 to about 9.0, filtration is performed, and washing is performed until the pH of the discharged washing water obtains a pH of about 5.0 to about 7.0. The silica hydrogel may be produced by heating while mixing the raw materials together, or before or after washing with water, or may be produced at normal temperature.
As the alumina source, for example, aluminum sulfate, alkali aluminum sulfate, or sodium aluminate can be used. However, the use of sodium aluminate is particularly desirable.
When trying to obtain SiO of a more desirable MFI-type zeolite2/Al2O3High molar ratio of SiO2/Al2O3At a molar ratio of MFI-type zeolite of, for example, 112, the mixed gel contains a Si component and an Al component such that SiO2/Al2O3The molar ratio is, for example, 120. In general, the mixed gel is obtained by mixing together a silica source and an alumina source in an aqueous medium at ordinary temperature.
Mixing together a silica source and an alumina source such that the SiO2/Al2O3(molar ratio) becomes a predetermined quantitative ratio. However, when trying to produce a composition containing particularly much Si (e.g., a molar ratio of 1000)Above), an alumina source may not be used. This is because the raw material for industrial purposes generally contains a small amount of Al component as an inevitable impurity.
The mixed gel comprising the silica source and the alumina source may further comprise a template, a seed, and preferably, an alkali metal hydroxide. The mixed gel containing the seed crystals is crystallized by reacting at low temperature in the presence of the template and the seed crystals, thereby obtaining the MFI-type zeolite.
There is no particular limitation on the method of adding the template, seed crystal or alkali metal hydroxide. They may be premixed to a part or all of the mixed gel and/or to a part or all of the raw materials of the mixed gel before crystallization.
The template is a structure directing agent for forming pores in the form of a 10-membered ring peculiar to the MFI-type zeolite, and is an amine compound having a n-alkyl group having 2 to 4 carbon atoms and a nitrogen cation in its molecule. Examples thereof are the cations and anions of tetraalkyl (ethyl, n-propyl or n-butyl) ammonium (e.g. Br)-) Salts, and hydroxides of the above mentioned ammonium.
That is, in the reaction of the silica-alumina hydrosol (SiO chain by condensation), as shown in the following schematic formula, an intermediate product having a negative charge is formed to form Si-O-Si chain,
OH-Si-O-+Si-OH→[OH-Si-O…SiOH]-
→OH-Si-O-Si--OH
→OH-Si-O-Si(-OH)-O-+H2O
in forming the above-mentioned Si-O-Si chain, the cation of the template protects the intermediate product, and at the same time, the Si-O-Si chain is formed to surround the cation of the template. As a result, a 10-membered ring structure peculiar to MFI-type zeolite is formed.
If the template is, for example, tetrapropylammonium bromide (TPA-Br), TPA/SiO is present as the Si component relative to the mixed gel2The template is used in an amount of 0.03 to 0.20 (molar ratio). However, the amount greatly differs depending on the kind of template, and particularly depending on the number of carbon atoms in the alkyl group.
Although not required when the above-mentioned hydroxide of the quaternary ammonium is used as a template, when a salt of the quaternary ammonium and an anion such as Br or Cl is used as a template, in order to dissolve the silica source, A is used as a component relative to Si in the mixed gel2O/SiO2An alkali metal hydroxide (for example, caustic soda or the like) is added in an amount of 0.01 to 0.20 (molar ratio, a is an alkali metal element). In this case, the time required for crystallization is shorter as the amount of the alkali metal hydroxide added is larger. However, if A2O/SiO2If the ratio exceeds 0.20, a large amount of alkali metal having a hydrophilic action remains in the obtained MFI zeolite, and the adsorptivity of the present invention may not be often exhibited to a sufficient degree. Thus, A2O/SiO2The ratio is preferably 0.15 or less, and particularly preferably 0.10 or less.
