JP4666826B2 - Method for producing X-type zeolite-hydrophilic polymer composite - Google Patents

Description

【００５７】
表１および図２より、実施例４の複合体の硫化水素ガス吸着速度は、比較例３の複合体の約２倍であった。また、実施例４の複合体では、５分の時点で硫化水素ガス濃度がほとんど０ｐｐｍとなったのに対して、比較例３の複合体では１４０ｐｐｍ残存していた。
【００５８】
実験例２
実施例４および比較例３で得られた銅イオン担持ゼオライト−パルプ複合体を１．０ｇ量り取り、それぞれＰＥ製のバッグ（容量４Ｌ）に入れ、脱気した。次に１８０ｐｐｍの亜硫酸ガス１．５Ｌを注入し、亜硫酸ガスの系内濃度の経時変化をガステック（株）製検知管により測定した。その結果を表２および図３に示す。
【００５９】
【表２】

【００６０】
表２および図３より、実施例４の複合体の亜硫酸ガス吸着速度は、比較例３の複合体の約２倍であった。また、実施例４の複合体では、５分の時点で亜硫酸ガス濃度が１ｐｐｍとなったのに対して、比較例３の複合体では８５ｐｐｍ残存していた。
【００６１】
以上のことから、セルロースの実体内に含有させるゼオライトを、Ａ型から細孔口径の大きなＸ型にすることにより、硫化水素ガス、亜硫酸ガス等の吸着速度を著しく向上させることができることが判明した。
【００６２】
実験例３
実施例３および比較例２で得られた複合体を１０５℃で２４時間乾燥し、それぞれ１．０ｇを量り取った。これらをそれぞれｐＨ＝４．０および５．０の１．０ｍＭ酢酸−酢酸ナトリウム緩衝液２００ｍＬに入れ、２５℃で２４時間静置した。２４時間後に小型遠心分離機（（株）三陽理化機械製作所製：ＳＹＫ−５０００−１５Ａ）を用いて複合体を取りだし、水２．０Ｌで洗浄後、１０５℃で２４時間乾燥し、重量を測定した。結果を表３に示す。
【００６３】
【表３】

【００６４】
表３より、ｐＨ＝４．０では実施例３で得られた複合体の減少重量は、複合体中に含有されているゼオライト量の３９％分に過ぎず、一部のゼオライトしか溶解しなかったのに対して、比較例２で得られた複合体の減少重量は、複合体中に含有されているゼオライト量にほぼ一致し、ほとんど全てのゼオライトが溶解していた。
【００６５】
ｐＨ＝５．０では、実施例３で得られた複合体の減少重量は、複合体中に含有しているゼオライト量の１７％であり、ほとんどのゼオライトは残存していたのに対して、比較例２で得られた複合体の減少重量は、複合体中に含有しているゼオライト量にほぼ一致し、ｐＨ＝４．０と同様にほとんど全てのゼオライトが溶解していた。
【００６６】
以上の結果より、ゼオライト−親水性高分子複合体において、セルロースの実体内に含有させるゼオライトをＸ型ゼオライトとすることにより、Ａ型ゼオライトでは耐酸性が問題となるような用途に好適に用いることができることが判明した。
【００６７】
【発明の効果】
本発明の複合体は、Ａ型ゼオライトに比べて細孔口径が大きく、耐酸性に優れたＸ型ゼオライトを性能的に充分な量で含有するため、Ａ型ゼオライトでは満足できる吸着能力が得られなかった比較的大きい分子（例えば、硫化水素ガス、亜硫酸ガス、亜硝酸ガス、次亜硝酸ガス、ジメチルアミン、トリメチルアミン、メチルメルカプタン、ＶＯＣ（揮発性有機化合物；例えば、キシレン、トルエン、ピリジン、アセトアルデヒド等）、エタノール、プロパノール、ブタノール、酢酸、酪酸、プロピオン酸、イソ吉草酸、トリクロロエチレン、ジクロロメタン等）を効率的に吸着することができる。すなわち、このようなガスの吸着剤として好適に使用することができる。また、当該複合体は、Ａ型ゼオライトを含有した複合体では耐酸性が問題となるような用途（例えば、果汁の濾材、酸性廃液中の重金属イオン、放射性金属イオン、貴金属イオンの回収濾材、強酸性ガスの吸着濾材等）において、好適に用いることができる。
【図面の簡単な説明】
【図１】実施例１〜４および比較例１における材料温度の変化を示すグラフである。
【図２】実施例４および比較例３で得られた各複合体の硫化水素ガス吸着能力を示すグラフである。
【図３】実施例４および比較例３で得られた各複合体の亜硫酸ガス吸着能力を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an X-type zeolite-hydrophilic polymer composite having excellent adsorption ability and a method for producing the same.
[0002]
[Prior art]
X-type zeolite is a hydrous aluminosilicate of the same genus as A-type zeolite containing Na, Al, Si, O, and H as main constituent components. Typical unit composition is Na ₈₆ (Al ₈₆ Si ₁₀₆ O ₃₈₄ ) ・ 264H ₂ O. The difference from the A-type zeolite is that the Si / Al of the A-type zeolite is 1, whereas the X-type zeolite has a Si / Al greater than 1 and less than 1.5. As a result, the pore diameter of the X-type zeolite is about 7.4 mm, which is larger than about 4.2 mm of the A-type zeolite and can adsorb substances that could not be adsorbed by the A-type zeolite. Moreover, since the ratio of Si is higher than A type zeolite, it is excellent in acid resistance.
