JP2009214094A - Oxidation catalyst, oxidizing method, oxidation apparatus, and antimicrobial agent - Google Patents

Oxidation catalyst, oxidizing method, oxidation apparatus, and antimicrobial agent Download PDF

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JP2009214094A
JP2009214094A JP2008272709A JP2008272709A JP2009214094A JP 2009214094 A JP2009214094 A JP 2009214094A JP 2008272709 A JP2008272709 A JP 2008272709A JP 2008272709 A JP2008272709 A JP 2008272709A JP 2009214094 A JP2009214094 A JP 2009214094A
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ionic liquid
acac
trifluoroacetate
metal
mixture
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Yoshikazu Makioka
Yuta Takaishi
Hiroki Taniguchi
良和 牧岡
裕樹 谷口
優太 高石
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Tokyo Institute Of Technology
国立大学法人東京工業大学
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<P>PROBLEM TO BE SOLVED: To provide a new oxidation catalyst and antimicrobial agent. <P>SOLUTION: The oxidation catalyst and the antimicrobial agent are manufactured by supporting an ionic liquid containing a metal compound on a carrier. The ionic liquid preferably includes an ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, phosphonium-based ionic liquid and the like. The metal compound preferably includes a metal salt, metal complex, metal oxide, metal hydroxide, metal sulfide, metal fine particles and the like. The carrier preferably includes granular silica, alumina, activated carbon, molecular sieve, fiber, glass plate. glass capillary, glass beads, metal plate, metal capillary, sawdust, paper, sponge and the like. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel oxidation catalyst. The present invention also relates to a novel oxidation method using this oxidation catalyst. The present invention also relates to a novel oxidation apparatus using this oxidation method. The present invention also relates to a novel antibacterial agent.

  Conventionally, as catalysts for the oxidation removal of volatile organic compounds (VOCs), many catalysts in which noble metals such as palladium and platinum and rare earth oxides are directly supported on silica and alumina are used. For this purpose, a high temperature of several hundred degrees is required (see Non-Patent Document 1, for example).

  Olefin (Pd / Cu catalyst), Thiol (Co catalyst), Alcohol (Cu catalyst, Ru catalyst, V catalyst), Aldehyde (Ni catalyst), Alkylbenzene (P catalyst) Several examples of air oxidation reactions of Co catalysts have been reported.

In the Wacker oxidation reaction of terminal olefins using PdCl 2 / CuCl 2 catalysts, ketones are synthesized using [BuMeIm] BF 4 as a solvent, but the reaction substrate (2 mmol) or ionic liquid (2 mL) is synthesized. The disadvantage is that the catalyst metal used has a high concentration (10 mol%). Also, it shall be used CuCl 2 and (2 mmol) against PdCl 2 (0.2 mmol) (see Non-Patent Document 2).

  Reactions using cobalt (II) -phthalocyanine complex (1 mol%) as a catalyst to synthesize thiols by air oxidation to synthesize disulfide have been reported, but the molecular weight of the ligand is large and the amount of catalyst used (weight) is large. Is a drawback (see Non-Patent Document 3).

[BuMeIm] PF6 is used as an ionic liquid in a reaction for synthesizing a ketone by oxidation of alcohol. TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) (5 mol%) must be used for the catalyst CuCl (5 mol%), and the catalyst system is complicated (non- (See Patent Document 4). When a RuCl 2 (PPh 3 ) 3 catalyst (1 mol%) is used, the ligand phosphine may be oxidized and the catalyst may be decomposed. Although there is a possibility that the catalyst metal is changed to ruthenium oxide, there is no description thereof (see Non-Patent Document 5). Although the reaction using V (O) (acac) 2 (5 mol%) as a catalyst has also been reported, the addition of a tertiary amine twice as much as the catalyst is essential, and the reaction system is complicated. (See Non-Patent Document 6). Further, there is no description that the catalyst is well dissolved in the ionic liquid and forms an oxide.

Aldehydes also undergo air oxidation using Ni (acac) 2 (3 mol%) as a catalyst and are easily converted to carboxylic acids (see Non-Patent Document 7). There is no description that the catalyst is completely dissolved in [BuMeIm] PF 6 and forms an oxide.

Air oxidation of the alkyl group of the side chain of alkylbenzene is performed in an acidic ionic liquid using Co (OAc) 2 , NaBr, AIBN (azobisisobutyronitrile) as a catalyst. In addition to the complicated catalyst system, acidic ionic liquid [HMeIm] CF 3 COO or neutral ionic liquid [BuMeIm] BF 4 and trifluoroacetic acid (CF 3 COOH) mixed solvent are used, so corrosion of the reaction vessel is a problem ( (See Patent Document 1).

  Also known is a liquid phase oxidation reaction of alkanes using a catalyst obtained by chemically bonding an art-type metal ammonium salt to the surface of silica gel (see Patent Document 2). These are all used as a catalyst for obtaining an oxidation product from the viewpoint of synthetic chemistry.

On the other hand, there are the following four examples as a document in which a metal oxide is generated in an ionic liquid.
As an example of the synthesis of titanium oxide, titanium tetraisopropoxide (Ti (OiPr) 4 is used as a raw material, and it is hydrolyzed in [BuMeIm] PF 6 to synthesize fine-grained TiO 2 with a nanostructure (non-patent literature) 8) Finally, TiO 2 fine powder is obtained by separation from the ionic liquid, but the fine particles synthesized in the ionic liquid have a BET specific surface area several times larger than those synthesized in the isopropanol. It is a report.

  In addition, zinc acetate pyramid-like microcrystals were successfully synthesized by hydrolysis while heating zinc acetate to 286 ° C in ethylenediamine oleate (a mixture of ethylenediamine and oleic acid) as an ionic liquid (Non-Patent Documents). 9).

Furthermore, in [BuMeIm] BF 4 , nanoneedle and nanorod-like manganese dioxide (MnO 2 ) were successfully synthesized by oxidation-reduction reaction of manganese chloride (MnCl 2 ) and potassium permanganate (KMnO 4 ) ( Non-patent document 10).

Furthermore, there is a report that iron oxide nanoparticles are synthesized by dissolving Fe (CO) 5 as an ionic liquid in [BuMeIm] (CF 3 SO 2 ) 2 N and thermally differentiating in air (non-patented). Reference 11).

  The inventor has disclosed the technical contents related to the present invention (see Non-Patent Document 12). This is considered to be applicable to Patent Act Article 30 (1).

In recent years, a wide variety of antibacterial products such as organic antibacterial materials and inorganic antibacterial materials have been developed. Among them, silver-based inorganic antibacterial materials that exhibit antibacterial properties by eluting a small amount of Ag + ions, and inorganic antibacterial materials mainly composed of compounds having photocatalytic activity typified by titanium oxide (non-patent literature) 13). Attempts have also been made to use a silver compound on a carrier such as activated carbon as a water treatment agent (see Patent Documents 3 to 6). It has also been found that silica fine particles having a mesospace prepared using an ionic liquid as a template have antibacterial activity (see Non-Patent Document 14). It has also been reported that vanadium oxide nanoparticles exhibit antibacterial activity (see Non-Patent Documents 15 to 16). There is also a report that a vanadium compound supported on a water-soluble polymer such as polyacrylic acid exhibits antibacterial activity (see Non-Patent Document 17).

  The inventor developed a catalyst prepared by impregnating silica gel with a metal compound such as vanadium dissolved in an ionic liquid for the purpose of performing oxidative decomposition of volatile organic compounds with air at a low temperature ( Non-patent document 12). Using this catalyst, air oxidative decomposition of various volatile organic compounds was performed.

