JP2011194393A - Harmful substance decomposition material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a harmful substance decomposition material which decomposes a harmful substance effectively without deteriorating the substrate and to provide a method for decomposing a harmful substance.SOLUTION: The harmful substance decomposition material contains a carbon catalyst having catalytic activities to decompose the harmful substance and the substrate to carry the carbon catalyst. The harmful substance may be a volatile organic compound. The carbon catalyst may be obtained by carbonization of the raw material containing an organic substance and a metal. The substrate may be a fibrous substrate.

Description

  The present invention relates to a hazardous substance decomposition material, and more particularly to a hazardous substance decomposition material containing a carbon catalyst for decomposing harmful substances.

  Conventionally, methods for removing harmful substances include, for example, a method using a photocatalyst such as titanium dioxide, a method using an adsorbent such as activated carbon or zeolite, and a method using a noble metal catalyst such as platinum. Patent Document 1 describes a photocatalyst-containing sheet obtained by coating the surface of a paper substrate with a coating agent containing a binder and a photocatalyst.

JP-A-10-128125

  However, the conventional harmful substance removal method has the following problems. That is, since the photocatalyst needs a sufficient amount of light to cause the photocatalytic reaction, it cannot be used in an environment without a light source. Adsorbents are unsuitable for repeated use because their adsorption capacity decreases with use. Precious metals are expensive and have limited versatility because they are limited by reserves.

  Further, when the photocatalyst is supported on a base material, the base material is deteriorated by a photocatalytic reaction. Therefore, conventionally, as described in Patent Document 1, in order to avoid direct contact between the photocatalyst and the base material, special measures such as coating the photocatalyst and the base material have been made.

  However, when coating with a photocatalyst, it was impossible to avoid a decrease in the performance of the photocatalyst. Further, special processing for reducing deterioration of the base material complicates the manufacturing method.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a hazardous substance decomposition material that effectively decomposes harmful substances without degrading the base material.

  A hazardous substance decomposition material according to an embodiment of the present invention for solving the above-described problem includes a carbon catalyst having catalytic activity for decomposing a harmful substance, and a base material supporting the carbon catalyst, To do. ADVANTAGE OF THE INVENTION According to this invention, the hazardous | toxic substance decomposition material which decomposes | disassembles a harmful | toxic substance effectively can be provided, without deteriorating a base material.

  The harmful substance may be a volatile organic compound. In this case, the volatile organic compound may be aldehydes and oxides thereof. The carbon catalyst may be obtained by carbonization of a raw material containing an organic substance and a metal.

  The base material may be a fiber base material. In this case, the fiber base material may be an organic fiber base material. In this case, the organic fiber base material may be a paper base material. Furthermore, in this case, the harmful substance decomposition material may be obtained by papermaking of a raw slurry containing the carbon catalyst.

  ADVANTAGE OF THE INVENTION According to this invention, the harmful substance decomposition material which decomposes | disassembles a harmful substance effectively without deteriorating a base material can be provided.

In the Example which concerns on one Embodiment of this invention, it is explanatory drawing which shows an example of the result of having observed the harmful substance decomposition material formed by carrying | supporting a carbon catalyst on a paper base material with the scanning electron microscope. In the Example which concerns on one Embodiment of this invention, it is explanatory drawing which shows an example of the result of having observed the paper base material which does not carry | support the carbon catalyst with the scanning electron microscope. It is explanatory drawing which shows an example of the result of the formaldehyde decomposition test in the Example which concerns on one Embodiment of this invention. It is explanatory drawing which shows an example of the result of the deterioration test of the base material in the Example which concerns on one Embodiment of this invention. It is explanatory drawing which shows an example of the result of the carbon monoxide oxidation decomposition test in the Example which concerns on one Embodiment of this invention. It is explanatory drawing which shows an example of the result of the antimicrobial test in the Example which concerns on one Embodiment of this invention. It is explanatory drawing which shows an example of the result of the mold resistance test in the Example which concerns on one Embodiment of this invention.

  Hereinafter, an embodiment of the present invention will be described. Note that the present invention is not limited to the present embodiment.

  The harmful substance decomposition material (hereinafter referred to as “the present decomposition material”) according to the present embodiment includes a carbon catalyst having catalytic activity for decomposing a harmful substance and a base material supporting the carbon catalyst.

  The carbon catalyst contained in the present decomposition material is a carbon material having catalytic activity that decomposes harmful substances. That is, this decomposition material decomposes harmful substances by effectively utilizing the catalytic activity of the carbon catalyst supported on the substrate. The harmful substance decomposed by the present decomposition material may be a gas, or may be dissolved in water or another solvent.

  Examples of harmful substances decomposed by the present decomposition material (that is, harmful substances decomposed by the carbon catalyst) include, for example, volatile organic compounds (VOC).

  Examples of VOC include aldehydes such as formaldehyde, acetaldehyde, nonenal, and acrolein, carboxylic acids such as formic acid, acetic acid, isovaleric acid, butyric acid, and (meth) acrylic acid, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as butanol, ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, butyl ethyl ketone, ethyl acetate, butyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, methyl formate, phthalic acid Esters such as dibutyl, di-2-ethylhexyl phthalate, and fenocarb, toluene, xylene, phenol, styrene, benzene, ethylbenzene, benzoic acid, limonene, cumene and other aromatic hydrocarbons, methane, ethane, propane, hexa Aliphatic hydrocarbons such as pentane, tetradecane, cyclohexane, cyclopentanone, ethylcyclohexane, heterocycles such as indole, ammonia, trimethylamine, triethylamine, ethylenediamine, pyridine, cyclohexylamine, N-methyl-2-pyrrolidone And one or more selected from the group consisting of phosphorus compounds such as chloropyrifos and diazinon, and chlorine compounds such as carbon tetrachloride, chloromethane, chloroform, chloroethylene and paradichlorobenzene. That is, this decomposition material can be used as, for example, a decomposition material that decomposes aldehydes or aldehydes and oxides thereof.