[0003]
So far, the present inventors have studied various methods for synthesizing zeolite within a hydrophilic polymer entity, for example, zeolite-hydrophilicity containing an A-type zeolite or a Y-type zeolite within a hydrophilic polymer entity. A polymer composite has been manufactured (Japanese Patent Laid-Open No. 10-120923). However, it has been difficult to selectively synthesize X-type zeolite in a hydrophilic polymer entity so as to provide a sufficient amount in terms of performance.
[0004]
The reason for this is that if the concentration of alkali required to synthesize the X-type zeolite in the substance of the hydrophilic polymer is too high, it will change to A-type zeolite during the synthesis, On the other hand, when the alkali concentration is lowered or the raw material concentration is increased, a complex containing a sufficient amount of X-type zeolite cannot be obtained, and only a complex having a low industrial value can be obtained. It was.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a zeolite-hydrophilic polymer composite containing an X-type zeolite in a sufficient amount in terms of performance within the substance of the hydrophilic polymer and a method for producing the same.
[0006]
[Means for Solving the Problems]
In order to achieve this object, the present inventors have intensively studied. As a result, in the method of synthesizing zeolite within a hydrophilic polymer entity using a silicon compound, an aluminum compound, and a basic substance, A-type zeolite was synthesized. By reacting at a molar ratio between the silicon compound, the aluminum compound and the basic substance and at a basic substance concentration to form a fine alumino silica gel in the substance of the hydrophilic substrate, and then the silicon compound, the aluminum compound and the base It is possible to synthesize X-type zeolite in a sufficient amount in the substance of the hydrophilic polymer by reacting the molar ratio with the basic substance and the basic substance concentration under the conditions that the X-type zeolite can be synthesized. As a result, the present invention has been completed.
That is, the present invention is as follows.
[1] It comprises a hydrophilic polymer and a zeolite contained in the substance of the hydrophilic polymer, the content of the zeolite is 10% by weight or more, and the ratio of the X-type zeolite in the zeolite is 50% by weight. % -Zeolite-hydrophilic polymer composite, characterized by being at least%.
[2] The composite according to [1], wherein the hydrophilic polymer is cellulose.
[3] The composite according to [2], wherein the cellulose is natural cellulose.
[4] At least one metal selected from calcium, potassium, silver, copper, zinc, iron, nickel, cobalt, palladium, platinum, tungsten, yttrium and lanthanum is supported on zeolite, [1] to [3] The complex in any one of.
[5] The method for producing a zeolite-hydrophilic polymer composite according to [1], comprising the following steps (1) and (2):
(1) In the presence of a swelled hydrophilic polymer substrate, a silicon compound, an aluminum compound, and a basic substance are treated under the following conditions (a) and (b): A step of generating alumino silica gel in the hydrophilic polymer entity by reacting in the entity of:
(A) the molar ratio of the silicon compound, the aluminum compound and the basic substance is 1: 1 to 10: 4 to 50;
(B) the concentration of the basic substance is 1,000 to 10,000 mmol / l;
(2) The aluminosilica gel produced in the substance of the hydrophilic polymer in the step (1) is subjected to the following steps (c) and (d): The step of changing to X-type zeolite by reacting within the substance of the molecular substrate:
(C) The molar ratio of the silicon compound, the aluminum compound, and the basic substance is 1: 0.1 to 1: 1 and less than 4;
(D) The concentration of the basic substance is 500 mmol / l or more and less than 1,000 mmol / l.
[6] The method according to [5], wherein the step (2) includes adding water and a silicon compound to the reaction mixture of the step (1) to satisfy the conditions (c) and (d). .
[7] When the average particle size of the alumino silica gel produced in the reaction mixture of the step (1) is 0.001 to 0.1 μm, including adding water and a silicon compound to the reaction mixture. [6] The method according to the above.
[8] The method according to any one of [5] to [7], wherein the hydrophilic polymer substrate is cellulose.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The zeolite-hydrophilic polymer composite of the present invention comprises a hydrophilic polymer and a zeolite contained in the substance of the hydrophilic polymer, the zeolite content is 10% by weight or more, and the zeolite The ratio of the X-type zeolite is 50% by weight or more, and the adsorption ability of the X-type zeolite can be sufficiently exhibited.
[0008]
The hydrophilic polymer in the composite is not particularly limited as long as it swells with water. For example, natural cellulose (pulp, kenaf, cotton, hemp, etc.), regenerated cellulose (cellophane, cellulose beads, rayon, cellulose sponge, etc.), bacterial cellulose and ethyl cellulose chemically modified from cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl Cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose, as well as natural or artificial hydrophilic polymers such as silk, wool, polyvinyl alcohol, cross-linked polyvinyl alcohol, chitin, chitosan, ethylene vinyl acetate copolymer, polyvinyl formal, and polyacrylamide High water-absorbing polymer gel, collagen, propolis, lacquer, wood powder and the like.
Of these, natural cellulose (particularly pulp) and regenerated cellulose are preferably used from the standpoint of actual usage, price, and ease of handling.
[0009]
The X-type zeolite in the composite is not particularly limited as long as Si / Al is greater than 1 and less than 1.5. For example, Na ₂ (Al ₂ Si _2.5 O ₉ ) ・ 6.2H ₂ O, Na ₈₆ (Al ₈₆ Si ₁₀₆ O ₃₈₄ ) ・ 264H ₂ O, Na _86.5 (Al _86.5 Si _105.5 O ₃₈₄ ) ・ 258H ₂ O, Na ₈₈ (Al ₈₈ Si ₁₀₄ O ₃₈₄ ) ・ 220H ₂ O etc. are mentioned.