  There are several reports on the antibacterial activity of ionic liquids typified by imidazolium salts. It is known that the antibacterial activity increases as the alkyl group chain length constituting the ammonium salt increases (see Non-Patent Document 18). There is also a report of producing antibacterial fibers using an ionic liquid containing no halogen other than an imidazolium salt (see Patent Document 7).

J. Tang, F. Yang, H. Zhu, CN 1528726 (2004) W. F. Hoelderich, E. Modrogan, GB 2427192 Japanese Patent Laid-Open No. 5-84439 JP-A-6-135808 JP-A-6-287103 JP 11-278823 A JP 2007-39820 A P. Gelin, M. Primet, Applied Catalysis B: Environmental 39, 1-37 (2002) I. A. Ansari, S. Joyasawal, M. K. Gupta, J. S. Yadav, R. Gee, Tetrahedron Lett., 2005, 46, 7507-7510 S. M. S. Chauhan, A. Kumar, K. A. Srinivas, Chem. Commun., 2003, 2348-2349 I. A. Ansari, R. Gee, Org. Lett., 2002, 4, 1507-1509 A. Wolfson, S. Wuyts, D. E. D. Vos, I. F. J. Vankelecom, P. A. Jacobs, Tetrahedron Lett., 2002, 43, 8107-8110 N. Jiang, A. J. Ragauskas, Tetrahedron Lett., 2007, 48, 273-276 J. Howarth, Tetrahedron Lett., 2000, 41, 6627-6629 K. Yoo, H. Choi, D. D. Dionysiou, Chem. Commun., 2004, 2000-2001 X. Zhou, Z.-X. Xie, Z.-Y. Jiang, Q. Kuang, S.-H. Zhang, T. Xu, R.-B. Huang, L.-S. Zheng, Chem. Commun ., 2005, 5572-5574 L.-X. Yang, Y.-J. Zhu, W.-W. Wang, H. Tong, K.-L. Ruan, J. Phys. Chem., B, 2006, 110, 6609-6614. Y. Wang, S. Maksimuk, R. Shen, H. Yang, Green Chem., 2007, 9, 1051-1056 Yuki Taniguchi, Yoshikazu Makioka, Koji Inazu, Toshihide Baba, Yuta Takaishi, Takeki Takamura, The Japan Petroleum Institute Kansai Branch 16th Research Presentation Meeting, The Japan Institute of Energy Kansai Branch 52nd Joint Research Meeting, Kansai University, December 7, 2007, P08, pp66-67. Atsushi Uchida, Antibacterial and Antifungal, 2008, 36 (4), 273-280) B. G. Trewyn, C. M. Whitman, V. S.-Y. Lin, Nano Lett., 2004, 4, 2139-2143. J.-f. Ju, C.-j. Li, M. Xu, H. Ye, Fine Chemicals 2003, (20), 641-643 + 681. J.-f. Ju, M. Xu, C.-j. Li, Fine Chemicals 2006, (23), 10481055. D. Kalita, S. Sarmah, S. P. Das, D. Baishya, A. Patowary, S. Baruah, N. S. Islam, React. Func. Polym. 2008, 68, 876-890. J. Pernak, K. Sobaszkiewicz, I. Mirska, Green Chem., 2003, 5, 52-56.

  However, in the above-mentioned papers, all are reports of synthesizing and isolating metal oxide fine particles, and the synthesis process and purification process are complicated, such as adding various additives and taking a lot of time for washing. It is. Of course, any paper is intended for the synthesis of fine particles and analysis of physical properties, and the use is not described.

  On the other hand, as described above, the inventor has developed a catalyst prepared by impregnating silica gel with a small amount of a metal compound such as vanadium dissolved in an ionic liquid. Using this catalyst, air oxidative decomposition of various volatile organic compounds was performed. However, the evaluation of antibacterial activity has not been studied.

  Further, as described above, there are several reports on the antibacterial activity of ionic liquids typified by imidazolium salts. There is also a report of producing an antibacterial fiber using an ionic liquid containing no halogen other than an imidazolium salt. However, antibacterial activity has not been investigated for other ionic liquids.

  Therefore, development of a novel oxidation catalyst, oxidation method, oxidation apparatus and antibacterial agent that solves such problems is desired.

The present invention has been made in view of such problems, and an object thereof is to provide a novel oxidation catalyst.
Another object of the present invention is to provide a novel oxidation method using this oxidation catalyst.
Another object of the present invention is to provide a novel oxidation apparatus using this oxidation method.
Another object of the present invention is to provide a novel antibacterial agent.

  In order to solve the above problems and achieve the object of the present invention, an oxidation catalyst of the present invention is characterized in that an ionic liquid containing a metal compound is supported on a carrier in an oxidation catalyst for oxidizing a target substance.

Here, although not necessarily limited, the target substance is preferably a volatile organic compound. Moreover, although not necessarily limited, it is preferable that a target substance consists of 1 type chosen from styrene, benzene, ethylbenzene, p-xylene, trichloroethane, toluene, trichloroethylene, or any 2 or more types of mixture. Although not limited, the ionic liquid is composed of one or a mixture of two or more selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, and phosphonium-based ionic liquid. It is preferable. Also, but not limited to, ionic liquids include N-butyl-N'-methylimidazolium trifluoroacetate, N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N ' -Methylimidazolium hexafluorophosphate, N-octyl-N'-methylimidazolium trifluoroacetate, N-butylpyridinium trifluoroacetate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, It is preferably composed of one kind selected from N-butylpyridinium tetrafluoroborate, trihexyltetradecylphosphonium tetrafluoroborate and trihexyltetradecylphosphonium chloride, or a mixture of any two or more thereof. In addition, the metal compound is not limited, but the metal compound is selected from a metal salt, a metal complex, a metal oxide, a metal hydroxide, a metal sulfide, a metal fine particle, or a mixture of any two or more thereof. It is preferable to become. Although not limited, the metal compounds include VO (acac) 2 , V (acac) 3 , NaVO 3 , Na 3 VO 4 , VOSO 4 , Cu (OAc) 2 , Fe (acac) 3 , Pd 1 type selected from (acac) 2 , MoO 2 (acac) 2 , ( n Bu 4 N) 4 PVMo 11 O 40 , ( n Bu 4 N) 3 PMo 12 O 40 , or a mixture of any two or more types It is preferable to become. Further, the carrier is selected from, but not limited to, granular silica, alumina, activated carbon, molecular sieves, fiber, glass plate, glass fine glass, glass beads, metal plate, metal fine powder, sawdust, paper, and sponge. It is preferable that it consists of 1 type, or any 2 or more types of mixture.

  The oxidation method of the present invention is characterized in that the target substance is oxidized using an oxidation catalyst. The oxidation catalyst is characterized in that an ionic liquid containing a metal compound is supported on a carrier.

Here, although not necessarily limited, the target substance is preferably a volatile organic compound. Moreover, although not necessarily limited, it is preferable that a target substance consists of 1 type chosen from styrene, benzene, ethylbenzene, p-xylene, trichloroethane, toluene, trichloroethylene, or any 2 or more types of mixture. Although not limited, the ionic liquid is composed of one or a mixture of two or more selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, and phosphonium-based ionic liquid. It is preferable. Also, but not limited to, ionic liquids include N-butyl-N'-methylimidazolium trifluoroacetate, N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N ' -Methylimidazolium hexafluorophosphate, N-octyl-N'-methylimidazolium trifluoroacetate, N-butylpyridinium trifluoroacetate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, It is preferably composed of one kind selected from N-butylpyridinium tetrafluoroborate, trihexyltetradecylphosphonium tetrafluoroborate and trihexyltetradecylphosphonium chloride, or a mixture of any two or more thereof. In addition, the metal compound is not limited, but the metal compound is selected from a metal salt, a metal complex, a metal oxide, a metal hydroxide, a metal sulfide, a metal fine particle, or a mixture of any two or more thereof. It is preferable to become. Although not limited, the metal compounds include VO (acac) 2 , V (acac) 3 , NaVO 3 , Na 3 VO 4 , VOSO 4 , Cu (OAc) 2 , Fe (acac) 3 , Pd 1 type selected from (acac) 2 , MoO 2 (acac) 2 , ( n Bu 4 N) 4 PVMo 11 O 40 , ( n Bu 4 N) 3 PMo 12 O 40 , or a mixture of any two or more types It is preferable to become. Further, the carrier is selected from, but not limited to, granular silica, alumina, activated carbon, molecular sieves, fiber, glass plate, glass fine glass, glass beads, metal plate, metal fine powder, sawdust, paper, and sponge. It is preferable that it consists of 1 type, or any 2 or more types of mixture.

