JPH04210238A - Air cleaning agent and its production - Google Patents

Abstract

PURPOSE:To obtain a deodorant having high removing ability for NH3, H2S, (CH3)3N, and especially for CH3SH by bringing a specified elementary metal and a specified alloy to contact with dilute aqueous solution of acid, thereafter bringing the metal and the alloy to contact with a concentrated aqueous solution of an acid and sulfidizing it. CONSTITUTION:An elementary metal such as Fe, Mn, Cr, etc., and an alloy containing above elementary metals are brought to contact with a dilute aqueous solution of an acid such as ascorbic acid, citric acid, etc., in air, and allowed to react therewith for obtaining a composition being coexisted with the unreacted metals. Thereafter, the composition is brought into contact with a relatively concentrated aqueous solution of an acid to adsorb hydrogen sulfide after drying. Thus, obtained deodorant has high removing activity for NH3, H2S, (CH3)3N and is especially very excellent in removing ability of CH3SH.

Description

[Detailed description of the invention]

[00011

[Industrial Application Field] The present invention relates to an air purifier for purifying contaminated air containing malodorous gases such as NH3 and H2S, and a method for producing the air purifier. For example, it can be used as a household deodorizer. [0002] [0002] Bad-smelling gases in the air can be removed or the discomfort felt by an adsorption method using activated carbon, a masking method using other fragrances, or a chemical method that causes a chemical reaction of the odor. It is being said. [0003] The adsorption method using L oak and activated carbon has the problem that the deodorizing performance deteriorates in a short period of time, and the masking method using other fragrances has fundamental problems such as the fragrance may give a new unpleasant feeling. It's not a solution. to OO4] Chemical methods for biochemical reactions include, for example, methods of oxidizing and decondensing malodorous gases using ozone, etc.
Excess ozone is harmful to the human body and causes new harm. [0005] That is, since it is difficult to control the amount of chemical substances that react with malodorous gases, unnecessary chemical substances are generated, and it is difficult to solve them fundamentally [0006] As a technology to solve problems, the Journal of the Japan Textile Science Society [Textiles and Industry J Vol. 42. No, 12 (1
986), pp. 18-26, it is stated that a complex compound obtained by reacting a ferrous compound and ascorbic acid in an aqueous solution has deodorizing power against nitrogen compound-based odor gases. [0007] However, according to the findings of the present inventors, this complex compound has a problem in that it has a weak deodorizing power against sulfur compound-based odor gases. Furthermore, according to the findings of the present inventors, this complex compound has a problem in that its deodorizing ability deteriorates in a relatively short period of time. [00081 The present inventors previously invented a composition in which a reaction product produced by contacting metals such as iron and manganese with ascorbic acid, etc. coexisted with unreacted iron and manganese, and previously filed a patent application. The application was filed under No. 1-280776. [0009] This composition solved the problems of the prior art, such as being able to be manufactured at low cost and having extremely little deterioration in air purifying ability. [00101

