TW202135931A - Substance removal complex as well as fiber structure, resin molding and filter containing the complex - Google Patents

Abstract

In the past, various sulfur-based compound removers have been studied as countermeasures for solving those problems such as metal corrosion and the like, which are caused by sulfur-based compounds such as hydrogen sulfide and methyl mercaptan. However, there are problems such as that the raw materials are easily falling off from the base material, and various adverse effects on the human body are caused thereby using the same, or it is necessary to use expensive metal compounds. An object of the present invention is to provide a substance removal complex which is safe, inexpensive, and has excellent removal performance of removing sulfur-based compounds and others. A substance removal complex characterized in comprising an organic polymer having a carboxyl group amount in the range of 0.3 to 12.0 mmol/g, and a ferric hydroxide and/or a ferric oxide.

Description

Substance removal composite, and fiber structure, resin molded product, and filter containing the composite

The present invention relates to a substance-removable composite capable of removing substances such as hydrogen sulfide or sulfur compounds present in gas or liquid, and a fiber structure, resin molded product, and filter containing the composite.

In recent years, sulfur-based gases such as hydrogen sulfide and methyl mercaptan generated by various major factors such as industrial drainage and domestic drainage have caused problems such as metal corrosion. For countermeasures to such problems, various sulfur-based gas removers have been reviewed. For example, Patent Document 1 examines a zinc oxide fine powder adsorbent that controls the pore volume, and it has a high sulfur-based gas deodorizing capacity. The deodorizing composition disclosed in this patent document is a kind of deodorizing fiber; for example, when it is produced, for example, zinc oxide fine powder is used as an aqueous dispersion to impregnate and adhere to the fiber. The method and so on. However, when this method is used, since the amount of zinc oxide fine powder adhering to the fiber is greatly restricted, the deodorizing capacity may decrease. In addition, there is no particularly strong interaction between the zinc oxide fine powder and the fiber, and because it is only a simple physical adsorption, problems such as easy falling off may also occur when immersed in water.

On the other hand, Patent Document 2 cited a method by adding permanganese oxide and polyoxyalkylene to a carboxyl-containing support to support manganese oxide to form a deodorant for hydrogen sulfide. The method of performance complex. In the above method, although the amount of metal supported can be controlled and the hydrogen sulfide removal capacity can be controlled according to the ratio; however, the permanganate used is a compound with strong oxidizing power, so that such raw materials remain during production. There will be various adverse effects on the human body, etc. From this point of view, there will be problems in safety, so it is not a practical technology.

In addition, Patent Document 3 lists a deodorant fiber containing silver and copper in a crosslinked acrylic fiber. However, in order to produce such fibers, relatively expensive metal compounds such as silver nitrate and copper nitrate have to be used, which is not economical. ＜Advanced Technical Documents＞ ＜Patent Literature＞

<Patent Document 1> JP 2003-052800 A <Patent Document 2> Patent No. 5152669 <Patent Document 3> Patent Publication No. 3991748

The present invention is the inventor of innovative research and development in view of the current state of the prior art, and its purpose is to provide a substance-removing composite that is safe, inexpensive, and has excellent removal performance for sulfur-based gases and the like. ＜Means to solve the problem＞

The inventors of the present invention conducted intensive studies to achieve the above-mentioned objects and found that a complex of carboxyl groups, ferrous hydroxide, and/or ferrous oxide can provide excellent removal performance for sulfur-based gases and the like. this invention.