  The oxidation apparatus of the present invention oxidizes a target substance using an oxidation catalyst. The oxidation catalyst is characterized in that an ionic liquid containing a metal compound is supported on a carrier.

Here, although not necessarily limited, the target substance is preferably a volatile organic compound. Moreover, although not necessarily limited, it is preferable that a target substance consists of 1 type chosen from styrene, benzene, ethylbenzene, p-xylene, trichloroethane, toluene, trichloroethylene, or any 2 or more types of mixture. Although not limited, the ionic liquid is composed of one or a mixture of two or more selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, and phosphonium-based ionic liquid. It is preferable. Also, but not limited to, ionic liquids include N-butyl-N'-methylimidazolium trifluoroacetate, N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N ' -Methylimidazolium hexafluorophosphate, N-octyl-N'-methylimidazolium trifluoroacetate, N-butylpyridinium trifluoroacetate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, It is preferably composed of one kind selected from N-butylpyridinium tetrafluoroborate, trihexyltetradecylphosphonium tetrafluoroborate and trihexyltetradecylphosphonium chloride, or a mixture of any two or more thereof. In addition, the metal compound is not limited, but the metal compound is selected from a metal salt, a metal complex, a metal oxide, a metal hydroxide, a metal sulfide, a metal fine particle, or a mixture of any two or more thereof. It is preferable to become. Although not limited, the metal compounds include VO (acac) 2 , V (acac) 3 , NaVO 3 , Na 3 VO 4 , VOSO 4 , Cu (OAc) 2 , Fe (acac) 3 , Pd 1 type selected from (acac) 2 , MoO 2 (acac) 2 , ( n Bu 4 N) 4 PVMo 11 O 40 , ( n Bu 4 N) 3 PMo 12 O 40 , or a mixture of any two or more types It is preferable to become. Further, the carrier is selected from, but not limited to, granular silica, alumina, activated carbon, molecular sieves, fiber, glass plate, glass fine glass, glass beads, metal plate, metal fine powder, sawdust, paper, and sponge. It is preferable that it consists of 1 type, or any 2 or more types of mixture.

  The antibacterial agent of the present invention is one in which an ionic liquid containing a metal compound is supported on a carrier.

Here, the ionic liquid is not limited, but the ionic liquid is one selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, and phosphonium-based ionic liquid, or a mixture of any two or more thereof. It is preferable to become. In addition, although not limited thereto, the ionic liquid includes an imidazolium tetrafluoroborate derivative, an imidazolium trifluoromethanesulfonate derivative, an imidazolium hexafluorophosphate derivative, an imidazolium bis (trifluoromethanesulfonyl) imide derivative, and an imidazolium. Trifluoroacetate derivatives, imidazolium alkyl sulfate derivatives, imidazolium hydrogen sulfate derivatives, imidazolium dialkyl phosphate derivatives, imidazolium chloride derivatives, imidazolium bromide derivatives, imidazolium iodide derivatives, imidazolium thiocyanide derivatives, Midazolium carboxylate derivatives, imidazolium bisoxazatoborate derivatives, imidazolium dicyanamide derivatives, pyridi Um tetrafluoroborate derivatives, pyridinium trifluoroacetate derivatives, pyridinium trifluoromethanesulfonate derivatives, pyridinium chloride derivatives, pyridinium bromide derivatives, pyridinium iodide derivatives, pyridinium thiocyanide derivatives, pyridinium dicyanamide derivatives, pyridinium alkyl sulfate derivatives , Pyridinium hydrogen sulfate derivatives, pyridinium dialkyl phosphate derivatives, pyridinium carboxylate derivatives, pyridinium bisoxalatoborate derivatives, pyridinium dicyanamide derivatives, or a mixture of any two or more thereof. Also, but not limited to, ionic liquids include N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N'-methylimidazolium trifluoromethanesulfonate, N-butyl-N ' -Methylimidazolium hexafluorophosphate, N-butyl-N'-methylimidazolium bis (trifluoromethanesulfonyl) imide, N-hexyl-N'-methylimidazolium trifluoroacetate, N-octyl-N'-methylimidazo It may be composed of one or a mixture of two or more selected from trifluorotrifluoroacetate, N-butylpyridinium tetrafluoroborate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate preferable. In addition, the metal compound is not limited, but the metal compound is selected from a metal salt, a metal complex, a metal oxide, a metal hydroxide, a metal sulfide, a metal fine particle, or a mixture of any two or more thereof. It is preferable to become. In addition, but not limited to, metal compounds include VO (acac) 2 , Mn (acac) 2 , Ni (acac) 2 , Co (acac) 3 , Fe (acac) 3 , MoO 2 (acac) 2 , Pd (acac) 2 , NaVO 3 , VOSO 4 (H 2 O) n , or a mixture of any two or more thereof. In addition, although not limited, the carrier is granular silica, alumina, activated carbon, molecular sieves, ceramics, brick, wood, fiber, glass plate, glass fine rod, glass beads, metal plate, metal fine rod, sawdust, It is preferably made of one kind selected from paper and sponge, or a mixture of any two or more kinds.

  The antibacterial agent of the present invention is obtained by supporting an ionic liquid on a carrier.

  Here, the ionic liquid is not limited, but the ionic liquid is one selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, and phosphonium-based ionic liquid, or a mixture of any two or more thereof. It is preferable to become. In addition, although not limited thereto, the ionic liquid includes imidazolium tetrafluoroborate derivatives, imidazolium trifluoroacetate derivatives, imidazolium alkyl sulfate derivatives, imidazolium hydrogen sulfate derivatives, imidazolium dialkyl phosphate derivatives. Imidazolium chloride derivatives, imidazolium bromide derivatives, imidazolium iodide derivatives, thiocyanide imidazolium derivatives, midazolium carboxylate derivatives, imidazolium bisoxazatoborate derivatives, imidazolium dicyanamide derivatives, pyridinium trifluoroacetates Tart derivatives, pyridinium trifluoromethanesulfonate derivatives, pyridinium chloride derivatives, pyridinium bromide derivatives, pyridinium iodide derivatives, thio One selected from pyridinium anion derivatives, pyridinium dicyanamide derivatives, pyridinium alkyl sulfate derivatives, pyridinium hydrogen sulfate derivatives, pyridinium dialkyl phosphate derivatives, pyridinium carboxylate derivatives, pyridinium bisoxalatoborate derivatives, pyridinium dicyanamide derivatives Or any two or more mixtures, and the ionic liquid is preferably water-soluble. Also, but not limited to, ionic liquids include N-butyl-N'-methylimidazolium tetrafluoroborate, N-hexyl-N'-methylimidazolium trifluoroacetate, N-octyl-N ' It is preferably made of one kind selected from -methylimidazolium trifluoroacetate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, or a mixture of any two or more kinds. In addition, although not limited, the carrier is granular silica, alumina, activated carbon, molecular sieves, ceramics, brick, wood, fiber, glass plate, glass fine rod, glass beads, metal plate, metal fine rod, sawdust, It is preferably made of one kind selected from paper and sponge, or a mixture of any two or more kinds.