In order to produce the above MFI-type zeolite, the reaction must be carried out at low temperature, or specifically at 80 to 130 ℃, preferably at 95 to 120 ℃, and particularly preferably at 95 to 98 ℃. Therefore, the above reaction must be carried out in the presence of a seed crystal. This promotes crystallization, and therefore, the reaction is still carried out at low temperature, and the crystallization can be completed in a short time, for example, in 48 hours or less, and particularly in 20 hours or less.
As the seed crystal, it is necessary to use a previously prepared MFI-type zeolite. However, among those zeolites produced by a method to be described later, MFI-type zeolites containing a template, or MFI-type zeolites from which a template is removed by, for example, firing, may also be used. The seed crystal is appropriately pulverized and added with respect to 100 parts by mass of SiO as the Si component in the mixed gel2Is added in an amount of 0.02 to 20 parts by mass, and preferably 0.05 to 5.0 parts by mass.
If the amount of the seed crystal added is 0.05 parts by mass or less, the effect of shortening the crystallization time is weak. If the amount added is too large, the composition of the seed crystal affects the composition of the resulting MFI-type zeolite. Furthermore, the formation of the core and the shell also leads to the formation of undesirable interfaces, which prevent the formation of densely distributed pores and are therefore undesirable. In particular, although the addition amount is 5.0 parts by mass or more, the time required for crystallization does not significantly change; that is, simply using the seed crystal in an increased amount increases the cost, which is also undesirable.
Further, as described above, the mixed gel (mixed gel containing seed crystals) is reacted at 80 to 130 ℃ in the presence of the template and the seed crystals, and the silica-rich MFI-type zeolite having the above d-value and nitrogen adsorption amount is obtained.
For example, when MFI-type zeolite is produced by a conventional method, setting the reaction temperature to about 180 ℃ higher or about 150 ℃ lower enables crystallization to be completed in a short time. However, according to the studies conducted by the present inventors, if the reaction is carried out at a temperature of not lower than 130 ℃, the obtained MFI-type zeolite is obtained in excess of
D value of (interplanar spacing between (053) planes) and a nitrogen partial pressure P of 0.005N2(P/P0) Lower has a height of less than 100 (cm)3Nitrogen adsorption amount per g). Although the reason has not been fully elucidated, the present inventors speculate that, if the reaction is carried out at a high temperature, the template is thermally decomposed while the MFI-type zeolite is crystallized, or even if the template is not thermally decomposed, the vibration of the template is amplified by its thermal energy, and as a result, the template exhibits a reduced effect of protecting the intermediate. Therefore, it is presumed that the crystal structure of the obtained MFI-type zeolite is deformed (distor) or the formed pores are deformed.
That is, since the present invention performs the reaction at a low temperature as described above, the template is prevented from being decomposed or vibrated by thermal energy. As a result, the resulting zeolite is prevented from being deformed or the pores therein are prevented from being deformed (deform), and thus, the pores of uniform size are densely distributed. Therefore, it is considered that the obtained MFI-type zeolite has a small value of the interplanar spacing d between specific faces ((053) faces) and shows a large nitrogen adsorption amount. Particularly, the invention is as small as
The d value of the following (053) plane means that the MFI-type zeolite has a very dense crystal structure in which micro-sized pores are densely and uniformly distributed. Generally, boiling can be analyzedThe d value of the stone, which involves little confusion with other peaks in the range of XRD measurements, and it is desirable to use peaks on a relatively high angle side (e.g., close to 30 °). In the case of the MFI-type zeolite, the (053) plane satisfied this condition, and thus it was analyzed that the volatile organic compound adsorbent comprising the MFI-type zeolite of the present invention had a dense crystal structure.
The MFI-type zeolite can be crystallized even if the reaction temperature is 80 ℃ or lower. However, in this case, the reaction proceeds very slowly and becomes impractical.
According to the present invention, as described above, the obtained zeolite is free from deformation and contains pores of uniform size densely distributed in the zeolite without deformation. Therefore, as shown in the examples described later, the zeolite has a high BET specific surface area. That is, the BET specific surface area of the volatile organic compound adsorbent of the present invention is 430m2A ratio of 440m or more per gram2More than g, and particularly preferably 450m2More than g.