Among these, Na is relatively easy to synthesize. ₈₆ (Al ₈₆ Si ₁₀₆ O ₃₈₄ ) ・ 264H ₂ O is preferred.
[0010]
Further, the zeolite other than the X-type zeolite contained in the composite is not particularly limited. For example, A-type zeolite (Si / Al ratio: 1), Y-type zeolite (Si / Al ratio: 1.5 to 3.0), ZSM-5 type zeolite (Si / Al ratio: 10 or more), ZSM-11 type zeolite (Si / Al ratio: 10 or more), silicalite (Si / Al ratio: infinity), synthetic mordenite ( Si / Al ratio: 4.5-12) etc. are mentioned. Two or more of these may be contained.
[0011]
The zeolite content in the composite is 10% by weight or more. When the content of the zeolite is less than 10% by weight, the composite does not have a sufficient adsorption capacity. Further, the content of the zeolite is preferably 20 to 59% by weight, more preferably 30 to 59% by weight in order to exhibit a sufficient initial adsorption rate, adsorption capacity, antibacterial property, and ion exchange property.
The zeolite content is the amount of ash per dry weight determined from the dry weight of the composite and the amount of ash obtained by ashing the composite.
[0012]
Moreover, the ratio of the X-type zeolite in the zeolite contained in the composite is 50% by weight or more. When the ratio of the X-type zeolite is less than 50% by weight, the composite does not sufficiently exhibit the adsorption ability of the X-type zeolite. The ratio of the X-type zeolite is preferably as high as possible, and is preferably 60 to 100% by weight, more preferably 80 to 100% by weight from the viewpoint that a significant difference appears in the adsorption rate.
The ratio of the X-type zeolite in the zeolite can be obtained by performing X-ray diffraction on the ash obtained by ashing the composite.
[0013]
The composite may contain an inorganic porous material other than zeolite. Preferably, an inorganic porous material having adsorption characteristics is used. Examples of such inorganic porous materials include hydrotalcite, hydroxyapatite, clay minerals, silica gel, alumina gel, alumino silica gel, and the like. Two or more of these may be contained.
[0014]
In the composite, the zeolite is contained within the hydrophilic polymer entity. Here, in the substance of the hydrophilic polymer, for example, when the hydrophilic polymer is natural cellulose such as pulp, the inside of the base material containing natural cellulose as a constituent component, more specifically, the microfibril constituting the cell wall. By swelling a region (site) generated by swelling the gap (100 to 5000 mm) between (φ about 0.1 μm) and the microfibril, or a region where the cellulose molecular chain is not crystallized in the microfibril. It means a site (site) that occurs, and does not include, for example, the cell wall surface of cellulose, pores or lumens originally present in the cell wall.
The phrase “containing a zeolite in the substance of the hydrophilic polymer” means that part or all of the zeolite is present in the substance of the cellulose substrate.
[0015]
The shape of the composite of the present invention is not particularly limited, and examples thereof include a sheet-like material, a granular material, a fibrous material, a thread-like material, a rod-like material, a tubular material, a plate-like material, a corrugated cardboard honeycomb-like material, and an irregularly shaped material. Can be mentioned. These may be porous. Although it can be processed into a predetermined form after it is made into a composite, a hydrophilic polymer that is flexible and easy to handle is manufactured or processed in a predetermined form in advance, and then the zeolite is contained within the substance. It is easy to form a complex by reacting, which is preferable.
[0016]
In the composite, (1) in the presence of a swelled hydrophilic polymer substrate, a silicon compound, an aluminum compound, and a basic substance are mixed with the hydrophilic compound under the following conditions (a) and (b): A step of generating alumino silica gel in the hydrophilic polymer substance by reacting in the substance of the hydrophilic polymer substrate:
(A) the molar ratio of the silicon compound, the aluminum compound and the basic substance is 1: 1 to 10: 4 to 50;
(B) the concentration of the basic substance is 1,000 to 10,000 mmol / l;
(2) The aluminosilica gel produced in the substance of the hydrophilic polymer in the step (1) is subjected to the following steps (c) and (d): The step of changing to X-type zeolite by reacting within the substance of the molecular substrate:
(C) The molar ratio of the silicon compound, the aluminum compound, and the basic substance is 1: 0.1 to 1: 1 and less than 4;
(D) the concentration of the basic substance is 500 mmol / l or more and less than 1000 mmol / l;
It can manufacture by the method containing these.
[0017]
Here, the molar ratio of the silicon compound, the aluminum compound, and the basic substance refers to the silicon contained in the silicon compound, the aluminum contained in the aluminum compound, and the hydroxide ion contained in the basic substance (which itself is In the case of producing hydroxide ions when not containing hydroxide ions and forming an aqueous solution, it means the molar ratio of the generated hydroxide ions). Similarly, the molar concentrations of the following components in the aqueous solution are also values for silicon, aluminum, and hydroxide ions.
[0018]
Hereafter, the manufacturing method of the composite_body | complex of this invention is demonstrated divided into each process (process (1) and process (2)).
[0019]
[Step (1)]
This step is performed under conditions under which the A-type zeolite can produce a silicon compound, an aluminum compound, and a basic substance in the presence of a swelled hydrophilic polymer substrate (that is, the above (a) and (b) In this step, the reaction is carried out in the substance of the hydrophilic polymer base material to produce fine aluminosilica gel which becomes the core of the X-type zeolite in the step (2) described later. This step can be performed according to the method for synthesizing zeolite in the substance of hydrophilic polymer described in JP-A-10-120923.