  The present invention has the following effects.

  The oxidation catalyst of the present invention can provide a novel oxidation catalyst because an ionic liquid containing a metal compound is supported on a carrier in an oxidation catalyst for oxidizing a target substance.

  The oxidation method of the present invention provides a novel oxidation method in which the target substance is oxidized using an oxidation catalyst, in which the oxidation catalyst is an ionic liquid containing a metal compound supported on a carrier. be able to.

  The oxidation apparatus of the present invention oxidizes a target substance using an oxidation catalyst. In the oxidation apparatus, since the oxidation catalyst is a carrier on which an ionic liquid containing a metal compound is supported, a novel oxidation apparatus is provided. be able to.

  Since the antibacterial agent of the present invention is obtained by supporting an ionic liquid containing a metal compound on a carrier, a novel antibacterial agent can be provided.

  Since the antibacterial agent of the present invention is obtained by supporting an ionic liquid on a carrier, a novel antibacterial agent can be provided.

  Hereinafter, the best mode for carrying out the invention relating to an oxidation catalyst, an oxidation method and an oxidation apparatus will be described.

  The oxidation catalyst will be described. The oxidation catalyst is an oxidation catalyst that oxidizes a target substance, in which an ionic liquid containing a metal compound is supported on a carrier.

As volatile organic compounds to be treated by the catalyst of the present invention, normal pentane, normal hexane, cyclohexane, normal heptane, benzene, toluene, ethylbenzene, styrene, p-xylene, m-xylene, o-xylene, anisole, furan, Diethyl ether, tetrahydrofuran, tert-butyl methyl ether, cyclohexyl methyl ether, 1,4-dioxane, dimethylformamide, formaldehyde, acetaldehyde, acetone, butanone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, methyl amine, dimethylamine, trimethylamine, pyridine, methyl mercaptan (CH 3 SH), chloromethane, dichloromethane, chloroform, carbon tetrachloride 1 selected from 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethylene, tetrachloroethylene, acetic acid, propionic acid, butyric acid, chloroacetic acid, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like A seed or a mixture of any two or more of them can be employed.

The processing target of the catalyst of the present invention is not limited to volatile organic compounds. In addition to this, the catalyst of the present invention is treated with one or more selected from ammonia, carbon monoxide, hydrogen sulfide (H 2 S), phosphine (PH 3 ), silane (SH 4 ) and the like. Mixtures can be employed.

  The catalyst of the present invention uses a metal compound. The reason for using the metal compound is that it has the ability to combine with oxygen by an oxidation-reduction reaction to oxygenate and decompose the organic compound and to act as a catalyst.

  The metal compounds include vanadium, molybdenum, copper, iron, palladium, titanium, zirconium, yttrium, lanthanum, niobium, tantalum, chromium, tungsten, manganese, rhenium, ruthenium, cobalt, rhodium, iridium, nickel, platinum, silver , One selected from zinc, tin, lead and the like, or a mixture of any two or more thereof.

  As the metal compound, one or a mixture of two or more selected from metal salts, metal complexes, metal oxides, metal hydroxides, metal sulfides, metal fine particles, and the like can be employed.

Specific examples of the metal salt include Cu (OAc) 2 , Zn (OAc) 2 , Rh (OAc) 2 , Ni (OAc) 2 , Mo 2 (OAc) 4 , Mn (OAc) 2 , Mn (OAc) 3 Acetic acid salts such as Fe (C 2 O 4 ), Fe 2 (C 2 O 4 ) 3 , Ni (C 2 O 4 ), etc., ZnCl 2 , VCl 3 , V (O) Cl 3 , WCl 6 , RhCl 3 , ReCl 5 , MoCl 5 , MnCl 2 , NiCl 2 , FeCl 2 , FeCl 3 , CuCl 2 , CuCl and other chlorides, ZnBr 2 , WBr 5 , RhBr 3 , MnBr 2 , FeBr 2 , NiBr 2 , CuBr, bromides such as CuBr 2, ZnI 2, RhI 3 , MnI 2, FeI 2, NiI 2, iodide CuI like, MnCO 3, NiCO 3, CuCO 3 like carbonates, Zn 3 (PO 4) 2 , Phosphate such as RhPO 4 and FePO 4 , Zn (NO 3 ) 2 , Rh (NO 3 ) 3 , Mn (NO 3 ) 2 , Ni (NO 3 ) 2 and other nitrates, ZnSO 4 , VOSO 4 , Rh 2 (SO 4) 3, MnSO 4 , FeSO 4, NiSO 4, CuSO 4 sulfates such as, Zn (CF 3 SO 3) 2, Cu (CF 3 SO 3) 1 kind selected from a sulfonic acid salt of 2 such as Or a mixture of two or more of them.

Specific examples of metal complexes include VO (acac) 2 , V (acac) 3 , MoO 2 (acac) 2 , Pd (acac) 2 , Fe (acac) 2, Fe (acac) 3, Cu (acac) 2 , Mn (acac) 2 , Ni (acac) 2 , Co (acac) 2 , Co (acac) 3 and other acetylacetonate complexes, RuCl 2 (PPh 3 ) 3 , RhCl (PPh 3 ) 3 and other phosphine complexes, Carbonyl complexes such as Mo (CO) 6 , Ni (CO) 4 , Fe (CO) 5 , Mn 2 (CO) 10 , W (CO) 6 , Ti (O i Pr) 4 , V (O) (O i One kind selected from metal alcoholates such as Pr) 3 or a mixture of any two or more kinds may be employed.

Specific examples of metal oxides include NaVO 3 , Na 3 VO 4 , V 2 O 3 , V 2 O 4 , V 2 O 5 , ( n Bu 4 N) 3 PMo 12 O 40 , ( n Bu 4 N) 4 PVMo 11 O 40 , MoO 2 , MoO 3 , MnO, Mn 2 O 3 , MnO 2 , Mn 3 O 4 , WO 3 , TiO 2 , ZnO, CuO, Cu 2 O, CoO, Co 3 O 4 , FeO, One kind selected from Fe 2 O 3 , Fe 3 O 4 , NiO, NiO 2 , Re 2 O 7 , Rh 2 O 3, etc., or a mixture of any two or more kinds can be adopted.

Specifically, one kind selected from Ni (OH) 2 , Cu (OH) 2 , or a mixture of any two or more kinds can be employed as the metal hydroxide.

Specific examples of metal sulfides include V 2 S 3 , V 2 S 5 , MoS 2 , MoS 3 , MnS, ZnS, CuS, Cu 2 S, FeS, NiS 2 , PdS, Re 2 S 7 , RuS 2, etc. 1 type chosen from these, or any 2 or more types of mixture can be employ | adopted.

  Specifically, as the metal fine particles, one kind selected from iron powder, zinc powder, palladium powder, vanadium powder, copper powder, cobalt powder, or a mixture of any two or more thereof can be employed.

  The catalyst of the present invention uses an ionic liquid. The reason for using the ionic liquid is that it is a quaternary ammonium salt, has no volatility, has oxidation resistance, has a high polarity and high solubility in a metal compound, and has an alkyl group Examples thereof include compatibility with volatile organic compounds and high solubility in oxygen.

  As the ionic liquid, one or a mixture of two or more selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, phosphonium-based ionic liquid, and the like can be employed at the cation site. . In the anion site, one or a mixture of two or more selected from halide ionic liquid, acetate ionic liquid, imide ionic liquid, borate ionic liquid, phosphate ionic liquid, sulfonate ionic liquid, etc. It can be adopted.

  Specific examples of ammonium-based ionic liquids include N-propyltrimethylammonium salt, N-methyl-N-propylpiperidinium salt, N-methyl-N-propylpyrrolidinium salt, N-methyl-trioctylammonium salt, etc. 1 type chosen from these, or any 2 or more types of mixture can be employ | adopted.