[Problems to be Solved by the Invention] The present inventors further extensively studied the composition of Japanese Patent Application No. 1-280776, and found that
Our goal is to provide a new material with air purifying power through a simpler process. In particular, a deodorizing material that improves the CH3SH removal rate and exhibits CH3SH removal performance over a long period of time is desired. [00111] Means for Solving the Problems The present invention provides Fe, Mn. On the surface of at least one metal selected from Cr, Ni, Zn, Al, Cu, and Co and alloys containing these metal elements, the metal, a metal oxide, a metal hydroxide, a metal sulfide, and a complex of a metal and an acid are added. An air purifying product characterized in that a complex of a metal and an acid is produced on the surface of these coexisting substances, [0012] the acid producing the above body is ascorbic acid,
The air purifying product according to claim 1, characterized in that it is one or more acids selected from citric acid, tartaric acid, gluconic acid, tannic acid, and gallic acid, [0013] the metal is an aggregate of particulate metals. The air purifier according to claim 1, characterized in that [00
14] Fe, Mn, Cr, Ni, Zn, Al, Cu,
and Co, and at least one metal selected from alloys containing these metal elements are brought into contact with a dilute aqueous acid solution to react in the atmosphere, and the reaction product coexists with the unreacted metal. [0015] A method for producing an air freshener, the method comprising: contacting the aqueous solution of an acid with a relatively high concentration, drying the aqueous solution, and then adsorbing hydrogen sulfide; 5. The method for producing an air freshener according to claim 4, wherein the aqueous solution is an aqueous solution of one or more acids selected from acid, citric acid, tartaric acid, gluconic acid, tannic acid, and gallic acid. [00161 Hereinafter, the present invention will be specifically explained. According to the research conducted by the present inventors, the deodorizing performance of basic gases such as NH3 and (NH:l)3N is very well adsorbed to metal complexes, which are reaction products of polybasic acids and metals, but CH1SH Gas adsorption power is weak. [0017] One solution is to use a solid base as described by the present inventors in Japanese Patent Application No. 63-273195. However, subsequent research revealed that
It was discovered that the substances that strongly adsorb acidic gases such as H2S are iron hydroxide and ferric oxide, which are produced when metallic iron is dissolved in an aqueous solution. [00181 Furthermore, in order to effectively generate iron hydroxide and maintain a stable effect over a long period of time, metallic iron and iron hydroxide,
It was also found that it was necessary to form a state in which ferric oxide and magnetite coexisted. [00191 The reason why the CH3SH removal stirring performance improves when the H2S removal performance improves is thought to be that H in the -SH group has properties similar to H2S. Therefore, it can be inferred that it is effective to effectively generate iron hydroxide. [0020] Good H2S removal performance makes it possible to remove CH
:1. The inventors' research has revealed that good SH performance is not a sufficient condition. For example, a reaction product obtained by contacting iron and an aqueous L-ascorbic acid solution in air and heat-treating the resulting complex salt and iron coexistence at 150° C. for 24 hours has extremely good H2S removal performance, but is slightly inferior in CH3SH removal performance. [00211 De-CH: ISH As a result of investigating and researching various measures to improve the stirring performance, it was found that iron hydroxide, ferric oxide, etc. Iron and magnetite are produced, resulting in a composition with extremely excellent H2S removal performance, but when hydrogen sulfide is adsorbed to it, iron sulfide is produced, resulting in extremely excellent CH3SH removal performance compared to the composition before hydrogen sulfide is adsorbed. It was found that the composition changes. [00221L, this has good dehydration CH3SH stirring performance
2S performance is extremely good, but it is difficult to remove NI (1 performance or remove (
CH3) 3N performance deteriorates considerably. Removes CH3 without deteriorating sharp tool 3 performance or de(CH3)3N performance as much as possible.
As a method for improving SH stirring performance, a method was adopted in which treatment was performed with a dilute aqueous acid solution in the first step, and treatment with a relatively highly concentrated acid in the second step. [0023] According to this method, coexistence products of magnetite, ferric oxide, iron hydroxide, and iron with excellent H2S removal performance are first generated, and complexes of iron and acid are also formed without significantly changing the composition. arise. [0024] When hydrogen sulfide is adsorbed on this, iron sulfide coexists, forming a composition that has extremely excellent CH33H removal performance without impairing H2S, NH3 removal, (CH3)3N removal performance, etc. [0025] The above phenomenon occurs when metals other than iron, Mn, C
It was confirmed that the same applies to at least one metal selected from r, Ni, Zn, AI, Cu, Co, and alloys containing these metal elements. [0026] CH3 removal by adsorbing hydrogen sulfide
The mechanism behind the improvement in SR performance is that there is almost no deterioration in hydrogen desulfide performance even after repeated use, and that most of the adsorbed hydrogen sulfide is decomposed according to the analysis results of the composition after hydrogen sulfide adsorption. Inferred from this, it is thought that iron sulfide and @yellow are generated in this composition, which significantly improves the adsorption performance of CL+SH. [0027] Examples Next, examples of the present invention will be described. [0028]

[Example 1] A porous iron body was produced by applying fine pig iron powder of 10 μm or less to a urethane foam having a mesh roughness of 20 PPI and firing it at 1150° C. for 2 hours in a non-oxidizing atmosphere. ]-Piece size is approximately 90mm x 80mm x i Om
The weight was approximately 40 g. [0029] The iron porous body is 0.02 in terms of gallic acid.
Impregnation in a tannic acid aqueous solution of mol/'1 1. 1 at room temperature
I left it for days. That's 0.5 mo in terms of gallic acid! - It was impregnated with the tannic acid aqueous solution of '1 and left at room temperature for one week. It was placed in an evaluation device with a structure as shown in Figure 1, and hydrogen sulfide was adsorbed. [00301 The internal volume of the wiping device was 401, and the air flow rate of the circulation fan was about 4001/min. First, first remove CH3
The SH stirring performance was evaluated, and then sulfide water was adsorbed. The starting concentration of hydrogen sulfide for one adsorption is 1000 ppm. I put it in with a syringe. [00311Almost all of the hydrogen sulfide was absorbed into the iron porous body after 10 minutes, and this process was repeated three times. The porous body was left in the air for one day, and the CH3SH removal test was conducted again the next day. The evaluation results are shown in Table 1. [0032] It was confirmed that the CH3SH removal stirring performance was significantly improved and the improvement effect was maintained even in subsequent repeated CH3SH removal tests. In addition, de-N before and after adsorbing hydrogen sulfide.
Regarding H3 performance, the comparison material is N-free! (It is shown in Table 2 along with the three performances.) [00331 comparative material has iron porous material with gallic acid equivalent of 0.0
It was impregnated with a 2 mol/I tannic acid aqueous solution and left for one week at room temperature, and was not subjected to the intermediate treatment of being impregnated with a 0.5 mol/I tannic acid aqueous solution, and the other conditions were the same as the products of the present invention. Almost the same processing was performed. The NH3 removal performance is extremely good compared to comparative materials. [00341