Further, as long as the reaction temperature is within the above-mentioned low temperature region, the reaction may be carried out under atmospheric pressure, or may be carried out under pressure by using an autoclave or the like. However, even when carried out under pressure, the reaction does not bring any advantage. That is, even if the reaction is carried out under atmospheric pressure while using the seed crystal, crystallization is promoted to a sufficient degree. Therefore, from the viewpoint of cost, it is desirable to carry out the reaction under atmospheric pressure.
After the reaction, the zeolite is filtered, washed with water and dried in a conventional manner, and then fired at a temperature of about 500 to about 800 ℃ for about 0.5 to about 10 hours. Thereby, a desired MFI-type zeolite is obtained from which the template has been removed and which contains pores densely distributed therein, said MFI-type zeolite being suitable for adsorbing VOCs, and in particular toluene.
If a large amount of alkali components such as Na and K are used in the synthesis of zeolite, the alkali content becomes large. The alkali component plays a role of imparting hydrophilicity, and therefore, the resulting MFI-type zeolite exhibits greatly reduced adsorption to organic compounds. In this case, it is desirable to disperse the MFI-type zeolite obtained by the firing step again in an aqueous solution, and to remove the alkali component therefrom by means of a dealkalization method using an acid such as hydrochloric acid or sulfuric acid, or by a series of dealkalization methods consisting of alkali and ammonium ion exchange by using various ammonium salts and a subsequent firing step for removing ammonium.
In particular, it is desirable to employ a series of dealkalization methods by using various ammonium salts. In this case, it is desirable to use ammonium chloride in an amount of about 10 to about 200 parts by mass relative to, for example, the MFI-type zeolite after firing. The subsequent firing to remove ammonium is desirably conducted at 300 to 600 c for about 0.5 to about 10 hours.
The MFI-type zeolite thus obtained generally has a median particle diameter of 0.1 to 20 μm, and preferably 0.5 to 10 μm, and is preferably suitably pulverized into a powder for use. Further, the MFI-type zeolite is used with the particle size of the MFI-type zeolite adjusted to 1.0 to 4.0 μm by taking ease of handling into consideration. However, when used by being kneaded with, for example, a resin composition, or mixed into a liquid containing a hydrophobic solvent such as a paint or a coating agent, the MFI-type zeolite may be used by being more finely pulverized into a submicron order (having a median particle diameter of 0.1 to 1.0 μm) to improve dispersibility or to increase a specific surface area. Further, when packed into an apparatus such as an adsorption column or an adsorption tower, the MFI-type zeolite is appropriately mixed with, for example, a binder that is generally used and shaped into a granular body.
The volatile organic compound adsorbent of the present invention comprising the above silica-rich MFI-type zeolite can exhibit high adsorption of volatile organic compounds such as toluene, xylene, and ethyl acetate, and can efficiently adsorb and remove these compounds even from an atmosphere in which these compounds are present at a low concentration. Therefore, in a chemical plant or a plant that discharges a gas containing a volatile organic compound, the adsorbent can be applied to an apparatus for environmental purification by being supported by a rotor for exhaust gas having a honeycomb structure, for example.
The volatile organic compound adsorbent of the present invention having the above-described characteristics is added to a resin to prepare a resin composition, and a master batch is preferably prepared therefrom to form various articles such as films and various materials. In this case, the volatile organic compound adsorbent of the present invention may be added to the resin alone, or may be added to the resin in combination with other adsorbents or additives. The amount of the volatile organic compound adsorbent to be added in the present invention is not limited. However, the adsorbent is added, for example, in an amount ranging from 0.001 to 1000 parts by mass, and preferably from 0.005 to 100 parts by mass, relative to 100 parts by mass of the resin. However, when the adsorbent of the present invention is added to a resin to adsorb odor peculiar to the resin generated from an unreacted monomer or a deteriorated monomer at the time of resin processing, it is desirable to use the adsorbent in an amount of 0.005 to 10 parts by mass relative to 100 parts by mass of the resin.