[0020]
The silicon compound is not particularly limited as long as it is soluble in water. Examples thereof include sodium metasilicate, potassium metasilicate, sodium orthosilicate, potassium orthosilicate, water glass, silica sol, and liquid sodium silicate. However, sodium metasilicate is preferable from the viewpoint of obtaining a zeolite having high solubility in water and high crystallinity. The concentration of the aqueous solution of the silicon compound is not particularly limited, but is preferably 50 to 1,000 mmol / l, more preferably 100 to 700 mmol / l.
[0021]
Examples of the aluminum compound include sodium aluminate, potassium aluminate, aluminum sulfate, aluminum chloride, aluminum nitrate, liquid sodium aluminate, liquid potassium aluminate, and the like, but have high solubility in water and high crystallinity. Liquid sodium aluminate is preferred from the viewpoint of obtaining zeolite. The concentration of the aqueous solution of the aluminum compound is not particularly limited, but is preferably 50 to 10,000 mmol / l, more preferably 100 to 5,000 mmol / l.
[0022]
Examples of the basic substance include sodium hydroxide, potassium hydroxide, liquid caustic soda, liquid caustic potash, and the like. Sodium hydroxide is preferable from the viewpoint of obtaining a zeolite having high solubility in water and high crystallinity. The concentration of the basic substance is 1,000 to 10,000 mmol / l, preferably 2,000 to 5,000 mmol / l, because a fairly high alkali concentration is required to crystallize the zeolite. It is.
[0023]
In the said process (1), the molar ratio of the silicon compound in a reaction mixture, an aluminum compound, and a basic substance is 1: 1-10: 4-50, Preferably it is 1: 2-7: 5-40. By setting the molar ratio of the silicon compound, the aluminum compound, and the basic substance within the above range and the concentration of the basic substance within the above range, the substance of the X-type zeolite is added to the substance of the hydrophilic polymer in the step (2) described later. A minute alumino silica gel as a core can be produced.
[0024]
Hereinafter, the step (1) will be described in detail by taking an example of the case where the hydrophilic polymer is cellulose.
[0025]
First, a cellulose base material is impregnated with a mixed aqueous solution of a silicon compound and a basic substance. The impregnation method is not particularly limited, and for example, a method of immersing the cellulose base material in the mixed aqueous solution, spraying the mixed aqueous solution onto the composite, or applying the mixed aqueous solution with various coaters can be used.
[0026]
The cellulose base material impregnated with the above mixed aqueous solution is preferably adjusted in the amount of the impregnated solution. As the method, scraping with a blade, squeezing between rolls, squeezing with a press, or the like is used. Although there is no restriction | limiting in particular in the quantity of the impregnation solution after adjustment, It is preferable to adjust to the range of 1.0-20 times with respect to the dry weight of a cellulose base material.
[0027]
The cellulose base material impregnated with the mixed aqueous solution may have an impregnation time before or after adjusting the amount of the solution so that the solution can sufficiently permeate. The impregnation time is 10 minutes to 2 hours, and can be appropriately selected depending on the type of the cellulose substrate.
[0028]
Next, the cellulose base material in which the amount of the mixed solution is adjusted is immersed in an aqueous solution of an aluminum compound. Thereby, in a post-process (2), minute alumino silica gel which becomes the core of the X-type zeolite is generated in the substance of the cellulose base material. However, if the reaction proceeds too much, the content of the A-type zeolite in the final product increases, so it is important to prevent the reaction from proceeding excessively by controlling the reaction temperature and reaction time.
[0029]
The reaction temperature is preferably 20 to 70 ° C, more preferably 40 to 60 ° C. The reaction is preferably carried out while gently raising the temperature from a relatively low temperature from the viewpoint of avoiding crystallization into A-type zeolite.
[0030]
The reaction time is preferably from the viewpoint of sufficiently producing a fine alumino silica gel as a nucleus of the X-type zeolite in the post-process (2) in the substance of the hydrophilic polymer and avoiding crystallization into the A-type zeolite. Is 10 to 180 minutes, more preferably 30 to 180 minutes.
[0031]
In addition, in the said process (1), since the gel produces | generates at the time of mixing each silicon compound, an aluminum compound, and each aqueous solution of a basic substance, when a silicon compound and an aluminum compound are mixed, both are simultaneously made to impregnate a cellulose base material. This is not possible, but there are no particular restrictions on other orders. That is, a mixed aqueous solution of an aluminum compound and a basic substance may be impregnated first, and then an aqueous solution of a silicon compound may be impregnated, or an aqueous solution of either a silicon compound or an aluminum compound may be impregnated first. Then, the mixed aqueous solution of the other compound and the basic substance may be impregnated. Furthermore, the cellulose base material is impregnated with an aqueous solution of a basic substance, and then an aqueous solution of either a silicon compound or an aluminum compound is impregnated, and finally the aqueous solution of the other compound is impregnated. Also good.
[0032]
[Step (2)]
This step is a step of changing the composition of the fine alumino silica gel produced in the substance of the hydrophilic polymer by the above step (1) to change to X-type zeolite.
[0033]
In the step (2), the molar ratio of the silicon compound, the aluminum compound and the basic substance in the reaction mixture is 1: 0.1 to 1: 1 and less than 4, preferably 1: 0.1 to 0.7: 1. And the concentration of the basic substance is 500 mmol / l or more and less than 1,000 mmol / l, preferably 500 to 700 mmol / l. When the molar ratio of the silicon compound, the aluminum compound and the basic substance and the concentration of the basic substance are not within the above ranges, a composite containing a sufficient amount of X-type zeolite cannot be obtained.