  Specifically, as the pyridinium-based ionic liquid, one type selected from N-butylpyridinium salt, N-hexylpyridinium salt, N-octylpyridinium salt, or a mixture of any two or more types can be adopted.

  Specific examples of the imidazolium-based ionic liquid include N-propyl-N′-methylimidazolium salt, N-allyl-N′-methylimidazolium salt, N-butyl-N′-methylimidazolium salt, N, N One type selected from '-dipropylimidazolium salt, N, N'-diallylimidazolium salt, N-octyl-N'-methylimidazolium salt, etc., or a mixture of any two or more types can be adopted. .

  Specifically, trihexyl tetradecylphosphonium salt or the like can be employed as the phosphonium-based ionic liquid.

  Specifically, one type selected from chloride, bromide, iodide, thiocyanate, or a mixture of any two or more types can be employed as the halide ionic liquid.

  Specifically, one or a mixture of any two or more selected from acetate, trifluoroacetate, and the like can be employed as the acetate ionic liquid.

  Specifically, as the imide-based ionic liquid, one type selected from bis (trifluoromethanesulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, dicyanamide, or a mixture of any two or more types can be adopted.

  Specifically, as the borate-based ionic liquid, one kind selected from tetrafluoroborate, bis [oxalato (2-)-O, O ′] borate, or a mixture of any two or more thereof can be employed. .

  Specifically, one type selected from hexafluorophosphate, dimethyl phosphate, diethyl phosphate, tris (pentafluoroethyl) trifluorophosphate, or a mixture of any two or more types can be adopted as the phosphate ionic liquid. .

  Specific examples of the sulfonate ionic liquid include one selected from methanesulfonate, trifluoromethanesulfonate, methyl sulfate, butyl sulfate, hexyl sulfate, hydrogen sulfate, p-toluenesulfonate, and the like. Or a mixture of two or more.

  The catalyst of the present invention uses a support. The reason for using the carrier is to prevent the flow of the ionic liquid by forming a film on the surface of the carrier, to increase the adsorption capacity of the volatile organic compound by utilizing the surface area of the carrier, and to utilize the large surface area for oxygen. Increasing the amount of dissolved gas and dissipating heat of reaction can be mentioned.

  As the carrier, one type selected from granular silica, alumina, activated carbon, molecular sieves, ceramics, brick, wood, or a mixture of any two or more types can be adopted.

The specific surface area of the support is preferably in the range of 100 to 5000 m 2 / g. When the specific surface area is 100 m 2 / g or more, there is an advantage that the ionic liquid does not flow and is sufficiently supported. When the specific surface area is 5000 m 2 / g or less, there is an advantage that the adsorption amount of gas molecules is large.

  The particle size distribution of the carrier is preferably in the range of 0.1 to 1000 μm. When the particle size distribution is 0.1 μm or more, there is an advantage that the ionic liquid is sufficiently supported. When the particle size distribution is 1000 μm or less, there is an advantage that reaction heat can be dissipated.

  The carrier is not limited to the above example. In addition, as the carrier, one type selected from fiber, glass plate, glass fine tube (capillary), glass bead, metal plate, metal fine plate, sawdust, paper, sponge, etc., or a mixture of any two or more types is adopted. can do.

  The amount of the metal compound supported on the catalyst is preferably in the range of 0.001 to 1000 μmol / 100 mg of catalyst. When the supported amount is 0.001 μmol / 100 mg or more of the catalyst, there is an advantage that the ability to decompose the volatile organic solvent is expressed. When the supported amount is 1000 μmol / 100 mg or less of the catalyst, there is an advantage that the duration of the catalyst activity is improved.

  The reaction temperature is preferably in the range of -20 to 300 ° C. When the reaction temperature is −20 ° C. or higher, there is an advantage that volatile gas having a low boiling point can be decomposed. When the reaction temperature is 300 ° C. or lower, there is an advantage that the ionic liquid is not decomposed and the catalytic ability can be maintained.

  The catalyst of the present invention can be used not only in a gas phase reaction but also in a liquid phase such as an organic solvent, an aqueous solvent, a fluorocarbon, or a supercritical fluid.

  The oxidation method will be described. The oxidation method is a method of oxidizing a target substance using an oxidation catalyst, and the oxidation catalyst is a carrier in which an ionic liquid containing a metal compound is supported.

  The oxidizer will be described. The oxidation apparatus is an apparatus that oxidizes a target substance using an oxidation catalyst, and the oxidation catalyst has an ionic liquid containing a metal compound supported on a carrier.

  Specifically, a deodorization device, an air purification device, a sewage treatment device, a pure water production device, or the like can be employed as the oxidation device.

  The present invention is not limited to the best mode for carrying out the above-described invention, and various other configurations can be adopted without departing from the gist of the present invention.

  Next, the best mode for carrying out the invention relating to the antibacterial agent will be described.

  An example of the first antibacterial agent will be described.

  The antibacterial agent is one in which an ionic liquid containing a metal compound is supported on a carrier.

  Antibacterial agents use metal compounds. The reason for using metal compounds is that, as is the case with many inorganic antibacterial agents, the metal ions themselves have antibacterial action, so the antibacterial activity is gradually released by gradually releasing metal ions and metal oxides. This is to maintain it.

  The metal compounds include vanadium, molybdenum, copper, iron, palladium, titanium, zirconium, yttrium, lanthanum, niobium, tantalum, chromium, tungsten, manganese, rhenium, ruthenium, cobalt, rhodium, iridium, nickel, platinum, silver , One selected from zinc, tin, lead and the like, or a mixture of any two or more thereof.

  As the metal compound, one or a mixture of two or more selected from metal salts, metal complexes, metal oxides, metal hydroxides, metal sulfides, metal fine particles, and the like can be employed.

Specific examples of the metal salt include Cu (OAc) 2 , Zn (OAc) 2 , Rh (OAc) 2 , Ni (OAc) 2 , Mo 2 (OAc) 4 , Mn (OAc) 2 , Mn (OAc) 3 Acetic acid salts such as Fe (C 2 O 4 ), Fe 2 (C 2 O 4 ) 3 , Ni (C 2 O 4 ), etc., ZnCl 2 , VCl 3 , V (O) Cl 3 , WCl 6 , RhCl 3 , ReCl 5 , MoCl 5 , MnCl 2 , NiCl 2 , FeCl 2 , FeCl 3 , CuCl 2 , CuCl and other chlorides, ZnBr 2 , WBr 5 , RhBr 3 , MnBr 2 , FeBr 2 , NiBr 2 , CuBr, bromides such as CuBr 2, ZnI 2, RhI 3 , MnI 2, FeI 2, NiI 2, iodide CuI like, MnCO 3, NiCO 3, CuCO 3 like carbonates, Zn 3 (PO 4) 2 , Phosphate such as RhPO 4 and FePO 4 , Zn (NO 3 ) 2 , Rh (NO 3 ) 3 , Mn (NO 3 ) 2 , Ni (NO 3 ) 2 and other nitrates, ZnSO 4 , VOSO 4 , Rh 2 (SO 4) 3, MnSO 4 , FeSO 4, NiSO 4, CuSO 4 sulfates such as, Zn (CF 3 SO 3) 2, Cu (CF 3 SO 3) 1 kind selected from a sulfonic acid salt of 2 such as Or a mixture of two or more of them.