That is, the present invention is achieved by the following means. (1) A substance-removing complex characterized by containing an organic polymer having a carboxyl group content in the range of 0.3 to 12.0 mmol/g, and ferrous hydroxide and/or ferrous oxide. (2) The substance-removable composite as described in (1), characterized in that the iron content is in the range of 0.01 to 5.0% by weight. (3) The substance-removing complex as described in (1) or (2), characterized in that the deodorizing amount of hydrogen sulfide is 0.1 to 6.0 ml/g. (4) The substance-removable composite as described in any one of (1) to (3), which is characterized in that the shape is fibrous. (5) The substance-removable composite as described in (4), characterized in that the fineness is 1.0 to 10.0 dtex. (6) The substance-removable composite as described in (4) or (5), characterized in that the iron abundance rate on the surface is divided by the iron abundance rate at the center point of the long axis of the cross-section of the composite, which is The surface abundance ratio of iron is 10 or more. (7) The substance-removable composite described in any one of (4) to (6), characterized by having a core-sheath structure composed of a surface layer portion and a center portion, and the surface layer portion is composed of a carboxyl group-containing The polymer is formed; the center part is formed by an acrylonitrile-based polymer. (8) The substance-removable composite as described in any one of (1) to (3), characterized in that the shape is particulate. (9) A method for producing a substance-removable complex, characterized by comprising a process of reacting an organic polymer having a carboxyl group content in the range of 0.3-12.0 mmol/g with an aqueous solution of iron (III) salt. (10) The method for producing a substance-removable complex as described in (9), characterized in that at least a part of the carboxyl group of the organic polymer is at least one of the group consisting of sodium, magnesium, calcium, potassium, and ammonium One forms salts. (11) A fiber structure or resin molded product characterized by containing the substance-removable composite as described in any one of (1) to (8). (12) A filter characterized by containing the fiber structure or resin molded product as described in (11). <The effect of the invention>

The substance-removable composite of the present invention has the feature that since ferrous hydroxide and/or ferrous oxide are locally present on the surface, the speed of removing sulfur compounds, etc. from gas or liquid is rapid . Furthermore, since this composite uses ferrous hydroxide and/or ferrous oxide as a component for removing sulfur compounds, it is very safe and inexpensive. In addition, as described below, by adjusting the amount of basic carboxyl groups, it can be used to adjust the content of ferrous hydroxide and/or ferrous oxide, so it can be adapted to various applications. The substance-removable composite of the present invention having such properties can be used, for example, as a remover for removing sulfur compounds contained in metal corrosion inhibitors, alcohol, and the like.

Hereinafter, the present invention will be described in detail. The substance-removable composite system of the present invention includes an organic polymer having a carboxyl group, and also includes ferrous hydroxide and/or ferrous oxide (hereinafter, the two are also collectively referred to as "ferrous hydroxide, etc."). Such a substance-removable complex is not particularly limited. However, for example, an organic polymer having a carboxyl group may be provided with ferrous hydroxide or the like, and an organic polymer having a carboxyl group may be combined with hydrogen hydroxide. Iron and other kneaded products, etc. In addition, although the shape of such a substance-removable composite is not particularly limited, it may be, for example, fibrous or particulate. In addition, the term "carboxyl" in the present invention is not only a functional group represented by -COOH, but is used as a term that also includes a salt formed by the functional group and a cation; depending on needs, the former is also used as The acid type carboxyl group is expressed, and the latter is expressed as a basic carboxyl group.

The organic polymer forming the substance-removable complex of the present invention has carboxyl groups, and the amount of carboxyl groups of this organic polymer is preferably 0.3-12.0 mmol/g; preferably 1.0-9.0 mmol/g; more preferably 2.0～6.5 mmol/g. In this context, the amount of carboxyl groups is measured by a method described later; it means the amount of acid carboxyl groups of 1 g on average when various basic carboxyl groups are converted into acidic forms with acid. When the amount of carboxyl groups of this organic polymer is less than 0.3 mmol/g, the supporting amount of ferrous hydroxide, etc., which is restricted by the mechanism described later, will be significantly reduced, which may not have sufficient substance removal properties. , So bad. In addition, when the amount of such carboxyl groups exceeds 12.0 mmol/g, the durability of the organic polymer is significantly reduced, so that there is a possibility that the shape cannot be maintained.