[0034]
The step (2) is performed by separating the reaction product from the reaction mixture of the step (1) so that the molar ratio of the silicon compound, the aluminum compound and the basic substance and the concentration of the basic substance are within the above ranges. However, since it is simple, it is preferable to change the molar ratio of the silicon compound, the aluminum compound and the basic substance and the concentration of the basic substance in the reaction mixture in the step (1).
[0035]
The method for changing the molar ratio of the silicon compound, the aluminum compound and the basic substance and the concentration of the basic substance in the reaction mixture in step (1) to the above ranges is not particularly limited, and for example, water and silicon in the reaction solution Examples include a method of adding a compound, a method of adding water, a silicon compound and an aluminum compound so as to result in the molar ratio to the reaction mixture, a method of adding water to the reaction mixture and removing the aluminum compound, and the like. Since it is simple, the method of adding water and a silicon compound to a reaction mixture is preferable.
[0036]
The method for adding water and the silicon compound is not particularly limited, and the silicon compound may be added after adding water, or the water may be added after adding the silicon compound. Moreover, you may add a silicon compound and water simultaneously. As the addition method, the whole amount may be added at once, or may be added as appropriate. From the viewpoint of changing the composition of the alumino silica gel all at once, the effect of greatly lowering the temperature and delaying the crystallization reaction to A-type zeolite is great. A method is preferred in which is dissolved in water and added all at once.
[0037]
The addition of water and silicon compound is preferably such that the average particle size of the aluminosilica gel produced in the reaction mixture of step (1) is 0.001 to 0.1 μm, more preferably 0.005 to 0.05 μm. Do it when there is. If the average particle size of the alumino silica gel is less than 0.001 μm, gel particles are released again into the liquid from the substance of the hydrophilic polymer by stirring or the like, and a sufficient amount of performance is obtained from the substance of the hydrophilic polymer. On the other hand, when it grows to a size exceeding 0.1 μm, it often crystallizes into A-type zeolite.
[0038]
Here, the average particle diameter is a median diameter and is measured by a particle size distribution measuring device (LA-920 manufactured by Horiba, Ltd.).
[0039]
Furthermore, the addition of water and the silicon compound is preferably such that the temperature of the reaction mixture is in the range of 20 to 70 ° C, more preferably in the range of 50 to 60 ° C, and the step (1) is more preferably performed for 10 to 180 minutes. Is preferably performed after 30 to 180 minutes. This is because it becomes difficult to prevent the aluminosilica gel from crystallizing into A-type zeolite when the reaction mixture is added at a temperature exceeding 70 ° C. On the other hand, at a temperature below 20 ° C. If added, it takes too much time to produce the zeolite, which is not preferable for production efficiency. In addition, when the process proceeds to step (2) in less than 10 minutes from the start of the reaction in the above step (1), a sufficient amount of fine aluminosilica gel cannot be fixed within the substance of the hydrophilic polymer. This is because the zeolite content itself becomes low. On the other hand, when it is performed for more than 180 minutes, the crystallization reaction to the A-type zeolite proceeds, and the ratio of the X-type zeolite in the zeolite in the final product is low. Because it becomes.
[0040]
The zeolite-hydrophilic polymer composite of the present invention obtained as described above contains X-type zeolite in a sufficient amount in terms of performance in the substance of the hydrophilic polymer substrate. Zeolite has a larger pore diameter than A-type zeolite and is excellent in acid resistance. Therefore, the composite of the present invention has relatively large molecules (for example, hydrogen sulfide gas, sulfurous acid gas, nitrous acid gas, hyponitrous acid gas, dimethylamine, trimethylamine, Efficiently adsorbs methyl mercaptan, VOC (volatile organic compounds; such as xylene, toluene, pyridine, acetaldehyde, ethanol, propanol, butanol, acetic acid, butyric acid, propionic acid, isovaleric acid, trichloroethylene, dichloromethane, etc.) be able to. That is, it can be suitably used as an adsorbent for such a gas. In addition, the composite is used in applications where acid resistance is a problem in the composite containing A-type zeolite (for example, a filter medium for fruit juice, a heavy metal ion in an acidic waste liquid, a radioactive metal ion, a recovery filter medium for precious metal ions, a strong acid And the like, and can be suitably used in adsorbent filter media for natural gas.
[0041]
Further, the zeolite-hydrophilic polymer composite is dehydrated, washed with water, and then immersed in an aqueous solution of a metal salt having a catalytic function to obtain a metal-supported zeolite-hydrophilic polymer composite. Examples of the metal used include calcium, potassium, silver, copper, zinc, iron, nickel, cobalt, palladium, platinum, tungsten, yttrium, and lanthanum. Copper is preferable because of its high catalytic function. , Iron, nickel and cobalt. A plurality of these metals may be used in combination. Although there is no restriction | limiting in particular in the density | concentration of the aqueous solution of a metal salt, Preferably it is 1.0-100 mmol / l, and there is no restriction | limiting in particular also in the temperature and time to immerse. At this time, since the hydrophilic polymer substrate can permeate the aqueous solution, the metal can be supported on the entire zeolite in the substance of the hydrophilic polymer substrate without waste.