Specific examples of metal complexes include VO (acac) 2 , V (acac) 3 , MoO 2 (acac) 2 , Pd (acac) 2 , Fe (acac) 2, Fe (acac) 3, Cu (acac) 2 , Mn (acac) 2 , Ni (acac) 2 , Co (acac) 2 , Co (acac) 3 and other acetylacetonate complexes, RuCl 2 (PPh 3 ) 3 , RhCl (PPh 3 ) 3 and other phosphine complexes, Carbonyl complexes such as Mo (CO) 6 , Ni (CO) 4 , Fe (CO) 5 , Mn 2 (CO) 10 , W (CO) 6 , Ti (O i Pr) 4 , V (O) (O i One kind selected from metal alcoholates such as Pr) 3 or a mixture of any two or more kinds may be employed.

Specific examples of metal oxides include NaVO 3 , Na 3 VO 4 , V 2 O 3 , V 2 O 4 , V 2 O 5 , ( n Bu 4 N) 3 PMo 12 O 40 , ( n Bu 4 N) 4 PVMo 11 O 40 , MoO 2 , MoO 3 , MnO, Mn 2 O 3 , MnO 2 , Mn 3 O 4 , WO 3 , TiO 2 , ZnO, CuO, Cu 2 O, CoO, Co 3 O 4 , FeO, One kind selected from Fe 2 O 3 , Fe 3 O 4 , NiO, NiO 2 , Re 2 O 7 , Rh 2 O 3, etc., or a mixture of any two or more kinds can be adopted.

Specifically, one kind selected from Ni (OH) 2 , Cu (OH) 2 , or a mixture of any two or more kinds can be employed as the metal hydroxide.

Specific examples of metal sulfides include V 2 S 3 , V 2 S 5 , MoS 2 , MoS 3 , MnS, ZnS, CuS, Cu 2 S, FeS, NiS 2 , PdS, Re 2 S 7 , RuS 2, etc. 1 type chosen from these, or any 2 or more types of mixture can be employ | adopted.

  Specifically, as the metal fine particles, one kind selected from iron powder, zinc powder, palladium powder, vanadium powder, copper powder, cobalt powder, or a mixture of any two or more thereof can be employed.

  Antibacterial agents use ionic liquids. The reasons for using ionic liquids are: (1) the ionic liquid itself has antibacterial activity, and (2) the metal compound is added to the ionic liquid by the action of oxygen and moisture in the air. It is used as a solvent for changing to oxide fine particles, (3) It is for gelling and stabilizing metal oxide fine particles in ionic liquid, (4) Using ionic liquid as a pool In order to gradually elute the metal oxide into the water system.

  As the ionic liquid, one or a mixture of two or more selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, phosphonium-based ionic liquid, and the like can be employed at the cation site. . In the anion site, one or any one selected from a halide ionic liquid, a carboxylate ionic liquid, an imide ionic liquid, a borate ionic liquid, a phosphate ionic liquid, a sulfonate ionic liquid, a sulfate ionic liquid, or the like A mixture of two or more can be employed.

  Specific examples of ammonium-based ionic liquids include N-propyltrimethylammonium salt, N-methyl-N-propylpiperidinium salt, N-methyl-N-propylpyrrolidinium salt, N-methyl-trioctylammonium salt, etc. 1 type chosen from these, or any 2 or more types of mixture can be employ | adopted.

  Specifically, as the pyridinium-based ionic liquid, one type selected from N-butylpyridinium salt, N-hexylpyridinium salt, N-octylpyridinium salt, or a mixture of any two or more types can be adopted.

  Specific examples of the imidazolium-based ionic liquid include N-propyl-N′-methylimidazolium salt, N-allyl-N′-methylimidazolium salt, N-butyl-N′-methylimidazolium salt, N, N 1 type selected from '-dipropylimidazolium salt, N, N'-diallylimidazolium salt, N-hexyl-N'-methylimidazolium salt, N-octyl-N'-methylimidazolium salt, etc. Or a mixture of two or more.

  Specifically, trihexyl tetradecylphosphonium salt or the like can be employed as the phosphonium-based ionic liquid.

  Specifically, one type selected from chloride, bromide, iodide, thiocyanate, or a mixture of any two or more types can be employed as the halide ionic liquid.

  Specifically, as the carboxylate-based ionic liquid, one kind selected from acetate, trifluoroacetate, or a mixture of any two or more thereof can be employed.

  Specifically, as the imide-based ionic liquid, one type selected from bis (trifluoromethanesulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, dicyanamide, or a mixture of any two or more types can be adopted.

  Specifically, as the borate-based ionic liquid, one kind selected from tetrafluoroborate, bis [oxalato (2-)-O, O ′] borate, or a mixture of any two or more thereof can be employed. .

  Specifically, one type selected from hexafluorophosphate, dimethyl phosphate, diethyl phosphate, tris (pentafluoroethyl) trifluorophosphate, or a mixture of any two or more types can be adopted as the phosphate ionic liquid. .

  Specifically, as the sulfonate ionic liquid, one kind selected from methane sulfonate, trifluoromethane sulfonate, p-toluene sulfonate, or a mixture of any two or more thereof can be employed.

  Specifically, one or a mixture of two or more selected from methyl sulfate, butyl sulfate, hexyl sulfate, hydrogen sulfate and the like can be employed as the sulfate ionic liquid.

  The antibacterial agent uses a carrier. The reason for using the carrier is as follows. The first reason is that an ionic liquid is easily impregnated with surface tension on a support having a large surface area such as silica. Further, the metal compound dissolved in the ionic liquid interacts with oxygen in the air and changes to a metal oxide. In that case, the second reason is that the greater the surface area, the greater the chance of contact with oxygen in the air and the greater the effect.

  As the carrier, one type selected from granular silica, alumina, activated carbon, molecular sieves, ceramics, brick, wood, or a mixture of any two or more types can be adopted.

  The carrier is not limited to the above example. In addition, as the carrier, one type selected from fiber, glass plate, glass fine tube (capillary), glass bead, metal plate, metal fine plate, sawdust, paper, sponge, etc., or a mixture of any two or more types is adopted. can do.

The specific surface area of the support is preferably in the range of 100 to 5000 m 2 / g. When the specific surface area is 100 m 2 / g or more, there is an advantage that the contact area with air is increased and the metal compound in the ionic liquid can be efficiently converted into a metal oxide. When the specific surface area is 5000 m 2 / g or less, there is an advantage that the amount of impregnation of the ionic liquid can be reduced.

  The particle size distribution of the carrier is preferably in the range of 0.1 to 1000 μm. When the particle size distribution is 0.1 μm or more, there is an advantage that the metal oxide fine particles in the ionic liquid can be efficiently released into the aqueous system. When the particle size distribution is 1000 μm or less, there is an advantage that the amount of impregnated ionic liquid and the amount of metal supported can be reduced.

  The amount of the metal compound supported on the antibacterial agent is preferably in the range of 0.001 to 1000 μmol / 100 mg of the antibacterial agent. When the supported amount is 0.001 μmol / 100 mg or more of the antibacterial agent, there is an advantage that metal oxide fine particles having an active antibacterial action are easily generated. When the loading amount is 1000 μmol / 100 mg or less of the antibacterial agent, there is an advantage that the antibacterial activity can be maintained for a long time.

  The antibacterial agent of the present invention can be used for antibacterial coating of residential building materials by mixing with paint, or kneaded into fiber and added to antibacterial fiber, nonwoven fabric, antibacterial nonwoven fabric, air purifier filter, water purifier filter, plastic Can be used as antibacterial plastics.

  An example of the second antibacterial agent will be described.

  The antibacterial agent is one in which an ionic liquid is supported on a carrier.

  Antibacterial agents use ionic liquids. The reasons for using ionic liquids are: (1) the ionic liquid itself has antibacterial activity, (2) the ionic liquid is non-volatile and durable, and (3) the ionic liquid is another organic antibacterial agent. (4) Since the ionic liquid is a kind of salt, it has a high polarity and is not hardly soluble in water.