又，關於氧化亞鐵，在製造之際的加熱過程（乾燥等）中，可推斷是因為引起脱水反應而生成氫氧化亞鐵。In the case of supplying ferrous hydroxide or the like to an organic polymer having a carboxyl group, it is preferable to replace the base type of the carboxyl group with a basic metal base type or an ammonium base type in advance, by making it and acidic The iron (Ⅲ) salt reacts and neutralizes, and uses various basic carboxyl groups as the reaction field to support ferrous hydroxide on the surface of the organic polymer. The type of iron (Ⅲ) salt and the type of basic carboxyl group used are not particularly limited; however, for example, ferrous nitrate can be used as the iron (Ⅲ) salt, and the basic type of organic polymer When the carboxyl group is used as the sodium-type carboxyl group, it can be inferred that ferrous hydroxide is formed on the surface of the organic polymer due to the reaction of Chem1 shown below. ＜化1＞

In addition, with regard to ferrous oxide, in the heating process (drying, etc.) during the production, it can be inferred that the dehydration reaction is caused to produce ferrous hydroxide.

The organic polymer having a carboxyl group used in the present invention may be, for example, an organic polymer such as an animal fiber such as wool or silk, a polyester having a carboxyl group, a polyamide, a vinyl polymer, and the like.

In addition, the iron content in the material-removable composite of the present invention is preferably 0.01 to 5.0% by weight, more preferably 0.1 to 3.0% by weight. In the case where the iron content is less than 0.01% by weight, the sulfur-based gas deodorizing performance of the composite body may be significantly reduced, which is not preferable. On the other hand, if it exceeds 5.0% by weight, it is conceivable that the possibility of ferrous hydroxide and the like falling off from the surface of the composite will increase, and the workability will deteriorate.

In addition, it is preferable that the ferrous hydroxide and the like of the substance-removable composite of the present invention are locally present on the surface. More specifically, it is preferable that the surface abundance ratio of iron is 10 or more, and more preferably 30 or more. In this article, the so-called iron surface abundance ratio refers to the value obtained by dividing the iron abundance rate on the surface of the composite by the iron abundance rate at the center point of the long axis of the composite cross-section, and they are measured according to the method described later . When the surface ratio of iron is less than 10, there will be a considerable amount of ferrous hydroxide in the composite; The contact confirmation rate will be significantly reduced, and as a result, the sulfur-based gas deodorizing performance may be reduced, which is not good.

The method of making the surface abundance ratio of iron of the substance-removable composite of the present invention 10 or more. For example, it is possible to use a substance with a carboxyl group locally present in the surface layer as an organic polymer, and combine it with iron (Ⅲ) The method of salt reaction. For example, when the organic polymer of the present invention is fibrous, it may be a core-sheath structure formed of a surface layer portion composed of a polymer having a carboxyl group and a center portion composed of an acrylonitrile-based polymer. . By having such a core-sheath structure, the carboxyl groups locally present on the polymer surface are used as the reaction field to cause the iron (III) salt to react, so that ferrous hydroxide and the like can locally exist on the polymer surface. In addition, such a structure is produced by using acrylic fibers as a starting material as a starting material and simultaneously performing methods such as cross-linking treatment with hydrazine-based compounds and hydrolysis treatment with alkali metals as described later.

The substance removal complex of the present invention preferably has a hydrogen sulfide deodorizing amount of 0.1 to 6.0 ml/g; more preferably, it is 0.8 to 4.0 ml/g. When the amount of hydrogen sulfide deodorizing is less than 0.1 ml/g, it does not have sufficient performance and is highly likely to be impractical. Furthermore, it is preferable that the amount of hydrogen sulfide deodorization does not exceed 6.0 ml/g. When the content of ferrous hydroxide and the like increases, although the amount of hydrogen sulfide deodorization may be further increased; however, as shown above, the ferrous hydroxide and the like may easily fall off.