  Moreover, as a harmful substance decomposed | disassembled by this decomposition material, a malodorous substance is mentioned, for example. Malodorous substances include, for example, sulfur compounds that produce an odor of eggs, amines that produce body odors and excrement odors, carboxylic acids and aldehydes, alcohols that produce fermented odors, ketones and esters contained in paints, etc. Aromatic hydrocarbons can be mentioned.

  More specifically, as malodorous substances, for example, sulfur compounds such as hydrogen sulfide, methyl sulfide, methyl disulfide, methyl mercaptan, ethyl mercaptan, amines such as ammonia, trimethylamine, propionic acid, normal butyric acid, normal valeric acid, Carboxylic acids such as isovaleric acid, acetaldehyde, propionaldehyde, normal butyraldehyde, isobutyraldehyde, normal valeraldehyde, aldehydes such as isovaleraldehyde, alcohols such as isobutanol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetic acid Examples thereof include one or more selected from the group consisting of esters such as ethyl, aromatic hydrocarbons such as toluene, styrene and xylene, and ozone.

  The carbon catalyst can also be a carbon material having catalytic activity for oxidative decomposition of toxic gases in addition to having catalytic activity for decomposing harmful substances as described above. The toxic gas that is oxidatively decomposed by the present decomposition material (that is, the toxic gas that is oxidatively decomposed by the carbon catalyst) includes, for example, carbon monoxide (CO), nitrogen oxide (NOx), and sulfur oxide (SOx). 1 type (s) or 2 or more types selected from a group are mentioned. That is, this decomposition material can oxidatively decompose carbon monoxide at room temperature or high temperature, for example. Moreover, this decomposition material can oxidatively decompose nitrogen oxides and / or sulfur oxides even at room temperature, for example. In this case, the present decomposition material can have a so-called self-cleaning function.

  In addition to having the catalytic activity of decomposing harmful substances as described above, the carbon catalyst can be a carbon material that does not substantially adsorb the harmful substances. In this case, for example, by using a base material that does not substantially adsorb harmful substances, the present decomposed material can be a decomposed material that does not substantially adsorb harmful substances.

  In addition, the carbon catalyst can decompose harmful substances even in a relatively low temperature environment. In this case, the present decomposition material can decompose harmful substances at, for example, 0 ° C. or higher. More specifically, the temperature at which this decomposition material decomposes harmful substances can be, for example, 0 ° C. or higher and 300 ° C. or lower, 0 ° C. or higher and 100 ° C. or lower, 0 ° C. or higher, 40 It can also be below ℃.

  The carbon catalyst can be a carbon material obtained by carbonization of a raw material containing an organic substance and a metal. In this case, the organic substance contained in the raw material is not particularly limited as long as it can be carbonized (can be used as a carbon source), and any one kind or two or more kinds can be used.

  That is, as the organic substance, for example, one or both of a high molecular weight organic compound (for example, a resin such as a thermoplastic resin or a thermosetting resin) and a low molecular weight organic compound can be used. Further, for example, biomass such as plant waste material can be used.

  As the organic substance, for example, an organic substance containing nitrogen can be preferably used. The organic substance containing nitrogen is not particularly limited as long as it contains an organic compound containing a nitrogen atom in the molecule, and any one kind or two or more kinds can be used.

  As the organic substance, for example, a ligand capable of coordinating with a metal can be preferably used. That is, in this case, an organic compound containing one or more coordination atoms in the molecule is used. More specifically, for example, as a coordination atom, an organic compound containing one or more selected from the group consisting of a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom in the molecule can be used. . Further, for example, an organic compound containing one or more selected from the group consisting of an amino group, a phosphino group, a carboxyl group, and a thiol group in the molecule can also be used as a coordination group.

  Specifically, examples of the organic compound include pyrrole, polypyrrole, polyvinylpyrrole, 3-methylpolypyrrole, furan, thiophene, oxazole, thiazole, pyrazole, vinylpyridine, polyvinylpyridine, pyridazine, pyrimidine, piperazine, pyran, morpholine, imidazole. 1-methylimidazole, 2-methylimidazole, quinoxaline, aniline, polyaniline, succinic acid dihydrazide, adipic acid dihydrazide, polysulfone, polyaminobismaleimide, polyimide, polyvinyl alcohol, polyvinyl butyral, benzoimidazole, polybenzoimidazole -Polyamide, Polyester, Polylactic acid, Acrylonitrile, Polyacrylonitrile, Polyether, Polyetheretherketone, Cell -Su, lignin, chitin, chitosan, silk, hair, polyamino acid, nucleic acid, DNA, RNA, hydrazine, hydrazide, urea, salen, polycarbazole, polybismaleimide, triazine, ionomer, polyacrylic acid, polyacrylate, Selected from the group consisting of polymethacrylic acid ester, polymethacrylic acid, polyurethane, polyamidoamine, polycarbodiimide, polyacrylonitrile-polymethacrylic acid copolymer, phenol resin, melamine, melamine resin, epoxy resin, furan resin, polyamideimide resin 1 type (s) or 2 or more types can be used.

  Examples of biomass such as waste wood include liquor waste, coffee lees, coffee grounds, tea grounds, beer squeezed rice, rice industry, food industry waste such as rice bran, woody waste such as forest land, building waste, and sewage sludge. 1 type (s) or 2 or more types selected from the group which consists of a system waste material can be used. The organic substance may further contain, for example, one or more selected from the group consisting of boron, phosphorus, oxygen, and sulfur as a component that improves the activity of the carbon catalyst.

  The metal contained in the raw material is not particularly limited as long as it does not inhibit the catalytic activity of the carbon catalyst, and any one type or two or more types can be used. That is, as the metal, for example, a transition metal can be preferably used, and a metal belonging to Group 4 to Group 12 of the periodic table can be particularly preferably used.

  Specifically, for example, one or more selected from the group consisting of cobalt, iron, nickel, manganese, zinc, copper, and chromium can be preferably used, and cobalt, iron, manganese, and nickel are particularly preferably used. can do.

  As the metal, a simple substance of the metal or a compound of the metal can be used. As the metal compound, for example, metal salts, metal oxides, metal hydroxides, metal nitrides, metal sulfides, metal carbonides, metal complexes can be used, and metal salts, metal oxides, metal sulfides can be used. A metal complex can be preferably used. In addition, when using a ligand as the above-mentioned organic compound, a metal complex is formed in the raw material.