Further, by adding the volatile organic compound adsorbent of the present invention to a resin used as an automobile member and a building material, effects of improving living environment such as adsorption of odors specific to new cars and new buildings, and in particular, adsorption of substances (toluene and aldehydes) that are causes of sick building syndrome can be expected. Further, by making the fiber contain the adsorbent of the present invention in the processing step of the fiber, a high functional fiber having a deodorizing function can be produced. In this case, the adsorbent is desirably contained in an amount of 1 to 100 parts by mass relative to 100 parts by mass of the fiber.
As the base resin, a thermoplastic resin or a thermosetting resin can be used. However, from the viewpoint of moldability, a thermoplastic resin is preferable. Examples of the thermoplastic resin are described below.
Olefin-based resins such as low density polyethylene, high density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or random or block copolymers of α -olefins such as ethylene, propylene, 1-butene or 4-methyl-1-pentene, or cyclic olefin copolymers thereof;
ethylene vinyl copolymers such as ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer and ethylene vinyl chloride copolymer;
styrenic resins such as polystyrene, acrylonitrile-styrene copolymer, ABS and alpha-methylstyrene-styrene copolymer;
vinyl-based resins such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, polymethyl acrylate and polymethyl methacrylate;
polyamide resins such as nylon 6, nylon 6-10, nylon 11 and nylon 12;
polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, and copolyesters thereof;
a polycarbonate resin;
a polyphenylene ether resin; and
biodegradable resins such as polylactic acid.
The thermoplastic resins may be used each alone, but may also be used as a blend of two or more thereof.
In the present invention, particularly, olefin-based resins and polyester resins are preferable, and as the base resin, olefin-based resins are most desirable.
In addition, the volatile organic compound adsorbent of the present invention contains micro-sized pores densely and uniformly distributed therein, and active sites (for example, solid acid sites) possessed by the MFI-type zeolite are expected to be also densely and uniformly distributed. That is, the volatile organic compound adsorbent of the present invention can be used as a catalyst generally using MFI type zeolite, such as an acid catalyst, a disproportionation catalyst, an isomerization catalyst, a catalyst for synthesizing hydrocarbons, a catalyst for FCC, a catalyst for olefin polymerization, and a denitration catalyst, or as a catalyst carrier without any limitation.
Examples
The present invention will now be described using the following experimental examples.
In the experiment, various measurements were made by the following methods.
(1) Diffraction by X-ray
(measurement and analysis conditions of d value of interplanar spacing)
The dried sample was put into a desiccator internally adjusted to a relative humidity of 75%, and allowed to stand at room temperature for 48 hours or more to adsorb water to its saturated amount. The sample was taken out and its X-ray diffraction was measured at 2 θ ═ 29.6 to 30.2 °. X-ray diffraction was measured with Cu — K α under the following conditions by using Ultima 4 manufactured by Rigaku co.
The target is as follows: cu
A filter: curved crystal graphite monochromator
A detector: SC (Single chip computer)
Voltage: 40kV
Current: 50mA
Step length: 0.005 degree
Counting time: 10 seconds per step
Slit: DS2/3 degree RS0.3mm SS2/3 degree
In X-ray diffraction in a desired range, the value of d showing the angle of the maximum peak is obtained from the following equation
(Bragg's conditions)
d＝nλ/2sinθ
d: interplanar spacing
n: integer number of
λ: wavelength of light
sin θ: angle of crystal face facing X-ray
(confirmation of Crystal type)
The crystals were confirmed by changing the following conditions from those used for the d-value measurement.