When the shape of the material-removable composite of the present invention is fibrous, the fineness is preferably 1.0 to 10.0 dtex, and more preferably 1.5 to 5 dtex. In the case where the fineness is less than 1.0 dtex, the fiber physical properties may be significantly deteriorated, which is not good. In addition, when the fineness is greater than 10.0 dtex, the specific surface area of the substance-removable composite may become smaller and the sulfur-based gas deodorization rate may be significantly reduced; therefore, it is not preferable.

In addition, the fiber structure of the substance-removable composite of the present invention is not particularly limited, and may be, for example, non-woven fabric, yarn, knitted fabric, woven fabric, paper, etc., for example. For example, non-woven fabrics are made by mixing the fibrous material-removable composite of the present invention with other fibers, making it a card machine and other devices several times, and passing it through a needle punch machine (needle punch machine). ), calendar machine, etc. In addition, in the case of the particulate matter-removable composite of the present invention, it is possible to impregnate and disperse an aqueous solution of such a material-removable composite into a non-woven fabric made in advance by using arbitrary fibers to make The method of drying and so on.

The ratio of the substance-removable composite used in the above-mentioned fiber structure is preferably 0.1 to 100% by weight; more preferably 1 to 80% by weight. When the ratio of the substance-removable complex is less than 0.1% by weight, the function of the substance-removable complex of the present invention may not be able to perform fully, which is not preferable.

Other materials that can be used in combination in the above-mentioned fiber structure are not particularly limited. However, for example, natural fibers, organic fibers, semi-synthetic fibers, and synthetic fibers may be used. Specific examples include, for example, cotton, linen, silk, wool, nylon, rayon, polyester, acrylic fiber, activated carbon fiber, thermal fusion fiber, and the like.

The resin molded article containing the substance-removable composite of the present invention is not particularly limited; for example, it may be, for example, fiber, film synthetic leather, artificial leather, sheet, and the like. The ratio of the substance-removable composite of the present invention used in these resin molded articles is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight. When the ratio of the material-removable composite of the present invention is less than 0.1% by weight, similar to the above-mentioned fiber structure, there is a possibility that the function of the material-removable composite of the present invention may not be fully exerted. Bad. In addition, when it exceeds 50% by weight, the durability of the molded product may be significantly deteriorated, which is not preferable.

The method for preparing the above-mentioned resin molded article, for example, in the case where the resin molded article is a fiber, it may be mixed with a spinning stock solution prepared by dissolving an acrylonitrile-based polymer in an aqueous solution of sodium thiocyanate, etc. of the present invention The particle-like substance-removing composite is processed into a fiber form by the usual spinning method.

A filter containing a fiber structure or a resin molded product formed by using the substance-removable composite body of the present invention is not particularly limited; however, it may be, for example, made of fibers and heat containing the substance-removable composite body The fused fiber is blended with a brush or the like, and further, it is fused to form a method while adjusting it to an appropriate density by a rolling mill or the like.

Hereinafter, the manufacturing method of the above-mentioned substance-removable composite of the present invention will be described. First, the method for producing an organic polymer having a carboxyl group will be described in the case of using acrylic fibers, hydrazine-based compounds, and alkali metal hydroxides. The acrylic fiber used may be a fiber formed by containing 40% by weight or more of acrylonitrile, and preferably containing 50% by weight or more of an acrylonitrile polymer. The monomer used in addition to acrylonitrile is not particularly limited; however, for example, it may be (meth)acrylic acid methyl, (meth)acrylic acid ethyl, vinyl acetate, ( Meth) acrylic acid, etc. The production method of such acrylic fiber is not limited, and a known method can be suitably used. In addition, the form of acrylic fiber may be any form among short fibers, long fibers, yarns, knitted fabrics, non-woven fabrics, etc., and may also be semi-finished products of manufacturing processes, waste fibers, and the like.