  The raw material for the carbon catalyst may further contain a carbon material. The carbon material is not particularly limited as long as the whole or a part of the carbon material is carbonized, and any one type or two or more types can be used. That is, as the carbon material, for example, a material that does not have catalytic activity can be used.

  Specifically, for example, a carbon material or natural mineral obtained by carbonization of an organic substance and having no catalytic activity can be used. More specifically, for example, carbon black (for example, ketjen black, acetylene black), graphite, coke, activated carbon, brown coal, peat, bean coal, carbon nanotube, carbon nanohorn, carbon nano One type or two or more types selected from the group consisting of fiber and carbon fibril can be used.

  Carbonization of the raw material is performed by heating the raw material containing the organic substance and the metal as described above and holding the raw material at a predetermined temperature (carbonization temperature) at which the raw material can be carbonized. The carbonization temperature is not particularly limited as long as the raw material can be carbonized, and can be, for example, 300 ° C. or higher, and preferably 700 ° C. or higher. More specifically, the carbonization temperature can be, for example, in the range of 300 to 3000 ° C, preferably in the range of 700 to 2000 ° C, and more preferably in the range of 700 to 1500 ° C. Can do.

  The rate of temperature rise to the carbonization temperature can be, for example, in the range of 0.5 to 300 ° C./min. The time for holding the raw material at the above carbonization temperature can be, for example, in the range of 5 minutes to 24 hours, and preferably in the range of 20 minutes to 5 hours. The carbonization is preferably performed under a flow of an inert gas such as nitrogen.

  For example, the carbon catalyst may be obtained by pulverizing a carbon material obtained by carbonization of a raw material. The pulverization method is not particularly limited, and for example, a pulverizer such as a ball mill or a bead mill can be used. The average particle size of the carbon catalyst after pulverization can be, for example, 1000 μm or less, and preferably 150 μm or less.

  The carbon catalyst can be a carbon material obtained by subjecting a carbon material obtained by carbonization of a raw material to a cleaning treatment for reducing the metal content or removing the metal, for example. For this washing treatment, for example, an acid such as hydrochloric acid or sulfuric acid can be preferably used.

  A carbon catalyst can also be made into the carbon material obtained by activating the carbon material obtained by carbonization of a raw material, for example. The activation method is not particularly limited, and for example, ammoxidation, carbon dioxide activation, phosphoric acid activation, alkali activation, and water vapor activation can be used.

  The carbon catalyst can be a carbon material obtained by subjecting a carbon material obtained by carbonization of a raw material to a heat treatment, for example. This heat treatment is performed by holding the carbon material obtained by carbonization at a predetermined temperature. The temperature of heat processing can be made into the range of 300-1500 degreeC, for example.

  The carbon catalyst can be a carbon material obtained by adding metal to a carbon material obtained by carbonization of a raw material by a method such as a metal impregnation method or a mechanical alloying method. The metal added after carbonization is not particularly limited as long as it does not inhibit the catalytic activity of the carbon material. For example, titanium, manganese, nickel, zirconium, cobalt, aluminum, iron, niobium, vanadium, magnesium, palladium, calcium, Zinc and platinum metals can be preferably used.

  The base material contained in the present decomposition material is not particularly limited as long as it can support the carbon catalyst as described above, and any one kind or two or more kinds can be used.

  As the substrate, for example, a fiber substrate can be used. As the fiber base material, an organic fiber base material can be used. As the organic fiber substrate, a paper substrate or an organic fiber cloth substrate can be used.

  Examples of organic fibers constituting the paper base include wood pulp such as softwood bleached kraft pulp, hardwood bleached kraft pulp, softwood unbleached kraft pulp, hardwood unbleached kraft pulp, conifer sulfite pulp, thermomechanical pulp, and cotton Non-wood pulps such as linter pulp, kenaf, bamboo, bagasse, hemp, banana, Kevlar (Twaron) are listed.

  As the cloth substrate, for example, an organic fiber nonwoven fabric, woven fabric or knitted fabric can be used. Examples of organic fibers constituting the cloth material include natural organic fibers such as cotton, silk, hemp, and hair, polyester fibers, polyethylene fibers, polypropylene fibers, acrylic fibers, nylon fibers, aramid fibers, rayon fibers, vinylon fibers, Examples include synthetic organic fibers such as acetate fibers, polyurethane fibers, polylactic acid fibers, and polyvinyl chloride fibers.

  Moreover, an inorganic fiber base material can also be used as a fiber base material. Examples of the inorganic fiber constituting the inorganic fiber substrate include carbon fiber, glass fiber, rock wool, ceramic fiber, silicon carbide fiber, boron fiber, and alumina fiber.

  In addition, the organic fiber base material contained in this decomposition material should just be a fiber base material which has an organic fiber as a main component which deteriorates by the photocatalytic reaction by the said photocatalyst, for example, when supporting a photocatalyst, What added other components, such as an inorganic fiber, may be used.

  Moreover, a resin molding can also be used as a base material. In this case, for example, polyethylene, polypropylene, polystyrene, poly (meth) acrylic acid, poly (meth) acrylate methyl, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, polyethylene glycol, polypropylene glycol, polyethylene terephthalate, polybutylene terephthalate, polyester Polylactic acid, polyether, polysulfone, phenol resin, phenol formaldehyde resin, epoxy resin, melamine resin, urethane resin, vinyl chloride resin, polyamide, polyimide, polyamideimide, carbodiimide resin, urea resin, etc. A resin molded body obtained by molding into a predetermined shape can be used. Moreover, as a base material, ceramics (for example, alumina, cordierite) tile, inorganic materials, such as glass, and a metal can also be used.

  The shape of the substrate is not particularly limited as long as the carbon catalyst can be supported by the substrate. For example, a sheet shape, a film shape, a fiber shape, a net shape, a plate shape, a plate shape, a honeycomb shape, a pleated shape, a corrugated shape Corrugated honeycomb, pellet, granular, cotton, wool, block, columnar, polygonal column, hollow body, foam, porous body.