Measurement range: 3 to 40 °
Current: 40mA
Step length: 0.02 degree
Counting time: 0.6 sec/step
(2) Measurement of nitrogen adsorption isotherms
Nitrogen adsorption was measured by using Tristar manufactured by Micrometrics co, and at nitrogen partial pressure PN2(P/P0) The adsorption isotherm was determined in the range of 0.005 to 0.95. The pretreatment was carried out in vacuo at 200 ℃ for 2 hours. At a nitrogen partial pressure P of 0.005N2(P/P0) The amount of nitrogen adsorbed (cm) by each adsorbent described later was measured3/g)。
(3) Measurement of toluene adsorption isotherm
Toluene adsorption was measured by using Belsorp Max manufactured by Microtrac BEL Co. and at a toluene partial pressure PT(P/P0) The adsorption isotherm was determined in the range of 0.0001 to 0.10. The pretreatment was carried out in vacuo at 150 ℃ for 2 hours. The equilibrium determination time was 300 seconds. Toluene is a chromatographic grade toluene produced by FUJIFILM Wako Pure Chemical co. At a toluene partial pressure P of 0.01T(P/P0) Each adsorbent to be described later is measured, and the measured value is converted into an adsorption amount per unit mass of the adsorbent and regarded as a toluene adsorption amount (mass%).
(4) Analysis of composition
Alkali metal content and SiO in terms of alkali metal oxide2/Al2O3Elemental analysis necessary for calculation of (molar ratio) was performed by using Rigaku zsxprimus II manufactured by Rigaku co. The measurement was performed by using a target of Rh, an analysis line of K α, and under the following conditions.
The sample was dried at 110 ℃ for 2 hours.
TABLE 1
(5) Measurement of median particle diameter (D50%)
The volume-based median particle diameter (μm) was measured by using a laser diffraction type particle size distribution measuring apparatus manufactured by Malvern Panalytical, Mastersizer 3000, and using water as a solvent.
(6) BET specific surface area
The specific surface area was calculated from the adsorption isotherm obtained in (2) above by the BET method.
Comparative example 1
SILTON MT-100 (SiO) which is an MFI type zeolite produced by Mizusawa Industrial Chemicals, Ltd2/Al2O3105). SILTON is of Mizusawa Industrial Chemicals, LtdA trademark is registered.
Comparative example 2
MFI-type zeolite HSZ890HOA produced by TOSOH co.
Comparative example 3
MFI-type zeolite ABSCENTS-3000 produced by Union Showa co.
Comparative example 4
(preparation of silica hydrogel)
By using 40 mass% of sulfuric acid and sodium silicate No. 3 (SiO)222.8% by mass of Na27.6% by mass of O, and H2O ═ 69.6 mass%) silica hydrogel was prepared by a conventional method. Composition of analysis is SiO238.5% by mass of Na2O0.02 mass% and H2O is 61.4 mass%.
(Synthesis of MFI-type zeolite)
To a 2 liter stainless steel kettle, SiO2Has a mass of 200g and the molar ratio of the components is SiO2:Na2O:TPA-Br:H2Silica hydrogel, TPA-Br, 49 mass% NaOH, and water were added in amounts of 1:0.025:0.045: 16. The components were mixed at room temperature with stirring to prepare a mixed gel thereof.
Subsequently, the mixed gel was transferred to a 1.5-liter autoclave equipped with a stirring blade therein, heated to 170 ℃ over 2.5 hours with stirring, and then subjected to a crystallization reaction for 12 hours while maintaining the temperature at 170 ℃. After completion of the reaction, the liquid was filtered and then washed with 3 times the volume of water of the mixed gel, thereby obtaining an MFI-type zeolite containing a template. The MFI-type zeolite after filtration and water washing had a median particle size of 10.0 μm.
The MFI-type zeolite was dried on a constant-temperature drying rack (constant-temperature drying rack) heated at 110 ℃ for 10 hours, and the template was removed therefrom under the condition of being maintained at 600 ℃ for 2 hours in a muffle furnace, thereby obtaining an MFI-type zeolite containing no template.
(pulverization of MFI-type zeolite)
The MFI-type zeolite is pulverized by using a swirl jet mill. The pulverized powder had a median particle size of 7.7 μm.