In addition, the fineness of the acrylic fiber is preferably such that the fineness of the material-removable composite finally obtained is 1.0 to 10.0 dtex; in normal cases, it is preferably 1.5 to 7.0 dtex. Since the fineness tends to increase due to the crosslinking treatment and the hydrolysis treatment described later, there is a need for an acrylic fiber having a finer fineness than the target fineness of the substance-removable composite.

In order to improve water resistance, such acrylic fibers have a cross-linked structure introduced by a hydrazine-based compound or the like. Hydrazine compounds, for example, hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine carbonate, and the like. As the conditions for the cross-linking treatment with the hydrazine compound, it is industrially preferable to use a means of treatment in an aqueous solution with a hydrazine compound concentration of 5 to 30% by weight at a temperature of 50 to 120°C for 1 to 8 hours.

The fiber subjected to such a crosslinking treatment may be subjected to an acid treatment after the agent remaining in the treatment is sufficiently removed. The acid used here is not particularly limited. For example, it may be an inorganic acid such as nitric acid, sulfuric acid, and hydrochloric acid, or an organic acid. Although the conditions of the acid treatment are not particularly limited; however, for example, the fiber may be immersed in an aqueous solution with an acid concentration of 3-20% by weight, preferably 7-15% by weight, at a temperature of 50- An example of immersion at 120°C for 0.5 to 10 hours.

The fibers subjected to the crosslinking treatment as described above, or the fibers further subjected to the acid treatment, are subsequently subjected to the hydrolysis treatment. By this treatment, during the crosslinking treatment, unreacted and remaining nitrile groups and the like are hydrolyzed to generate carboxyl groups. The means of such hydrolysis treatment, for example, may be basic aqueous solutions such as alkali metal hydroxides, alkali metal carbonates, ammonia, etc.; In the implementation of cross-linking treatment of the fiber heat treatment means. The specific processing conditions can be appropriately set in consideration of the amount of the target carboxyl group, etc., and various conditions such as the concentration of the treatment agent, the reaction temperature, and the reaction time are appropriately set. However, industrially, it is preferably 0.5-10% by weight, more preferably 1 The method of treating at a temperature of 50 to 120°C for 1 to 10 hours in an aqueous solution of ~5% by weight of the treatment agent is also preferable for the physical properties of the fiber.

When the organic polymer is formed into a core-sheath structure, the above-mentioned hydrolysis treatment and cross-linking treatment can be carried out at the same time, and a surface layer (sheath) containing a carboxyl group and an acrylonitrile-based part can be constructed by processing under appropriate conditions. The core sheath structure formed by the core of the polymer. Although the treatment conditions are not particularly limited, for example, it may be a mixture in which the concentration of the hydrazine compound is 0.3 to 3.0% by weight and the concentration of alkali metal hydroxide or alkali metal carbonate is 0.5 to 5.0% by weight. An example of immersing fibers in an aqueous solution at a temperature of 80 to 120°C for 0.5 to 8 hours. When the crosslinking treatment and the hydrolysis treatment are carried out at the same time, the concentration of the hydrazine-based compound becomes smaller. In order to further increase the consumption rate of the medicine compared with the case where the medicine is individually carried out, it is preferable to reduce the residual quantity of the medicine.

After performing such a treatment, the type or amount of the alkali type of the carboxyl group can be adjusted by treatment with an acidic solution such as nitric acid, sulfuric acid, etc., or an aqueous metal salt solution, etc., as necessary. The type of the base type is preferably at least one of the group consisting of sodium, magnesium, calcium, potassium, and ammonium. In addition, the amount of basic carboxyl groups at that time is preferably 0.1 mmol/g or more. If such an arbitrary basic carboxyl group does not exist at all, the neutralization reaction does not proceed between the iron (III) salts described later, and there is a fear that it will not be able to support ferrous hydroxide or the like.