[0042]
For example, a zeolite-hydrophilic polymer composite supporting silver, copper or zinc exhibits antibacterial properties, and a zeolite-hydrophilic polymer composite supporting palladium or platinum can adsorb ethylene. Zeolite-hydrophilic polymer composite supporting silver or copper has the effect of preserving the freshness of fruits and vegetables, so that it can adsorb and decompose hydrogen sulfide, so it has a metal rust prevention or deodorization effect, and also adsorbs ammonia. Because it can be decomposed, it has deodorizing effect. In addition, the zeolite-hydrophilic polymer composite supporting silver has a deodorizing effect because it can adsorb and decompose methyl mercaptan. The zeolite-hydrophilic polymer composite supporting tungsten, yttrium and lanthanum has a function of a solid acid catalyst, and has an effect of decomposing many malodorous molecules. At this time, since the hydrophilic polymer substrate can sufficiently permeate the gas, the entire metal-supported zeolite in the substance of the hydrophilic polymer substrate can be used without waste to adsorb and decompose the gas.
[0043]
In addition, various high function papers can be obtained by adding a volatile material to the zeolite-hydrophilic polymer composite. Examples of the volatile substance include L-menthol, hinokitiol, phytoncide, wasabiol, and limonene. These can be supported by a method known per se, for example, impregnation, coating, press-fitting and the like.
[0044]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these Examples. In the following examples and comparative examples, “%” represents “% by weight” unless otherwise specified. Moreover, the measuring method used by the Example and the comparative example is shown below.
[0045]
[Average particle diameter of alumino silica gel in the reaction mixture]
The average particle size (median size) of the alumino silica gel was measured by collecting 10 ml of exudate of the reaction mixture and measuring with a particle size distribution analyzer (LA-920) manufactured by Horiba, Ltd.
[0046]
[Zeolite content in composite]
The composite was dried at 60 ° C. to a constant weight, and then 1 g was precisely weighed in a crucible having a constant weight. Next, it was ashed in an electric furnace at 400 ° C., and the ash content was weighed. The amount of ash per dry weight of the composite was taken as the zeolite content.
[0047]
[Ratio of X-type zeolite in zeolite]
The ratio of the X-type zeolite in the zeolite was determined by analyzing the ash content of the composite obtained as described above with a powder X-ray diffractometer (Rigaku RINT-2000, Inc.), and from the peak intensity of 2θ = 6.120 °. It was determined by applying data to a calibration curve prepared by mixing pure A-type zeolite and X-type zeolite in various proportions in advance.
[0048]
Example 1
To 1 kg of NBKP (conifer bleached kraft pulp) was added 5160 ml of a mixed aqueous solution of 1500 g of 31% liquid sodium aluminate (Sumitomo Chemical Co., Ltd.) and 2100 g of 48% liquid caustic soda (Toagosei Co., Ltd.). Add 1080% 61% No. 1 L2 sodium silicate (Tosoh Sangyo Co., Ltd.) and stir well. This raw material was heated with a hot water circulation device (set temperature 90 ° C.), and after 70 minutes from the start of heating, when the material temperature reached 56 ° C. In addition, 660 g of 61% No. 1 L2 sodium silicate (Tosoh Sangyo Co., Ltd.) and 7500 ml of water were added as auxiliary materials, and after stirring well, it took 2 hours until the material temperature reached 84 ° C. And heated. Thereafter, the mixture was kept at 84 ° C. for 1 hour and 30 minutes, and then the product was taken out. This was subjected to solid-liquid separation using a small centrifugal dehydrator (manufactured by Sanyo Riken Chemical Co., Ltd .: SYK-5000-15A) to obtain a zeolite-pulp composite. The zeolite content of the obtained zeolite-pulp composite was 21.6% by weight, and the ratio of X-type zeolite in the zeolite was 81.2% by weight. Moreover, the change of the material temperature in the said Example is shown in FIG. 1 (♦).
[0049]
Example 2
To 1 kg of NBKP (conifer bleached kraft pulp) was added 5160 ml of a mixed aqueous solution of 1500 g of 31% liquid sodium aluminate (Sumitomo Chemical Co., Ltd.) and 2100 g of 48% liquid caustic soda (Toagosei Co., Ltd.). Add 1080% 61% No. 1 L2 sodium silicate (Tosoh Sangyo Co., Ltd.) and stir well. This raw material was heated with a hot water circulation device (set temperature 70 ° C.), and after 90 minutes from the start of heating, when the material temperature reached 57 ° C. (the average particle diameter of the alumino silica gel in the reaction mixture at this time was 0.03 μm). In addition, 660 g of 61% No. 1 L2 sodium silicate (Tosoh Sangyo Co., Ltd.) and 7500 ml of water were added as auxiliary materials, and after stirring well, a hot water circulator until the material temperature reached 84 ° C. The temperature was switched to 90 ° C. and heated for 2 hours. Thereafter, the mixture was kept at 84 ° C. for 1 hour and 30 minutes, and then the product was taken out. This was subjected to solid-liquid separation using a small centrifugal dehydrator (manufactured by Sanyo Riken Chemical Co., Ltd .: SYK-5000-15A) to obtain a zeolite-pulp composite. The zeolite content of the obtained zeolite-pulp composite was 29.7% by weight, and the ratio of X-type zeolite in the zeolite was 89.6% by weight. Moreover, the change of the material temperature in the said Example is shown in FIG.