  The ionic liquid is preferably water-soluble. The reason why it is preferable to be water-soluble is to bring the antibacterial agent into contact with bacteria through an aqueous medium.

  As the ionic liquid, one or a mixture of two or more selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, phosphonium-based ionic liquid, and the like can be employed at the cation site. . In the anion portion, 1 selected from halide ionic liquid, imide ionic liquid, borate ionic liquid, phosphate ionic liquid, sulfonate ionic liquid, sulfate ionic liquid, carboxylate ionic liquid, dicyanamide ionic liquid, and the like. A seed | species or any 2 or more types of mixture can be employ | adopted.

  Specific examples of ammonium-based ionic liquids include N-propyltrimethylammonium salt, N-methyl-N-propylpiperidinium salt, N-methyl-N-propylpyrrolidinium salt, N-methyl-trioctylammonium salt, etc. 1 type chosen from these, or any 2 or more types of mixture can be employ | adopted.

  Specifically, as the pyridinium-based ionic liquid, one type selected from N-butylpyridinium salt, N-hexylpyridinium salt, N-octylpyridinium salt, or a mixture of any two or more types can be adopted.

  Specific examples of the imidazolium-based ionic liquid include N-propyl-N′-methylimidazolium salt, N-allyl-N′-methylimidazolium salt, N-butyl-N′-methylimidazolium salt, N, N 1 type selected from '-dipropylimidazolium salt, N, N'-diallylimidazolium salt, N-hexyl-N'-methylimidazolium salt, N-octyl-N'-methylimidazolium salt, etc. Or a mixture of two or more.

  Specifically, trihexyl tetradecylphosphonium salt or the like can be employed as the phosphonium-based ionic liquid.

  Specifically, one type selected from chloride, bromide, iodide, thiocyanate, or a mixture of any two or more types can be employed as the halide ionic liquid.

  Specifically, as the carboxylate-based ionic liquid, one kind selected from acetate, trifluoroacetate, or a mixture of any two or more thereof can be employed.

  Specifically, as the imide-based ionic liquid, one type selected from bis (trifluoromethanesulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, dicyanamide, or a mixture of any two or more types can be adopted.

  Specifically, as the borate-based ionic liquid, one kind selected from tetrafluoroborate, bis [oxalato (2-)-O, O ′] borate, or a mixture of any two or more thereof can be employed. .

  Specifically, one type selected from hexafluorophosphate, dimethyl phosphate, diethyl phosphate, tris (pentafluoroethyl) trifluorophosphate, or a mixture of any two or more types can be adopted as the phosphate ionic liquid. .

  Specifically, as the sulfonate ionic liquid, one kind selected from methane sulfonate, trifluoromethane sulfonate, p-toluene sulfonate, or a mixture of any two or more thereof can be employed.

  Specifically, one or a mixture of two or more selected from methyl sulfate, butyl sulfate, hexyl sulfate, hydrogen sulfate and the like can be employed as the sulfate ionic liquid.

  The antibacterial agent uses a carrier. The reason for using the carrier is as follows. The first reason is that an ionic liquid is easily impregnated by surface tension on a support having many pores such as silica and a large surface area. Furthermore, once a compound having an antibacterial action taken into pores is intermittently eluted in water, the antibacterial agent can have long-lasting durability.

  As the carrier, one type selected from granular silica, alumina, activated carbon, molecular sieves, ceramics, brick, wood, or a mixture of any two or more types can be adopted.

  The carrier is not limited to the above example. In addition, as the carrier, one kind selected from fiber, glass plate, glass fine tube (capillary), glass bead, metal plate, metal fine plate, sawdust, paper, sponge, etc., or a mixture of any two or more types is adopted. can do.

The specific surface area of the support is preferably in the range of 100 to 5000 m 2 / g. When the specific surface area is 100 m 2 / g or more, the ionic liquid can be supported, and there is an advantage that it does not easily peel off. When the specific surface area is 5000 m 2 / g or less, there is an advantage that the amount of impregnation of the ionic liquid can be reduced.

  The particle size distribution of the carrier is preferably in the range of 0.1 to 1000 μm. When the particle size distribution is 0.1 μm or more, there is an advantage that handling as a powder is easy, and it can be processed into a paste by mixing with a solvent and can also be used for coating. When the particle size distribution is 1000 μm or less, there is an advantage that the ionic liquid impregnation amount can be reduced.

  The antibacterial agent of the present invention can be used for antibacterial coating of residential building materials by mixing with paint, or kneaded into fiber and added to antibacterial fiber, nonwoven fabric, antibacterial nonwoven fabric, air purifier filter, water purifier filter, plastic Can be used as antibacterial plastics.

  The present invention is not limited to the best mode for carrying out the above-described invention, and various other configurations can be adopted without departing from the gist of the present invention.

  Next, the first embodiment according to the present invention will be described in detail. However, it goes without saying that the present invention is not limited to these examples.

<Effect of ionic liquid>

  The preparation of the catalyst will be described.

Example 1
Weigh 0.66 g of spherical silica (AG-100 S-Itech D-100-40A, specific surface area 884 m 2 / g, pore volume 0.91 mL / g, pore diameter 4.1 nm, particle size distribution 63-210 μm) into a flask, and add methanol. Suspended in 10 mL. Methanol solution of N-butyl-N'-methylimidazolium trifluoroacetate [(BuMeIm) CF 3 COO] (0.33 g) and acetylacetone vanadyl (VO (acac) 2 , 26.5 mg, 0.10 mmol) as ionic liquid (10 mL) was gradually added dropwise at room temperature and mixed under air for 60 minutes. Using a rotary evaporator, methanol was distilled off from this suspension under reduced pressure (25 mmHg / 50 ° C.), followed by vacuum drying for 2 hours to obtain 0.93 g of a green catalyst.

Example 2
The preparation was carried out in the same manner as in Example 1 except that N-butyl-N′-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) was used as the ionic liquid, and 0.95 g of a green catalyst was obtained. .

Example 3
The preparation was carried out in the same manner as in Example 1 except that N-butyl-N′-methylimidazolium hexafluorophosphate [(BuMeIm) PF 6 ] (0.33 g) was used as the ionic liquid to obtain 0.94 g of a green catalyst.

Example 4
The same procedure as in Example 1 was conducted except that N-octyl-N′-methylimidazolium trifluoroacetate [(OctMeIm) CF 3 COO] (0.33 g) was used as the ionic liquid, and 0.91 g of a pale green catalyst was added. Obtained.

Example 5
The preparation was carried out in the same manner as in Example 1 except that N-butylpyridinium trifluoroacetate [(BuPy) CF 3 COO] (0.33 g) was used as the ionic liquid to obtain 1.02 g of a green catalyst.

Example 6
The preparation was carried out in the same manner as in Example 1 except that N-hexylpyridinium trifluoroacetate [(HexPy) CF 3 COO] (0.33 g) was used as the ionic liquid to obtain 0.98 g of a green catalyst.

Example 7
The preparation was carried out in the same manner as in Example 1 except that N-octylpyridinium trifluoroacetate [(OctPy) CF 3 COO] (0.33 g) was used as the ionic liquid to obtain 0.95 g of a green catalyst.

Example 8
The preparation was performed in the same manner as in Example 1 except that N-butylpyridinium tetrafluoroborate [(BuPy) BF 4 ] (0.33 g) was used as the ionic liquid to obtain 1.02 g of a green catalyst.

Example 9
The green catalyst was prepared in the same manner as in Example 1 except that trihexyl tetradecylphosphonium tetrafluoroborate [C 14 H 29 (C 6 H 13 ) 3 P] BF 4 ] (0.33 g) was used as the ionic liquid. 0.90 g was obtained.

Example 10
The same procedure as in Example 1 was carried out except that trihexyl tetradecylphosphonium chloride [C 14 H 29 (C 6 H 13 ) 3 P] Cl] (0.33 g) was used as the ionic liquid to obtain 0.77 g of a green catalyst. It was.