[Example 2] Using a porous iron body produced in the same manner as in Example 1, 0.02 mol of L-ascorbic acid was added to 11
It was impregnated with an aqueous solution dissolved in water and left at room temperature for one day. It was impregnated with an aqueous tannic acid solution of 0.5 m01/I in terms of gallic acid and left at room temperature for one week. [0035] Later CH3SH stirring performance was investigated. It was placed in an evaluation device with a structure as shown in Figure 1, and hydrogen sulfide was adsorbed. [00361 The internal volume of the test device is 401 mm, and the air volume of the circulation fan is approximately 400 mm. /minute. First, remove C
H3SH stirring performance was evaluated, and then sulfide water was adsorbed. Hydrogen sulfide was injected with a syringe so that the starting concentration for one adsorption was 100 ppm. [00371Almost the entire amount of hydrogen sulfide was absorbed into the iron porous body after 10 minutes, and this process was repeated three times. The porous body was left in the air for one day, and the membrane CH3SH test was conducted again the next day. As shown in Table 3, the evaluation results show that the CH3SH removal performance is significantly improved by hydrogen sulfide adsorption. [0038] Also, deNH3 before and after adsorbing hydrogen sulfide
The performance of the comparison material is shown in Table 4 along with the N1 (3 performances).
It was impregnated with 2 mol/'l of tannidic acid aqueous solution and left at room temperature for one week, and the intermediate concentration was 0.5 mol/'l.
This material was not impregnated with an aqueous tannic acid solution of 1 liter, and was treated under almost the same conditions as the product of the present invention.It has extremely good NH3 removal performance compared to the comparative material. The test results regarding the sustainability of the improvement effect on CH3SH performance confirmed that the improvement effect was sustained as shown in Table 5. [00411 [Example 3] Urethane foam with a mesh roughness of 13 PPI was coated with Cr, Ni, AI, Cu, Mn, Co, Z
A porous metal body was manufactured by welding each of n by low-temperature spraying. The size of one piece is approximately 100mm x 90mm x 12mm
The weight was about 40g to 50g. [0042] Using those metal porous bodies, impregnated with an aqueous solution of 0.02 mol of L-ascorbic acid, and
I left it for days. 0.5 mol/' in terms of gallic acid
1 of an aqueous tannic acid solution and left at room temperature for one week. It was placed in an evaluation device with a structure as shown in Figure 1, and hydrogen sulfide was adsorbed. [0043] The internal volume of the test device was 401, and the air flow rate of the circulation fan was about 4001 /min. First, first remove CH
The 3SH performance was evaluated, followed by hydrogen sulfide adsorption. Hydrogen sulfide was injected with a syringe so that the starting concentration for one adsorption was 1000 ppm. [00441Although there were variations in the hydrogen sulfide concentration after 10 minutes, one adsorption session was terminated after 10 minutes. I repeated that three times. The porous body was left in the air for one day, and the membrane CH:l SH test was conducted again the next day. Table 6 shows the evaluation results.
It was shown to. The deCH3SH performance was significantly improved. [00451 [Table 1] [0046] [Table 2] [0047]

[Table 3] [00481

[Table 4] [00491] [Table 5] [00501 [Effects of the invention] The present invention improves NH3 removal performance and H2S removal performance.
Performance, de(CH3)3N performance is good and further CH3SH is removed.
Air purifiers with extremely superior performance can be produced.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram showing the structure of a test device for evaluating deodorizing performance.

[Explanation of symbols]

1 Sealed container 2 Circulation fan 3. Deodorizing filter 4 Gas inlet 5 Gas sample sampling port 6 Direction of gas circulation

Claims (5)

[Claims] [Claim 1] Fe, Mn, Cr, Ni, Zn, Al, C
On the surface of at least one metal selected from u, Co, and alloys containing these metal elements, a coexistence of the metal, a metal oxide, a metal hydroxide, a metal sulfide, and a complex of a metal and an acid is generated. An air purifier characterized by the formation of a complex of metal and acid on the surface of an object. 2. The acid that forms the complex is ascorbic acid,
The air freshener according to claim 1, characterized in that it is one or more acids selected from citric acid, tartaric acid, gluconic acid, tannic acid, and gallic acid. 3. The air purifier according to claim 1, wherein the metal is an aggregate of granular metals. Claim 4: Fe, Mn, Cr, Ni, Zn, Al, C
A composition in which at least one metal selected from u, Co, and alloys containing these metal elements is brought into contact with a dilute aqueous acid solution and reacted in the atmosphere, and the reaction product coexists with the unreacted metal. 1. A method for producing an air purifying product, which comprises: first contacting the product with an aqueous solution of a relatively highly concentrated acid, drying the product, and then adsorbing hydrogen sulfide. 5. The air according to claim 4, wherein the aqueous acid solution is an aqueous solution of one or more acids selected from ascorbic acid, citric acid, tartaric acid, gluconic acid, tannic acid, and gallic acid. Method of manufacturing cleaning products.