[0050]
Example 3
To 1 kg of NBKP (conifer bleached kraft pulp) was added 5160 ml of a mixed aqueous solution of 1500 g of 31% liquid sodium aluminate (Sumitomo Chemical Co., Ltd.) and 2100 g of 48% liquid caustic soda (Toagosei Co., Ltd.). Add 1080% 61% No. 1 L2 sodium silicate (Tosoh Sangyo Co., Ltd.) and stir well. This raw material was heated with a hot water circulation device (set temperature 60 ° C.), and after 135 minutes from the start of heating, when the material temperature reached 58 ° C. (the average particle size of the alumino silica gel in the reaction mixture at this time was 0.02 μm). In addition, 660 g of 61% No. 1 L2 sodium silicate (Tosoh Sangyo Co., Ltd.) and 7500 ml of water were added as auxiliary materials, and after stirring well, a hot water circulator until the material temperature reached 84 ° C. The temperature was switched to 90 ° C. and heated for 2 hours. Thereafter, the mixture was kept at 84 ° C. for 1 hour and 30 minutes, and then the product was taken out. This was subjected to solid-liquid separation using a small centrifugal dehydrator (manufactured by Sanyo Riken Chemical Co., Ltd .: SYK-5000-15A) to obtain a zeolite-pulp composite. The zeolite content of the obtained zeolite-pulp composite was 41.0% by weight, and the ratio of X-type zeolite in the zeolite was 92.0% by weight. Moreover, the change of the material temperature in the said Example is shown in FIG.
[0051]
Example 4
2.0 g of copper sulfate pentahydrate (Wako Pure Chemical Industries, Ltd., special grade Mw = 249.69) was weighed out and dissolved in 1.0 L of water. The copper ion concentration of the copper ion aqueous solution thus prepared was 508 ppm. To this aqueous solution, 2.0 g of the composite obtained in Example 3 was added and stirred for 30 minutes. This was subjected to solid-liquid separation using a small centrifugal dehydrator (manufactured by Sanyo Riken Chemical Co., Ltd .: SYK-5000-15A) to obtain a copper ion-supported zeolite-pulp composite. From the copper ion concentration of the filtrate, it was found that 25.4 mg / g of copper ions was supported in the obtained composite.
[0052]
Comparative Example 1
To 1 kg of NBKP (conifer bleached kraft pulp) was added a mixed aqueous solution 12660 ml of 1500 g of 31% liquid sodium aluminate (Sumitomo Chemical Co., Ltd.) and 2100 g of 48% liquid caustic soda (Toagosei Co., Ltd.). 1740 g of 61% No. 1 L2 sodium silicate (Tosoh Sangyo Co., Ltd.) was added and stirred well. This raw material was heated with a hot water circulation device (set temperature 90 ° C.) and heated for 2 hours until the material temperature reached 84 ° C. Thereafter, the mixture was kept at 84 ° C. for 1 hour and 30 minutes, and then the product was taken out. This was subjected to solid-liquid separation using a small centrifugal dehydrator (manufactured by Sanyo Riken Chemical Co., Ltd .: SYK-5000-15A) to obtain a zeolite-pulp composite. The zeolite content of the obtained zeolite-pulp composite was 8.6% by weight, the proportion of zeolite A in the zeolite was 4.8% by weight, and the proportion of zeolite X was 95.2% by weight. It was. Further, the change in material temperature in the comparative example is shown in FIG.
[0053]
Comparative Example 2
To 1 kg of NBKP (conifer bleached kraft pulp) was added 5160 ml of a mixed aqueous solution of 1500 g of 31% liquid sodium aluminate (Sumitomo Chemical Co., Ltd.) and 2100 g of 48% liquid caustic soda (Toagosei Co., Ltd.). Add 1080% 61% No. 1 L2 sodium silicate (Tosoh Sangyo Co., Ltd.) and stir well. This raw material was heated with a hot water circulation device (set temperature 90 ° C.) and heated for 2 hours until the material temperature reached 84 ° C. Thereafter, the mixture was kept at 84 ° C. for 1 hour and 30 minutes, and then the product was taken out. This was subjected to solid-liquid separation using a small centrifugal dehydrator (manufactured by Sanyo Riken Chemical Co., Ltd .: SYK-5000-15A) to obtain a zeolite-pulp composite. The zeolite content of the obtained zeolite-pulp composite was 38.5% by weight, the ratio of A-type zeolite in this zeolite was 99.5% by weight, and the ratio of X-type zeolite was 0.5% by weight. It was.
[0054]
Comparative Example 3
Using the composite obtained in Comparative Example 2, a copper ion-supported zeolite-pulp composite was obtained in the same manner as in Example 4. From the copper ion concentration of the filtrate, it was found that 25.4 mg / g of copper ions was supported in the obtained composite.
[0055]
Experimental example 1
1.0 g of the copper ion-carrying zeolite-pulp composite obtained in Example 4 and Comparative Example 3 was weighed, put in a PE bag (capacity 4 L), and deaerated. Next, 1.5 L of 320 ppm hydrogen sulfide gas was injected, and the change over time in the system concentration of the hydrogen sulfide gas was measured with a detector tube manufactured by Gastec Corporation. The results are shown in Table 1 and FIG.
[0056]
[Table 1]

[0057]
From Table 1 and FIG. 2, the hydrogen sulfide gas adsorption rate of the composite of Example 4 was about twice that of the composite of Comparative Example 3. Further, in the composite of Example 4, the hydrogen sulfide gas concentration was almost 0 ppm at 5 minutes, whereas in the composite of Comparative Example 3, 140 ppm remained.
[0058]
Experimental example 2
1.0 g of the copper ion-carrying zeolite-pulp composite obtained in Example 4 and Comparative Example 3 was weighed, put in a PE bag (capacity 4 L), and deaerated. Next, 1.5 L of 180 ppm sulfurous acid gas was injected, and the change over time in the system concentration of sulfurous acid gas was measured with a detector tube manufactured by Gastec Corporation. The results are shown in Table 2 and FIG.
[0059]
[Table 2]

[0060]
From Table 2 and FIG. 3, the sulfurous acid gas adsorption rate of the composite of Example 4 was about twice that of the composite of Comparative Example 3. Further, in the composite of Example 4, the sulfurous acid gas concentration became 1 ppm at 5 minutes, whereas in the composite of Comparative Example 3, 85 ppm remained.