In addition, the organic polymer obtained by the above-mentioned method is supported by ferrous hydroxide or the like. The iron (III) salt used when supporting ferrous hydroxide or the like is not particularly limited; for example, it may be, for example, ferrous nitrate, ferrous sulfate, ferrous salt, ferrous bromide, and the like. The amount of iron (III) salt provided is preferably a molar amount of 50-100% of the amount of basic carboxyl groups retained by the organic polymer. When the iron (Ⅲ) salt is supplied to the organic polymer, by immersing the organic polymer in an iron (Ⅲ) salt aqueous solution adjusted to an arbitrary concentration, the organic polymer is retained in the organic polymer due to the above-mentioned reaction Agglomeration occurs near the basic carboxyl group of the product, and ferrous hydroxide is formed.

It is of course suitable to use the acrylic fiber obtained as described above as a starting material to form a composite that supports ferrous hydroxide and the like on the surface of the fiber as the substance-removable composite used in the present invention. <Example>

Hereinafter, examples are listed for easy understanding of the present invention. However, they are exemplary after all, and therefore the gist of the present invention is not limited by them. In addition, the "parts" and "percentages" in the examples indicate that they are based on weight unless otherwise specified.

<Amount of carboxyl group> Weigh about 5 g of the fully dried sample, add 200 ml of 1 mol/l hydrochloric acid aqueous solution to it, leave it for 30 minutes, filter with a glass filter, and wash with water. Then, after the sample is fully dried, weigh approximately 1g (W1[g]), add 200ml of water and add 1 mol/l hydrochloric acid aqueous solution to make pH2, and then use 0.1 mol/l sodium hydroxide aqueous solution according to the usual method. The titration curve is obtained by titration. From this titration curve, the amount of sodium hydroxide aqueous solution consumed by the carboxyl group (V1 [ml]) was calculated, and the amount of carboxyl group was calculated by the following formula. The amount of carboxyl group [mmol/g] = 0.1×V1/W1

＜Amount of basic carboxyl group＞ Accurately weigh about 1g (W2[g]) of the fully dried sample, add 200 ml of water and add 1 mol/l hydrochloric acid aqueous solution to make the pH 2 and then titrate with 0.1 mol/l sodium hydroxide aqueous solution according to the usual method And find the titration curve. From this titration curve, the consumption of sodium hydroxide aqueous solution (V2 [ml]) consumed by the carboxyl group was calculated, and the amount of the basic carboxyl group was calculated by the following formula. Amount of basic carboxyl group [mmol/g]=Amount of carboxyl group [mmol/g]-0.1×V2/W2

＜Fineness＞ The fineness is measured in accordance with JIS "L" 1015: 2010" 8.5.

＜Iron content＞ Using a sample that has been sufficiently dried, the iron content is measured by a flame atomic absorption analyzer, and the ratio to the weight of the sample is calculated.

＜Deodorization amount of hydrogen sulfide＞ Accurately weigh about 20 mg (W3[g]) of the evaluation sample, add it to a 3L Tedler (registered trademark) bag and heat seal it. Next, air and hydrogen sulfide gas with a relative humidity of 65% at 20°C were added so that the hydrogen sulfide gas concentration became 165 ppm by volume and the total amount of gas was 2 L, and it was allowed to stand at 20°C. Then, measure the hydrogen sulfide gas concentration (C3 [ppm]) in the Tedler (registered trademark) bag after 24 hours using a detection tube (manufactured by Gas Technology Co., Ltd.), and calculate the amount of hydrogen sulfide deodorized by the following formula. The amount of hydrogen sulfide deodorization [ml/g]=2000×(165－C3)×10-6/W3