  That is, in these cases, the shape of the decomposed material is also a sheet shape, a film shape, a fiber shape, a net shape, a plate shape, a plate shape, a honeycomb shape, a pleated shape, a corrugated shape, a corrugated honeycomb shape, a pellet shape, a granular shape, a cotton Shape, wool shape, block shape, columnar shape, polygonal column shape, hollow body, foamed body, porous body. Moreover, this decomposition material can be used as fiber bodies, such as paper, a textile fabric, a knitted fabric, a nonwoven fabric, a filter, a coating sheet, and a multilayer body, for example.

  In the present decomposition material, the base material supports the carbon catalyst on the surface and / or inside of the base material such that at least a part of the surface of the carbon catalyst is exposed.

  In the case of using a fiber base material, for example, when the fiber base material is manufactured, the carbon base material is captured by incorporating a carbon catalyst between the fibers or by attaching the carbon catalyst to the fiber base material manufactured in advance. The catalyst can be supported on the fiber substrate.

  The carbon catalyst can be supported on the fiber base material by, for example, attaching the carbon catalyst to the fiber base material via a binder. Moreover, a carbon catalyst can also be made to adhere to the said fiber base material by melt | fusion in the vicinity of melting | fusing point of the fiber which comprises a fiber base material. In this case, the carbon catalyst can be directly supported on the fiber base material without using a binder.

  When using a paper base material, this decomposition material can be made into the decomposition material obtained by the papermaking of the raw material slurry containing a carbon catalyst, for example. That is, in this case, first, a raw material slurry (for example, pulp slurry) containing the paper fiber raw material and the carbon material is prepared by mixing a paper fiber raw material (for example, pulp) and a carbon catalyst, By performing paper making using the raw material slurry, the present decomposed material can be produced. As a papermaking method, a known method can be used.

  In this case, the carbon catalyst can be directly supported on the paper substrate without using a binder. In papermaking, conventionally known additives such as sizing agents, fillers, paper strength enhancers, dyes, paints, etc. can be used, and the additives can be omitted. By these methods, it is possible to effectively avoid the problem of the carbon catalyst falling off from the paper substrate (so-called powder falling). In addition, since a general papermaking method can be used as it is, the present decomposed material having excellent harmful substance decomposition performance can be reliably produced by a simple method. In addition, loading of the carbon catalyst on the paper base material is not limited to the above-mentioned papermaking, and for example, the carbon catalyst can be attached to the paper base material manufactured in advance via a binder.

  When an inorganic fiber substrate is used, the present decomposition material can be produced by, for example, fusion with a resin, surface treatment of inorganic fibers, or hybridization. Moreover, this decomposition material can also contain the fiber base material which comprises a filter (for example, honeycomb-shaped filter), and the carbon catalyst with which the said filter was filled, for example.

  When using a resin molding as a base material, a carbon catalyst can be made to adhere to the said resin base material, for example by melt | fusion in the vicinity of melting | fusing point of resin which comprises the said resin molding. Moreover, this decomposition material can also be made into the molded object of the mixture of resin and a carbon catalyst, for example. In this case, for example, the present raw material can be produced by melting the resin raw material or dissolving it with a solvent, and then dispersing the carbon catalyst in the resin raw material, and then molding the obtained mixture into a predetermined shape. it can.

  This decomposition material effectively decomposes harmful substances without degrading the base material. That is, the carbon catalyst contained in the present cracking material has excellent catalytic activity for effectively decomposing harmful substances, and does not deteriorate the substrate due to the development of the catalytic activity.

  For this reason, in this decomposition material, a carbon catalyst can be directly carry | supported on a base material as mentioned above, for example. Therefore, the present decomposition material can exhibit an excellent performance of decomposing harmful substances by making maximum use of the catalytic activity of the carbon catalyst. In addition, the present decomposed material can be efficiently and reliably produced by a simple method that is complicated and does not include special processing.

  Moreover, this decomposition material can have a hazardous | toxic substance decomposition performance higher than the carbon catalyst which is not carry | supported by the base material, for example. That is, for example, the present decomposition material formed by supporting a predetermined amount of carbon catalyst on a base material can exhibit a higher rate of decomposition of harmful substances than the predetermined amount of carbon catalyst not supported on the base material. .

  In addition, in order for the photocatalyst to exhibit its catalytic activity, it is necessary to irradiate the photocatalyst with light, but such light irradiation is not necessary for the decomposition of harmful substances by the decomposition material. Therefore, the present decomposition material can effectively decompose harmful substances even in an environment without a light source (for example, under light shielding).

  Further, the decomposition of harmful substances by the present decomposition material is based on the catalytic activity of the carbon catalyst, and the catalytic reaction of the carbon catalyst does not deteriorate the base material. For this reason, this decomposition material can be repeatedly used over a long period of time. Therefore, by using this decomposition material, harmful substances can be efficiently decomposed while effectively reducing the environmental load and running cost.

  Moreover, since the carbon catalyst contained in this decomposition material shows the outstanding catalytic activity by itself, this decomposition material can decompose | disassemble a harmful substance effectively, without including a photocatalyst and a noble metal catalyst. Therefore, the present decomposed material can be an inexpensive and highly versatile harmful material decomposed material.

  Moreover, this decomposition material can also have the outstanding antibacterial property and mold resistance. Therefore, this decomposition material can be used also for the use as which antibacterial property and mold resistance are requested | required, for example.

  In the method of decomposing a harmful substance using the present decomposing material, for example, the decomposing material is brought into contact with a fluid (gas or liquid) containing the harmful substance to be removed. Specifically, for example, the decomposition material is decomposed by bringing the decomposition material into contact with a gas containing a hazardous material such as VOC. For example, the toxic gas can be oxidatively decomposed by bringing the decomposition material into contact with a gas containing a toxic gas such as CO, NOx, and SOx.

  In addition, this decomposition material can also be used together with another harmful substance removal material. That is, for example, the present decomposed material can be used in combination with another harmful substance decomposed material and / or a harmful substance adsorbent.