(example 1)
Except that SiO2Is set to 200g, and the compositional molar ratio of each component is changed to SiO2:Na2O:TPA-Br:H2A mixed gel was prepared in the same manner as in comparative example 4 except that O was 1:0.03:0.05: 16. Finally, to SiO2Seed crystals (MFI-type zeolite having a median particle diameter of 7.7 μm obtained in comparative example 4) were added in an amount of 1.0 mass%, and the mixture thereof was further stirred for 5 minutes, thereby preparing a mixed gel containing the seed crystals.
Next, the mixed gel containing the seed crystal was heated to 95 ℃ over 1 hour in a temperature-controlled hot water bath with stirring, and the crystallization reaction was carried out for 20 hours while maintaining the temperature at 95 ℃. After the reaction was completed, the reaction solution was filtered and then washed with 3 times the volume of water of the mixed gel, thereby obtaining an MFI-type zeolite containing a template. The MFI-type zeolite after filtration and water washing had a median particle size of 1.0 μm.
The MFI-type zeolite was dried on a constant-temperature drying rack heated at 110 ℃ for 10 hours, and then the template was removed therefrom in a muffle furnace at 600 ℃ for 2 hours, thereby obtaining a template-free MFI-type zeolite.
Then, in the same manner as in comparative example 4, the MFI-type zeolite was pulverized by using a swirl-type jet mill, thereby obtaining a volatile organic compound adsorbent comprising the MFI-type zeolite. The adsorbent had a median particle size of 1.0 μm.
(example 2)
To 10g of the volatile organic compound adsorbent comprising MFI-type zeolite of example 1, 90g of water was added so that the adsorbent was again dispersed therein with stirring. Thereafter, 10g of ammonium chloride was added thereto to perform an exchange treatment for 3 hours. After filtration and water washing, the resulting ammonium-MFI type zeolite was dried on a constant temperature drying rack heated at 110 ℃ for 10 hours, and ammonium was removed therefrom under holding at 500 ℃ for 3 hours in a muffle furnace to obtain an alkali-removed MFI type zeolite. The zeolite is pulverized again by using a cyclone type jet mill, thereby obtaining a volatile organic compound adsorbent comprising an MFI-type zeolite. The adsorbent had a median particle size of 1.0 μm.
(example 3)
A volatile organic compound adsorbent comprising an MFI-type zeolite was obtained in the same manner as in example 1, except that a 1.5-liter autoclave equipped with a stirrer was used as the reaction vessel, and the reaction was carried out at 105 ℃ for 16 hours. The adsorbent had a median particle size of 2.0 μm.
(example 4)
Except that the composition molar ratio of the mixed gel was changed to SiO2:Na2O:TPA-Br:H2A volatile organic compound adsorbent including MFI-type zeolite was obtained in the same manner as in example 1, except that a 1.5-liter autoclave equipped with a stirrer was used as the reaction vessel and the reaction was carried out at 110 ℃ for 18 hours, O ═ 1:0.025:0.045: 16. The adsorbent had a median particle size of 4.0 μm.
(example 5)
By using sodium aluminate (Al) in addition to the raw material shown in example 12O323.0% by mass of Na219.2% by mass of O, H2O57.8 mass%), they were mixed together under stirring at room temperature so that the compositional molar ratio of their mixed gel was SiO2:Al2O3:Na2O:TPA-Br:H2O ═ 1:0.008:0.05:0.04:16, and finally as opposed to SiO2Seed crystals (MFI-type zeolite having a median particle diameter of 7.7 μm obtained in comparative example 4) were added in an amount of 1.0 mass% to prepare a seed crystal-containing mixed gel. Thereafter, a volatile organic compound adsorbent including MFI-type zeolite was obtained in the same manner as in example 1, except that a 1.5-liter autoclave having a built-in stirrer was used as the reaction vessel, and the reaction was performed at 120 ℃. The adsorbent had a median particle size of 1.8 μm.