[0061]
From the above, it has been found that the adsorption rate of hydrogen sulfide gas, sulfurous acid gas, etc. can be remarkably improved by changing the zeolite contained in the substance of cellulose from the A type to the X type having a large pore diameter. .
[0062]
Experimental example 3
The composites obtained in Example 3 and Comparative Example 2 were dried at 105 ° C. for 24 hours, and 1.0 g was weighed out. These were placed in 200 mL of 1.0 mM acetic acid-sodium acetate buffer at pH = 4.0 and 5.0, respectively, and allowed to stand at 25 ° C. for 24 hours. After 24 hours, the complex was taken out using a small centrifuge (manufactured by Sanyo Rika Machinery Co., Ltd .: SYK-5000-15A), washed with 2.0 L of water, dried at 105 ° C. for 24 hours, It was measured. The results are shown in Table 3.
[0063]
[Table 3]

[0064]
From Table 3, at pH = 4.0, the reduced weight of the composite obtained in Example 3 was only 39% of the amount of zeolite contained in the composite, and only a part of the zeolite was dissolved. In contrast, the reduced weight of the composite obtained in Comparative Example 2 substantially matched the amount of zeolite contained in the composite, and almost all the zeolite was dissolved.
[0065]
At pH = 5.0, the reduced weight of the composite obtained in Example 3 was 17% of the amount of zeolite contained in the composite, and most of the zeolite remained, whereas The reduced weight of the composite obtained in Comparative Example 2 almost coincided with the amount of zeolite contained in the composite, and almost all of the zeolite was dissolved in the same manner as at pH = 4.0.
[0066]
Based on the above results, in the zeolite-hydrophilic polymer composite, the zeolite contained in the substance of cellulose is X-type zeolite, so that it can be suitably used for applications where acid resistance is a problem with A-type zeolite. Turned out to be possible.
[0067]
【The invention's effect】
Since the composite of the present invention contains a sufficient amount of X-type zeolite having a large pore diameter and excellent acid resistance as compared with A-type zeolite, satisfactory adsorption capacity can be obtained with A-type zeolite. Relatively large molecules (for example, hydrogen sulfide gas, sulfurous acid gas, nitrous acid gas, hyponitrous acid gas, dimethylamine, trimethylamine, methyl mercaptan, VOC (volatile organic compounds; for example, xylene, toluene, pyridine, acetaldehyde, etc. ), Ethanol, propanol, butanol, acetic acid, butyric acid, propionic acid, isovaleric acid, trichloroethylene, dichloromethane, etc.) can be adsorbed efficiently. That is, it can be suitably used as an adsorbent for such a gas. In addition, the composite is used in applications where acid resistance is a problem in the composite containing A-type zeolite (for example, a filter medium for fruit juice, a heavy metal ion in an acidic waste liquid, a radioactive metal ion, a recovery filter medium for precious metal ions, a strong acid And the like, and can be suitably used in adsorbent filter media for natural gas.
[Brief description of the drawings]
1 is a graph showing changes in material temperature in Examples 1 to 4 and Comparative Example 1. FIG.
2 is a graph showing the hydrogen sulfide gas adsorption capacity of each composite obtained in Example 4 and Comparative Example 3. FIG.
3 is a graph showing the sulfurous acid gas adsorption ability of each composite obtained in Example 4 and Comparative Example 3. FIG.

Claims (6)

It comprises the following steps (1) and (2), characterized in that it comprises a hydrophilic polymer and a zeolite contained in the substance of the hydrophilic polymer, and the zeolite content is 10% by weight or more. And a method for producing a zeolite-hydrophilic polymer composite in which the ratio of the X-type zeolite in the zeolite is 50% by weight or more :
(1) In the presence of a swelled hydrophilic polymer substrate, a silicon compound, an aluminum compound, and a basic substance are treated under the following conditions (a) and (b): A step of generating alumino silica gel in the hydrophilic polymer entity by reacting in the entity of:
(A) the molar ratio of the silicon compound, the aluminum compound and the basic substance is 1: 1 to 10: 4 to 50;
(B) the concentration of the basic substance is 1,000 to 10,000 mmol / l;
(2) The aluminosilica gel produced in the substance of the hydrophilic polymer in the step (1) is subjected to the following steps (c) and (d): The step of changing to X-type zeolite by reacting within the substance of the molecular substrate:
(C) The molar ratio of the silicon compound, the aluminum compound, and the basic substance is 1: 0.1 to 1: 1 and less than 4;
(D) The concentration of the basic substance is 500 mmol / l or more and less than 1,000 mmol / l. Step (2) is, by adding water and a silicon compound to the reaction mixture of step (1), the (c) and comprises a condition (d), The method of claim 1, wherein. When the average particle diameter of the aluminosilicate silica gel formed in the reaction mixture of step (1) is 0.001～0.1Myuemu, comprising the reaction mixture is added to water and silicon compound, according to claim 2 The method described. The method according to any one of claims 1 to 3 , wherein the hydrophilic polymer substrate is cellulose. The method according to claim 4, wherein the cellulose is natural cellulose. Calcium, potassium, silver, copper, zinc, iron, nickel, cobalt, by immersing the zeolite-hydrophilic polymer composite produced by the method according to any one of claims 1 to 5 in a metal salt aqueous solution. A method for producing a metal-supported zeolite-hydrophilic polymer composite in which at least one metal selected from palladium, platinum, tungsten, yttrium and lanthanum is supported on zeolite.

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