  In addition, the use of this decomposition material is related to, for example, the decomposition of harmful substances and the oxidative decomposition of carbon monoxide, exhaust gas purification in internal combustion engines, smoking goods (cigarette filters), and CO selection in reformed gas Oxidation (for example, removal of CO in fuel reformed gas such as hydrogen rich gas), gas sensor (including electrochemical oxidation), purification of high purity gas, photocatalytic reactor (combined with photocatalyst), aquatic gas shift catalyst, methanol reforming Quality microreactor, production of acetic acid by ethanol oxidation, gas mask, gas filter of oil stove, air cleaner filter. In addition, examples of the use of this decomposition material include outdoor wall materials having self-cleaning and antifouling functions indoors and outdoors in connection with decomposition of harmful substances and oxidative decomposition of nitrogen oxides and / or sulfur oxides. Window glass, tiles, and automotive door mirrors with anti-fogging function.

  Next, specific examples according to the present embodiment will be described.

[Electron microscope observation]
Using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), a photograph was taken at 100 magnification.

[Aldehyde degradation test]
The sample was stored in a Tedlar bag at 25 ° C., and 3 L of air containing formaldehyde at a concentration of 1000 ppm was injected and left in a dark room. After 3 hours and 24 hours, the concentration of formaldehyde in the Tedlar bag and the concentration of carbon dioxide generated by the decomposition of the formaldehyde were measured. The concentration of formaldehyde and the concentration of carbon dioxide were measured with a detector tube for formaldehyde and a detector tube for carbon dioxide (manufactured by Gastec Co., Ltd.).

  The formaldehyde decomposition rate (%) is expressed by the following formula: formaldehyde decomposition rate (%) = [carbon dioxide concentration (ppm) after 3 hours or 24 hours−carbon dioxide amount (ppm) in the atmosphere] / initial formaldehyde Concentration (ppm) × 100; Further, the formaldehyde disappearance rate (%) is expressed by the following formula: formaldehyde disappearance rate (%) = [(initial formaldehyde concentration (ppm) —after 3 hours or after 24 hours formaldehyde concentration (ppm)) / initial formaldehyde concentration ( ppm)] × 100; Furthermore, the formaldehyde adsorption rate (%) was determined by the following formula: formaldehyde adsorption rate (%) = formaldehyde disappearance rate (%) − formaldehyde decomposition rate (%).

[Deterioration test]
A sample was stored in a 25 ° C. Tedlar bag and 3 L of air was injected. Next, using a UV lamp (black light fluorescent lamp FL15BLB-A: peak wavelength 352 nm, manufactured by Toshiba Lighting & Technology Co., Ltd.), irradiation of UV light with a strength of 0.1 mW / cm ² was started on the Tedlar bag.

  After 24 hours, the concentrations of carbon dioxide and carbon monoxide generated by the decomposition of the substrate in the Tedlar bag were measured with a carbon dioxide and carbon monoxide detector tube (manufactured by Gastec Corporation).

  The concentration of carbon dioxide and carbon monoxide in the Tedlar bag after 24 hours was calculated as a value obtained by subtracting the concentration in the atmosphere from the measured concentration. Moreover, the presence or absence of the yellow change of the base material before and behind a test was confirmed visually.

[Example 1]
1.5 g of polyacrylonitrile-polymethacrylic acid copolymer (PAN / PMA) is dissolved in 30 mL of dimethylformamide, and 1.5 g of 2-methylimidazole and 1.5 g of cobalt chloride hexahydrate (CoCl and ₂ · _6H 2 O) (manufactured by Kanto Chemical Co., Inc.), and the mixture was stirred for 2 hours at room temperature. To the mixture thus obtained, ketjen black (ECP600JD, manufactured by Lion Corporation) was added so that the content in the component excluding the solvent would be 30% by weight, and mixed using a mortar. The resulting mixture was vacuum dried at 60 ° C. for 12 hours.

  Further, this mixture was heated in the air, and the temperature was raised from room temperature to 150 ° C. in 30 minutes. Subsequently, the temperature was raised from 150 ° C. to 220 ° C. over 2 hours. Thereafter, the mixture was kept at 220 ° C. for 3 hours to infusibilize the mixture. In this way, the raw material was prepared.

  Next, the raw material obtained as described above was put in a quartz tube, purged with nitrogen for 20 minutes in an image furnace, and heated from room temperature to 900 ° C. over 18 minutes by heating in a nitrogen atmosphere. Thereafter, this raw material was held at 900 ° C. for 1 hour. In this way, the raw material was carbonized.

  Further, a zirconia ball having a diameter of 10 mm was set in a planetary ball mill (P-7, manufactured by Fritsch Japan Co., Ltd.), and the carbon material was pulverized at a rotational speed of 650 rpm for 5 minutes by the planetary ball mill for 10 cycles. Thus, the carbon material was pulverized. Thereafter, the pulverized carbon material was taken out and passed through a sieve having an aperture of 106 μm. And the carbon material which passed the sieve was obtained as the pulverized particulate carbon catalyst 1 (PCo).

  Next, the carbon catalyst 1 (PCo) obtained as described above was supported on a paper substrate. That is, 50 parts by mass of softwood bleached kraft pulp and 50 parts by mass of hardwood kraft pulp were disaggregated in water to prepare 3.5% pulp slurry. This pulp slurry was beaten to give 400 mlc.s. Adjusted to f.

  There, 0.5% by weight of wet paper strength enhancer is added in solid content, 1% by weight of dry paper strength enhancer is added and dispersed, and carbon catalyst 1 (PCo) is added in solid content of 40%. Mass% was added and stirred.

Thereafter, using this pulp slurry, a sheet-like harmful substance decomposition material formed by supporting the carbon catalyst 1 (PCo) on a paper base material by a papermaking method in accordance with JIS P 8222, the basis weight is 70 g / m ² . A paper sheet was produced.

  The paper sheet thus obtained was observed with a scanning electron microscope. Moreover, the aldehyde decomposition | disassembly test and the deterioration test were done using the paper sheet (10 cm x 10 cm) containing the carbon catalyst 1 (PCo) of 200 mg as a sample.