＜Ratio of surface existence of iron＞ Prepare a fibrous sample, and measure the presence rate of iron at any three points on the fiber surface by an energy dispersive X-ray spectrometer (EDS) The characteristic X-ray intensity ratio), and record its average value as A[%]. In addition, a plurality of fibrous samples described above were tied into a bundle, and the samples were prepared by cutting perpendicularly with respect to the fiber axis direction to expose the fiber section. For any three fiber sections, the iron element at the center point of the major axis was measured by EDS. Existence rate, and record its average value as B [%]. Use the following formula to calculate the surface abundance ratio of iron using the obtained values. The surface existence ratio of iron = B/A

<Example 1> Spinning stock solution formed by dissolving 10 parts of acrylonitrile polymer composed of 90% acrylonitrile and 10% acrylic acid methyl in 90 parts of a 48% rhodan soda aqueous solution, spinning, drawing, and drying according to conventional methods And acrylic fiber a is obtained. For this acrylic fiber, 110°C×3 hours of cross-linking hydrolysis treatment and water washing were carried out in 0.5% hydrazine hydrate and 1.5% sodium hydroxide solution; the organic polymerization of the core-sheath structure of sodium alkali type carboxyl groups was generated on the surface.物A. The organic polymer A was treated in a 1.3% ferrous nitrate aqueous solution at room temperature×2 hours and washed with water; dried in a dryer at 80° C. for 3 hours to obtain a substance-removable composite. Table 1 shows the evaluation results of the obtained substance-removable composite.

<Example 2> The organic polymer A obtained in Example 1 was treated with 4% nitric acid aqueous solution at room temperature×1 hour and washed with water; then, treated with 5% ammonia water at room temperature×3 hours and washed with water to obtain Organic polymer B with core-sheath structure of ammonium base carboxyl group. This organic polymer B was treated in a 1.3% ferrous nitrate aqueous solution at room temperature×2 hours, washed with water, and dried in a dryer at 80°C for 3 hours to obtain a substance-removable composite. Table 1 shows the evaluation results of the obtained substance-removable composite.

<Example 3> Except that a 1.1% ferrous sulfate aqueous solution was used instead of the 1.3% ferrous nitrate aqueous solution in Example 1, similarly, the evaluation results of the obtained substance-removable composite are shown in Table 1.

<Example 4> In the same manner, the evaluation results of the obtained substance-removable composite are shown in Table 1, except that a 0.9% ferrous salt aqueous solution was used instead of the 1.3% ferrous nitrate aqueous solution in Example 1.

<Example 5> For the weakly acidic cation exchange resin in the form of particles with carboxyl groups (Dow. Chemical Company: DOWXMAC-3, particle size 0.3～1.2mm), it is treated in a 1.3% ferrous nitrate aqueous solution at room temperature for 2 hours and washed with water It was dried in a dryer at 80°C for 3 hours to obtain a substance-removable composite. Table 1 shows the evaluation results of the obtained substance-removable composite.

<Comparative example 1> The acrylic fiber a obtained in Example 1 was treated in a 1.3% ferrous nitrate aqueous solution at room temperature×2 hours, washed with water, and dried in a dryer at 80°C for 3 hours; the obtained fiber was evaluated. Shown in Table 1.

＜Comparative example 2＞ For the organic polymer A obtained in Example 1, the evaluation results are shown in Table 1.

＜Comparative example 3＞ For the organic polymer B obtained in Example 2, the evaluation results are shown in Table 1.

<Comparative Example 4> Except for using the 1.0% first iron nitrate aqueous solution instead of the 1.3% ferrous nitrate aqueous solution in Example 1, similarly, the evaluation results of the obtained fibers are shown in Table 1.