(example 6)
By mixing SiO2Was set to 380g, the MFI-type zeolite having a median particle diameter of 1.0 μm obtained in example 1 was used as a seed crystal in an amount of 3.0 mass%, and raw materials including the seed crystal were mixed together under stirring so that the compositional molar ratio of the components was SiO2:Na2O:TPA-Br:H2O ═ 1:0.03:0.045:20 to prepare a mixed gel containing seed crystals. Thereafter, the operation was performed in the same manner as in example 1, thereby obtaining a volatile organic compound adsorbent comprising an MFI-type zeolite. The adsorbent had a median particle size of 0.7 μm.
(example 7)
SiO was prepared by using the same raw material as used in example 52Was set to 240g, the MFI-type zeolite having a median particle diameter of 0.7 μm obtained in example 6 was used as a seed crystal in an amount of 2.0 mass%, and raw materials including the seed crystal were mixed together under stirring so that the compositional molar ratio of the components was SiO2:Al2O3:Na2O:TPA-Br:H2O ═ 1:0.0077:0.12:0.04:20.3 to prepare a mixed gel containing seed crystals. Thereafter, the operation was performed in the same manner as in example 1 except that the crystallization reaction was performed for 48 hours, thereby obtaining a volatile organic compound adsorbent including MFI-type zeolite. The adsorbent had a median particle size of 0.5 μm.
The MFI-type zeolites of comparative examples 1 to 4, and the volatile organic compound adsorbents prepared in examples 1 to 7 were tested for properties, nitrogen adsorption amount, and toluene adsorption amount. The results are shown in tables 2 and 3.
[ Table 2]
[ Table 3]
Application example; preparation of resin composition blended with adsorbent
Pellet-shaped polyethylene (trade name; LF440B) produced by Japan Polypropylene co. was mixed with the adsorbent of example 6, and the mixture thereof was melt-kneaded at 170 ℃ by using LABO plastics manufactured by Toyo Seiki mfg.co. and cut into chips, thereby obtaining a resin composition containing the adsorbent in an amount of 0.5 parts relative to 100 parts by mass of the resin. No components other than the adsorbent were added.
Evaluation of resin odor adsorption capacity;
the ability to reduce the odor of the resin was evaluated by using the adsorbent-blended resin composition obtained in the preparation of the above-described resin composition, and by using pellet-like polyethylene containing no adsorbent.
5g each of the resin composition blended with the adsorbent and the pellet-shaped polyethylene containing no adsorbent were put into a 500mL screw cap bottle. The teflon tape was wound three times on the spiral portion of the bottle, and then a cap was attached thereto to seal. Bottles were provided for each tester (five). The bottles containing the pelletized polyethylene were stored in a constant temperature drying rack preheated at 50 ℃ and left at 50 ℃ for 90 hours. The two bottles were then removed from the thermostatic drying rack and opened to allow the examiner to smell immediately and to assess the degree of smell (0: not smelled at all, 1: slightly smelled, 2: smelled). The test was performed in a state where the examiner was not made aware of which bottle contained the particles. The test results are shown in table 4.
[ Table 4]
Claims (6)
1. A volatile organic compound adsorbent comprising an MFI-type zeolite,
wherein the zeolite has:
SiO in a molar ratio of 50 or more2/Al2O3；
In X-ray diffraction spectroscopy
The interplanar spacing (d value) of the following (053) plane;
430m2BET specific surface area of,/g or more;
at 0.005Partial pressure of nitrogen PN2(P/P0) Lower 100cm3A nitrogen adsorption amount of not less than g, and
at a toluene partial pressure P of 0.01T( P/P0) The toluene adsorption amount was 8.2 mass% or more.
2. The adsorbent of claim 1, wherein the SiO in terms of mole ratios2/Al2O3Is 90 or more.
3. The adsorbent according to claim 1 or 2, wherein the alkali metal content in terms of oxide is suppressed to 0.1 mass% or less.
4. A resin composition obtained by blending a resin with the adsorbent according to any one of claims 1 to 3.
5. The resin composition according to claim 4, wherein the adsorbent is blended in an amount of 0.005 to 100 parts by mass relative to 100 parts by mass of the resin.