[Example 2]
5 g of graphite AG. B (manufactured by Ito Graphite Industries, Ltd.), (manufactured by Nippon Finechem) succinic acid dihydrazide 5g, were mixed and dissolved cobalt chloride hexahydrate 5g of _(CoCl 2 · _6H 2 O) in distilled water 50 mL. The solution thus obtained was dried at 100 ° C. for 12 hours and further pulverized in a mortar to obtain a raw material.

  Next, the raw material obtained as described above was put in a quartz tube, purged with nitrogen for 20 minutes in a tubular furnace, and heated from room temperature to 900 ° C. over 90 minutes by heating in a nitrogen atmosphere. Thereafter, this raw material was held at 900 ° C. for 1 hour. In this way, the raw material was carbonized.

  Further, the carbon material thus obtained was pulverized with a mortar. Thereafter, the pulverized carbon material was taken out and passed through a sieve having an aperture of 106 μm. And the carbon material which passed the sieve was obtained as the pulverized particulate carbon catalyst 2 (AGBCo).

Except for using carbon catalyst 2 (AGBCo) instead of carbon catalyst 1 (PCo), a sheet-like harmful article formed by supporting the carbon catalyst 2 (AGBCo) on a paper substrate in the same manner as in Example 1 above. A paper sheet having a basis weight of 70 g / m ² was manufactured as a material decomposition material. And the aldehyde decomposition | disassembly test was done using the paper sheet (10 cm x 10 cm) containing 200 mg of carbon catalyst 2 (AGBCo) as a sample.

[Example 3]
Carbon catalyst 1 (PCo) was obtained in the same manner as in Example 1 described above. Next, the carbon catalyst 1 (PCo) was supported on an organic fiber nonwoven fabric. That is, after 5.16 g of polyvinyl alcohol-based aqueous binder (PVA R1130, manufactured by Kuraray Co., Ltd.) was dissolved in 78.4 g of tap water, 13.94 g of carbon catalyst 1 ( PCo) was added. After mixing all the components, the mixture was stirred at 1000 rpm for 10 minutes. After stirring, the mixed liquid is infiltrated into a cotton non-woven fabric (Oikos: basis weight 40 g / m ² , manufactured by Nisshinbo Textile Co., Ltd.) and dried in a hot air dryer at 100 ° C. for 1 minute, whereby the carbon catalyst 1 (PCo) is organic. A sheet-like material for decomposing a harmful substance formed on a fiber nonwoven fabric substrate was produced. And the aldehyde decomposition | disassembly test was done using the nonwoven fabric (10 cm x 10 cm) containing 200 mg of carbon catalyst 1 (PCo) as a sample.

[Example 4]
1 g of graphite AG. B (manufactured by Ito Graphite Industries Co., Ltd.), 5 g of 20 wt% polyacrylamide paper strength agent (manufactured by Seiko PMC Co., Ltd.), and 1 g of cobalt sulfate heptahydrate (CoSO ₄ · 7H ₂ O) were mixed to obtain The resulting viscous solution was dried at 80 ° C. for 12 hours.

  Next, the raw material was carbonized. That is, the raw material obtained as described above was placed in a quartz tube, purged with nitrogen for 20 minutes in an image furnace, and heated from room temperature to 900 ° C. over 90 minutes. Thereafter, this raw material was held at 900 ° C. for 1 hour to obtain a carbonized material.

  Further, the carbonized material was pulverized with a mortar. Thereafter, the pulverized carbonized material was taken out, and a carbonized material that passed through a sieve having an aperture of 106 μm was obtained as a pulverized particulate carbon catalyst 3 (AASCo).

Except for using carbon catalyst 3 (AASCo) instead of carbon catalyst 1 (PCo), in the same manner as in Example 1 above, a sheet-like harmful article formed by supporting the carbon catalyst 3 (AASCo) on a paper substrate A paper sheet having a basis weight of 70 g / m ² was manufactured as a material decomposition material. And the aldehyde decomposition | disassembly test was done using the paper sheet (10 cm x 10 cm) containing 200 mg of carbon catalysts 3 (AASCo) as a sample.

[Comparative Example 1]
The powder of carbon catalyst 1 (PCo) was used as it was as a harmful substance decomposition material. An aldehyde decomposition test was performed using 200 mg of powder of carbon catalyst 1 (PCo) as a sample.

[Comparative Example 2]
The carbon catalyst 2 (AGBCo) powder was used as it was as a harmful substance decomposition material. An aldehyde decomposition test was performed using 200 mg of carbon catalyst 2 (AGBCo) powder as a sample.

[Comparative Example 3]
A paper sheet (that is, only the paper substrate of the hazardous substance decomposing material according to Example 1) was produced in the same manner as in Example 1 except that the carbon catalyst 1 (PCo) was not used. The obtained paper sheet was observed with an electron microscope. Moreover, the aldehyde decomposition | disassembly test and the deterioration test were done using this paper sheet (10 cm x 10 cm) as a sample.

[Comparative Example 4]
A paper sheet obtained by supporting the activated carbon on a paper substrate in the same manner as in Example 1 except that high-performance activated carbon (MSC-30, manufactured by Kansai Thermal Chemical Co., Ltd.) was used instead of the carbon catalyst. Manufactured. And the aldehyde decomposition | disassembly test was done using the paper sheet (10 cm x 10 cm) containing 200 mg activated carbon as a sample.

[Comparative Example 5]
A paper sheet is produced by supporting the Y-type zeolite on a paper substrate in the same manner as in Example 1 except that Y-type zeolite (HISIV6000, manufactured by Union Showa Co., Ltd.) is used instead of the carbon catalyst. did. And the aldehyde decomposition | disassembly test was done using the paper sheet (10 cm x 10 cm) containing 200 mg Y-type zeolite as a sample.

[Comparative Example 6]
A paper sheet in which the A-type zeolite is supported on a paper substrate in the same manner as in Example 1 except that A-type zeolite (Molecular Sieve 4A powder, Union Showa Co., Ltd.) is used instead of the carbon catalyst. Manufactured. And the aldehyde decomposition | disassembly test was done using the paper sheet (10 cm x 10 cm) containing 200 mg A-type zeolite as a sample.