<Table 1> shape The amount of carboxyl group of organic polymer The amount of basic carboxyl group of organic polymer Fineness Hydrogen sulfide deodorization amount Iron content Iron surface ratio ― mmo/g mmol/g dtex ml/g % ― Example 1 fiber 3.3 2.9 5.8 3.8 0.8 63 Example 2 fiber 3.3 2.9 5.8 3.7 0.8 58 Example 3 fiber 3.3 2.9 5.8 3.7 0.8 60 Example 4 fiber 3.3 2.9 5.8 3.7 0.8 60 Example 5 particle 5.8 4.7 ― 0.7 0.9 ― Comparative example 1 fiber 0.1 0 3.3 0 Less than detection limit ― Comparative example 2 fiber 3.3 2.9 6.2 0 Less than detection limit ― Comparative example 3 fiber 3.3 2.9 6.2 0 Less than detection limit ― Comparative example 4 fiber 3.3 2.9 5.9 0 7.5 11.5

As shown in Table 1, the material removal composite systems of Examples 1 to 4 have sufficient carboxyl groups and iron content; the surface presence ratio of iron is also high; because iron is locally present on the surface, it has sufficient hydrogen sulfide Deodorizing performance. On the other hand, since Comparative Example 1 has almost no carboxyl group content, even if ferrous nitrate treatment is performed, it cannot support ferrous hydroxide or the like, so that it cannot exhibit hydrogen sulfide deodorizing performance. In addition, in Comparative Examples 2 and 3, although the amount of hydrogen sulfide deodorization was measured for the organic polymer before iron support, since it does not contain ferrous hydroxide, etc., it does not contain other hydrogen sulfide deodorization. It is the active ingredient, so the amount of hydrogen sulfide deodorization is completely invisible.

In Example 5, as a result of supporting ferrous hydroxide and the like on particles having a sufficient amount of carboxyl groups, it has a relatively high iron content and a sufficient amount of hydrogen sulfide deodorization. However, since the particle diameter becomes larger and the specific surface area becomes smaller, the hydrogen sulfide deodorizing performance is lower than that of Examples 1-4.

In Comparative Example 4, when the first iron nitrate is used to support iron on the same organic polymer as in Example 1, although it can support a larger amount of iron than in Examples 1 to 4, it is completely The deodorizing performance of hydrogen sulfide is not seen. It is inferred that this is because the ion valence of iron is divalent, and it is stable even at a relatively high pH; therefore, iron carboxylate, which does not have hydrogen sulfide deodorizing performance, does not produce iron hydroxide and the like under neutral conditions. Caused by compounding with organic polymers.

Claims (12)

A substance-removable complex characterized by an organic polymer with a carboxyl group content in the range of 0.3-12.0 mmol/g, and ferrous hydroxide and/or ferrous oxide. The substance-removable composite described in claim 1, wherein the iron content is in the range of 0.01 to 5.0% by weight. The substance-removing complex described in claim 1 or 2, wherein the amount of hydrogen sulfide deodorizing is 0.1 to 6.0 ml/g. The substance-removable composite described in any one of claims 1 to 3 has a fibrous shape. The substance-removable composite as described in claim 4, wherein the fineness is 1.0 to 10.0 dtex. The substance-removable composite described in claim 4 or 5, which has a core-sheath structure formed by a surface layer portion and a center portion: the surface layer portion is composed of a carboxyl group-containing polymer, and the center portion is made of propylene Composed of nitrile polymer. The substance-removable composite body described in any one of claims 4 to 6, wherein the iron presence rate on the surface is divided by the iron presence rate at the center point of the long axis of the composite body, that is, the iron is present on the surface The ratio is 10 or more. The substance-removable composite described in any one of claims 1 to 3 has a particle shape. A method for producing a substance-removable complex, which is characterized by including a process of reacting an organic polymer having a carboxyl group content in the range of 0.3-12.0 mmol/g with an aqueous solution of iron (III) salt. The method for producing a substance-removable complex as described in claim 9, wherein at least a part of the carboxyl group of the organic polymer forms a salt with at least one of the group consisting of sodium, magnesium, calcium, potassium, and ammonium. A fiber structure or resin molded product characterized by containing the substance-removable composite as described in any one of claims 1 to 8. A filter characterized by containing the fiber structure or resin molded product as described in claim 11.