6. The resin composition according to claim 4, wherein the resin is a thermoplastic resin.
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| US20220259054A1 (en) * | 2019-07-25 | 2022-08-18 | Tosoh Corporation | Hydrophobic zeolite, method for producing same and use of same |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01171554A (en) * | 1987-12-28 | 1989-07-06 | Mizusawa Ind Chem Ltd | Deodorant |
| JPH09253483A (en) * | 1996-03-21 | 1997-09-30 | Idemitsu Kosan Co Ltd | Adsorbent for cleaning off hydrocarbons in exhaust gas |
| CN1557707A (en) * | 2004-01-19 | 2004-12-29 | 复旦大学 | Method for preparing Fe-ZSM-5 zeolite microsphere using kieselguhr as raw material |
| JP2011157406A (en) * | 2010-01-28 | 2011-08-18 | Kuraray Co Ltd | Method for suppressing generation of odor component from oxygen-absorbing resin composition |
| CN103379954A (en) * | 2010-12-10 | 2013-10-30 | 南方化学知识产权有限公司 | Granulated zeolites with high adsorption capacity for adsorption of organic molecules |
| CN104148010A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | High-silicon MFI zeolite adsorbent without adhesive and preparation method thereof |
| CN104709923A (en) * | 2013-12-14 | 2015-06-17 | 上海泉灵信息科技有限公司 | Novel technology for direct method synthesis of ZSM-5 molecular sieve |
| CN104888694A (en) * | 2015-05-28 | 2015-09-09 | 同济大学 | Adsorbing material for efficiently adsorbing indoor formaldehyde and methylbenzene gases |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1190205A (en) * | 1982-03-03 | 1985-07-09 | Brent M. Lok | Synthesis process for high silica zeolites |
| DE10020621A1 (en) * | 2000-04-27 | 2001-11-08 | Degussa | Colorless, low-emission polymer |
| US9132410B2 (en) * | 2013-12-31 | 2015-09-15 | Algenol Biotech LLC | Compositions, systems and methods for separating ethanol from water and methods of making compositions for separating ethanol from water |
-
2017
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-
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01171554A (en) * | 1987-12-28 | 1989-07-06 | Mizusawa Ind Chem Ltd | Deodorant |
| JPH09253483A (en) * | 1996-03-21 | 1997-09-30 | Idemitsu Kosan Co Ltd | Adsorbent for cleaning off hydrocarbons in exhaust gas |
| CN1557707A (en) * | 2004-01-19 | 2004-12-29 | 复旦大学 | Method for preparing Fe-ZSM-5 zeolite microsphere using kieselguhr as raw material |
| JP2011157406A (en) * | 2010-01-28 | 2011-08-18 | Kuraray Co Ltd | Method for suppressing generation of odor component from oxygen-absorbing resin composition |
| CN103379954A (en) * | 2010-12-10 | 2013-10-30 | 南方化学知识产权有限公司 | Granulated zeolites with high adsorption capacity for adsorption of organic molecules |
| CN104148010A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | High-silicon MFI zeolite adsorbent without adhesive and preparation method thereof |
| CN104709923A (en) * | 2013-12-14 | 2015-06-17 | 上海泉灵信息科技有限公司 | Novel technology for direct method synthesis of ZSM-5 molecular sieve |
| CN104888694A (en) * | 2015-05-28 | 2015-09-09 | 同济大学 | Adsorbing material for efficiently adsorbing indoor formaldehyde and methylbenzene gases |
Non-Patent Citations (2)
| Title |
|---|
| "low temperature synthesis and properties of ZSM-5 aggregates formed by ultra-small nanocrystals";J.Auado et al.;《Microporous and Mesoprous Materials》;20040828;第75卷;摘要、第2.1节、第3.2-3.3节、第4节 * |
| "Low-temperature synthesis, structure, sorption properties and acidity of zeolite ZSM-5";Roman Barakov et al.;《J. Porous Mater 》;20151214;第23卷;第517-528页 * |
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