[Comparative Example 7]
A paper sheet in which the X-type zeolite is supported on a paper substrate in the same manner as in Example 1 except that X-type zeolite (Zeoram F-9, manufactured by Tosoh Corporation) is used instead of the carbon catalyst. Manufactured. And the aldehyde decomposition | disassembly test was done using the paper sheet (10 cm x 10 cm) containing 200 mg X-type zeolite as a sample.

[Comparative Example 8]
A paper sheet is produced by supporting the photocatalyst A on a paper substrate in the same manner as in Example 1 except that the photocatalyst A (manufactured by Ishihara Sangyo Co., Ltd., ST-01) is used instead of the carbon catalyst. did. And the aldehyde decomposition | disassembly test and the deterioration test were done using the paper sheet (10 cm x 10 cm) containing 200 mg of photocatalysts A as a sample.

In the aldehyde decomposition test and the deterioration test, an ultraviolet lamp (black light fluorescent lamp FL15BLB-A: peak wavelength 352 nm, manufactured by Toshiba Lighting & Technology Co., Ltd.) was used, with an intensity of 0.1 mW / cm ² to the paper sheet. Irradiated with ultraviolet rays.

[Comparative Example 9]
Using a paper sheet (10 cm × 10 cm) containing 200 mg of photocatalyst A obtained by the same method as in Comparative Example 8 described above as a sample, the aldehyde decomposition test was performed in the same manner as in Comparative Example 8 except that UV irradiation was not performed. Went.

[Comparative Example 10]
A paper sheet is produced by supporting the photocatalyst B on a paper substrate in the same manner as in Example 1 except that the photocatalyst B (TP-S201, manufactured by Sumitomo Chemical Co., Ltd.) is used instead of the carbon catalyst. did. And the aldehyde decomposition | disassembly test and the deterioration test were done using the paper sheet (10 cm x 10 cm) containing 200 mg of photocatalyst B as a sample.

In the aldehyde decomposition test and the deterioration test, an ultraviolet lamp (black light fluorescent lamp FL15BLB-A: peak wavelength 352 nm, manufactured by Toshiba Lighting & Technology Co., Ltd.) was used, with an intensity of 0.1 mW / cm ² to the paper sheet. Irradiated with ultraviolet rays.

[Comparative Example 11]
Using a paper sheet (10 cm × 10 cm) containing 200 mg of photocatalyst B obtained by the same method as in Comparative Example 10 described above as a sample, an aldehyde decomposition test was performed in the same manner as in Comparative Example 10 except that UV irradiation was not performed. Went.

[Comparative Example 12]
The ZSM-5 zeolite was supported on an organic fiber nonwoven fabric substrate in the same manner as in Example 3 except that ZSM-5 zeolite (Union Showa Co., Ltd., HISIV3000) was used instead of the carbon catalyst 1. A nonwoven fabric was produced. And the aldehyde decomposition | disassembly test was done using the nonwoven fabric (10 cm x 10 cm) containing 200 mg of ZSM-5 zeolite as a sample.

[Results of electron microscope observation]
1A and 1B show electron micrographs obtained in Example 1 and Comparative Example 3 described above, respectively. As shown in FIG. 1A, in the paper sheet manufactured in Example 1, it was confirmed that the fine particles of the carbon catalyst were dispersed and supported between the paper fibers of the paper base material. Moreover, the carbon catalyst was firmly attached to the paper base material with most of its surface exposed.

[Results of aldehyde decomposition test]
FIG. 2 shows the results obtained in the aldehyde decomposition test. FIG. 2 shows formaldehyde (HCHO) concentration (ppm), carbon dioxide (CO ₂ ) concentration (ppm), and formaldehyde after 3 hours and 24 hours for each of Examples 1 to 4 and Comparative Examples 1 to 12. The results of evaluation of decomposition rate (%), formaldehyde disappearance rate (%) and formaldehyde adsorption rate (%) are shown. The carbon dioxide concentration is a value obtained by subtracting the measured value in the atmosphere (outside the Tedlar bag) from the measured value in the Tedlar bag.

  As shown in FIG. 2, a paper sheet containing carbon catalyst 1 (PCo) according to Example 1, a paper sheet containing carbon catalyst 2 (AGBCo) according to Example 2, and a carbon catalyst 1 (PCo) according to Example 3. Both the organic fiber nonwoven fabric containing and the paper sheet containing the carbon catalyst 3 (AASCo) achieved a formaldehyde decomposition rate of 100% after 24 hours. That is, it was confirmed that the hazardous substance decomposition materials according to Examples 1 to 4 have excellent aldehyde decomposition performance.

  Further, as apparent from the aldehyde decomposition rate after 3 hours, the aldehyde decomposition rates of the hazardous substance decomposition materials according to Examples 1 to 4 are the same as those of the carbon catalyst 1 (PCo) powder according to Comparative Example 1 and Comparative Example 2. It was significantly larger than the carbon catalyst 2 (AGBCo) powder. That is, carbon catalyst 1 (PCo) powder, carbon catalyst 2 (AGBCo) powder and carbon catalyst 3 (AASCo) powder are supported on a fiber base material such as a paper base material or a non-woven fabric, so that their harmful substance decomposition rate is remarkable. Improved. Moreover, the harmful substance decomposition material which concerns on Examples 1-4 did not adsorb | suck formaldehyde substantially.

In addition, from the paper sheet containing the photocatalyst according to Comparative Example 8 and Comparative Example 10, a large amount of CO ₂ having an initial aldehyde concentration of 1000 ppm or more was generated by ultraviolet irradiation for 24 hours. Therefore, in the paper sheet containing a photocatalyst, it was thought that remarkable deterioration of the paper base material occurred.

[Results of deterioration test]
FIG. 3 shows the results obtained in the deterioration test. As shown in FIG. 3, from the paper sheet which carries the carbon catalyst 1 (PCo) which concerns on Example 1 on the paper base material, and the paper sheet which consists of the said paper base material which concerns on the comparative example 3, ultraviolet rays for 24 hours are shown. Irradiation produced no carbon dioxide (CO ₂ ) or carbon monoxide (CO). Further, in these paper sheets, no yellow change in appearance due to ultraviolet irradiation was observed.

  In contrast, a large amount of carbon dioxide and carbon monoxide were generated from the paper sheet containing the photocatalyst according to Comparative Example 8 and Comparative Example 10 by ultraviolet irradiation for 24 hours. The generation of this large amount of carbon dioxide and carbon monoxide was thought to be due to the deterioration of the paper substrate in the paper sheet containing the photocatalyst. Further, the paper sheet containing the photocatalyst was yellowed in appearance when irradiated with ultraviolet rays.

  By such an aldehyde decomposition test and degradation test, it was confirmed that the hazardous substance decomposition material containing the carbon catalyst according to Examples 1 to 4 effectively decomposes the hazardous substance without deteriorating the base material.

[Oxidative decomposition test of carbon monoxide]
A paper sheet (5 cm × 10 cm) containing 100 mg of carbon catalyst 1 (PCo) according to Example 1 or 100 mg of carbon catalyst 1 (PCo) powder according to Comparative Example 1 is housed in a 25 ° C. Tedlar bag, and the Tedlar bag Then, 3 L of air containing carbon monoxide at a concentration of 2100 ppm was injected and left in a dark room.

  After 24 hours and 60 hours, the carbon monoxide concentration in the Tedlar bag and the concentration of carbon dioxide generated by the oxidative decomposition of the carbon monoxide were measured. The concentration of carbon monoxide and the concentration of carbon dioxide were measured with a carbon monoxide detector tube and a carbon dioxide detector tube (manufactured by Gastec Co., Ltd.).

  The carbon monoxide decomposition rate (%) is expressed by the following formula; carbon monoxide decomposition rate (%) = [carbon dioxide concentration (ppm) after 24 hours or 60 hours−carbon dioxide amount in the atmosphere (ppm)] / Initial carbon monoxide concentration (ppm) × 100; Further, the carbon monoxide disappearance rate (%) is expressed by the following formula: carbon monoxide disappearance rate (%) = [(initial carbon monoxide concentration (ppm) −carbon monoxide concentration after 24 hours or 60 hours (ppm )) / Initial carbon monoxide concentration (ppm)] × 100. Furthermore, the carbon monoxide adsorption rate (%) was determined by the following formula: carbon monoxide adsorption rate (%) = carbon monoxide disappearance rate (%) − carbon monoxide decomposition rate (%).

  FIG. 4 shows the results of the oxidative decomposition test of carbon monoxide. As shown in FIG. 4, the paper sheet according to Example 1 was confirmed to oxidatively decompose carbon monoxide, and the paper sheet was compared with the carbon catalyst 1 (PCo) powder itself according to Comparative Example 1. It was confirmed to have high carbon monoxide oxidative decomposition performance. Moreover, the paper sheet which concerns on Example 1 did not adsorb | suck carbon monoxide substantially similarly to the carbon catalyst 1 (PCo) which concerns on the comparative example 1. FIG.

[Antimicrobial test]
A paper sheet obtained by carrying the carbon catalyst 1 (PCo) according to Example 1 on a paper base material, a paper sheet comprising the paper base material according to Comparative Example 3, and a photocatalyst according to Comparative Example 8 carried on a paper base material The antibacterial properties of the paper sheets were evaluated.

  The antibacterial property was evaluated by the presence and width of a halo (growth inhibition zone) in a qualitative test (halo test) based on the antibacterial method of textile products specified by JIS L 1902-2008. As a test bacterium, Staphylococcus aureus ATCC 6538P or Escherichia coli NBRC3301 was used.

  FIG. 5 shows the results of the antibacterial test. As shown in FIG. 5, the growth inhibition zone was generated only when the paper sheet according to Example 1 was used. That is, it was confirmed that the paper sheet according to Example 1 exhibits antibacterial properties.

[Mold resistance test]
A paper sheet obtained by carrying the carbon catalyst 1 (PCo) according to Example 1 on a paper base material, a paper sheet comprising the paper base material according to Comparative Example 3, and a photocatalyst according to Comparative Example 8 carried on a paper base material The mold resistance of the paper sheet was evaluated.

  Mold resistance was evaluated by a test based on the mold resistance test method of JIS Z 2911-2000 (wet method). That is, a test piece (5 cm × 5 cm) of a paper sheet was stuck on and adhered to a flat plate medium, and then the mold mixed spore suspension was sprayed on the test piece and cultured at 28 ± 2 ° C. for 1 week. As a test bacterium, Aspergillus niger NBRC 6341, Penicillium citrinum NBRC 6352, Chaetmium globosum NBRC 6347 or Myrothecerium verrucaria NBRC 6113 was used.

  Then, the mold resistance of the sample was evaluated based on the area of the mold grown on the sample. Specifically, when the mycelium growth is not observed in the part where the fungus spores are contacted with the sample, it is evaluated as “0”, and the area of the mycelial growth part recognized in the part where the fungus spores are contacted with the sample is When it does not exceed 1/3 of the total area, it is evaluated as “1”, and when the area of the mycelial growth part observed in the part where the fungus spores are in contact with the sample exceeds 1/3 of the total area, 2 ”.

  FIG. 6 shows the results of the mold resistance test. As shown in FIG. 6, only in the paper sheet which concerns on Example 1, the growth of mold | fungi hypha was not recognized. That is, it was confirmed that the paper sheet according to Example 1 has mold resistance.

Claims (8)

A carbon catalyst having catalytic activity to decompose harmful substances;
A base material carrying the carbon catalyst;
Hazardous substance decomposition material characterized by containing. The hazardous substance decomposition material according to claim 1, wherein the harmful substance is a volatile organic compound. The volatile organic compound is an aldehyde or an oxide thereof. The hazardous substance decomposing material according to claim 2. The hazardous substance decomposition material according to any one of claims 1 to 3, wherein the carbon catalyst is obtained by carbonization of a raw material containing an organic substance and a metal. The harmful substance-decomposing material according to any one of claims 1 to 4, wherein the base material is a fiber base material. The harmful substance decomposition material according to claim 5, wherein the fiber base material is an organic fiber base material. The toxic substance decomposition material according to claim 6, wherein the organic fiber base material is a paper base material. The harmful substance decomposition material according to claim 7, which is obtained by papermaking of a raw slurry containing the carbon catalyst.