Comparative Example 1
Prepared in the same manner as in Example 1 except that N-butyl-N'-methylimidazolium trifluoroacetate (BuMeIm) CF 3 COO] (0.33 g) was used as the ionic liquid, and VO (acac) 2 was not added. And 0.99 g of a white catalyst was obtained.

The evaluation method will be described.
XPS measurement was performed using ULVAC-PHI 1700R ESCA using AlKα X-ray (1486.6 eV) as a radiation source.

  The transmission electron microscope observation was measured using a field emission transmission electron microscope (JEM-2010F, manufactured by JEOL Ltd.). Elemental analysis at the measurement point was performed using an energy dispersive X-ray fluorescence apparatus (NORAN Instruments) attached to this apparatus.

Evaluation of catalyst activity was performed as follows.
The catalytic activity was evaluated using a pulse injection method using a flame ionization detector (FID) type gas chromatography as shown in FIG. A catalyst column packed with 100 mg of catalyst in a 4 mmφ × 25 mm stainless steel pipe is attached to the sample inlet side, followed by a filter column (Porapak QS, 2 for removing partial oxidation products such as alcohol, ketone and carboxylic acid) mmφ × 100 mm) was attached between the catalyst column and the FID detector, and styrene as VOC was introduced into the 1.00 μL catalyst column with a microsyringe at a predetermined temperature while flowing air (flow rate 25 mL / min) as a carrier gas.

Unreacted VOC was detected with an FID detector, and the conversion rate X (removal rate) was calculated. The conversion rate is obtained by the following equation.
X = 100 × (S I −S A ) / S I
Incidentally, each of the S A and S I Here,
S A : VOC peak area detected through the catalyst column and filter column S I : VOC peak area detected through the filter column without the catalyst column (blank measurement)
Indicates. The measurement was performed 3 times and the average value was calculated.

The evaluation result will be described.
The XPS measurement will be described. FIG. 2 shows a V 2p spectrum in XPS measurement at the time of preparation of VO (acac) 2 / [BuMeIm] BF 4 / SiO 2 catalyst (Example 2). A peak derived from V 2 O 5 characteristic of 517.5 eV was observed. In general, tetravalent VO 2+ such as VO (acac) 2 is observed at 513 eV, but was not detected in this measurement. From this, it is considered that the V species in the catalyst prepared in this experiment was already oxidized by air at the time of catalyst preparation and changed to V 2 O 5 .

It is considered that tetravalent VO (acac) 2 used as a catalyst raw material was oxidized by oxygen in the air and changed to V 2 O 5 according to the following reaction formula (1) (Chemical formula 1). In general, VO (acac) 2 dissolves in an organic solvent and is not easily oxidized by air even when exposed to air. It is considered that such an oxidation reaction has progressed by supplying sufficient oxygen in the ionic liquid film having a large surface area.

The electron microscope observation will be described. FIG. 3A shows the result of transmission electron microscope observation of the VO (acac) 2 / [BuMeIm] BF 4 / SiO 2 catalyst (Example 2). In the figure, the black part on the right side is silica, and a film-like ionic liquid is observed on the surface. You can observe spots like mottled spots. From the X-ray fluorescence analysis of the light-colored part (point a) and black part (point b) (Figs. 3 (B) and (C)), there is no catalytic metal at point a and V from point b. The X-ray pattern attributed to 2 O 5 was confirmed. The black spots were found to be aggregates of V compounds. When considered together with the XPS result, the speckle (point b) is presumed to be V 2 O 5 in an amorphous state.

The evaluation results of catalyst activity will be described with reference to Table 1. The example which does not contain a metal in Comparative Example 1 is shown. Since no metal is contained, styrene does not react at all and the conversion is 0%. When the catalytic activity was evaluated using a catalyst to which VO (acac) 2 was added as a metal, it was found that any ionic liquid was subjected to oxidative decomposition and removed. Among them, the trifluoroacetate represented by [BuPy] CF 3 COO of Example 5 has high activity (Examples 1 and 4 to 7), but the decomposition point of the ionic liquid itself is as low as 150 ° C. [BuMeIm] BF 4 in Example 2 is slightly inferior in activity, but its own decomposition point is reported to be 300 ° C. or higher, and is considered to be highly versatile. Moreover, the ionic liquid which shows high solubility with respect to styrene also showed similar catalytic activity (Examples 9 and 10). In the above reaction, although the reaction mechanism is unknown, it is considered that styrene reacts with air to form benzaldehyde and carbon dioxide, and then oxidatively decomposes to benzoic acid and finally to carbon dioxide.

<Effect of metal compound>

  The preparation of the catalyst will be described.

Example 11
Example 1 except that N-butyl-N′-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and V (acac) 3 (28.6 mg, 0.10 mmol) as the catalyst were used And 0.95 g of a yellow catalyst was obtained.

Example 12
Similar to Example 1 except that N-butyl-N′-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and NaVO 3 (13.2 mg, 0.10 mmol) as the catalyst are used. Preparation was carried out to obtain 0.77 g of a white catalyst.

Example 13
Example 1 except that N-butyl-N′-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and Na 3 VO 4 (19.4 mg, 0.10 mmol) as the catalyst are used. The same preparation was carried out to obtain 0.89 g of a white catalyst.

Example 14
Similar to Example 1 except that N-butyl-N′-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and VOSO 4 (17.6 mg, 0.10 mmol) as the catalyst are used. Preparation was carried out to obtain 1.01 g of a white catalyst.

Comparative Example 2
Example 1 except that N-butyl-N′-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and V 2 O 5 (18.2 mg, 0.10 mmol) as the catalyst are used. Preparation was carried out in the same manner to obtain 0.99 g of a yellow catalyst.

Example 15
Example 1 except that N-butyl-N′-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and Cu (OAc) 2 (19.2 mg, 0.10 mmol) as the catalyst are used And 0.95 g of a blue catalyst was obtained.

Example 16
Example 1 except that N-butyl-N′-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and Fe (acac) 3 (33.8 mg, 0.10 mmol) as the catalyst were used And 0.91 g of a deep red catalyst was obtained.

Example 17
Example 1 except that N-butyl-N′-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and Pd (acac) 2 (31.0 mg, 0.10 mmol) as the catalyst were used And 0.97 g of a deep red catalyst was obtained.

Example 18
Example using N-butyl-N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as ionic liquid and MoO 2 (acac) 2 (33.8 mg, 0.10 mmol) as catalyst 1 was prepared in the same manner as in 1 to obtain 0.71 g of an orange catalyst.

Example 19
N- butyl as ionic liquids - N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4] ( 0.33 g) and as a catalyst (n Bu 4 N) 4 PVMo 11 O 40 (20.2 mg, 6.7 × 10 - 4 mmol) was used in the same manner as in Example 1 to obtain 0.64 g of a yellow catalyst.

Example 20
N- butyl as ionic liquids - N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4] ( 0.33 g) and as a catalyst (n Bu 4 N) 3 PMo 12 O 40 (15.1 mg, 6.7 × 10 - 4 mmol) was used in the same manner as in Example 1 to obtain 0.78 g of a yellow catalyst.

  The evaluation method will be described. The evaluation of the catalytic activity was performed using styrene as VOC by the same method as that performed in “Effect of ionic liquid”.

The evaluation result will be described. Table 2 shows the ability to remove styrene by using [BuMeIm] BF 4 as an ionic liquid and a catalyst supported on silica together with various metal compounds. High activity was observed in VO (acac) 2 and MoO 2 (acac) 2 shown in Example 2 and Example 18. In particular, in the case of VO (acac) 2 , it has been confirmed that both exist as V 2 O 5 by XPS measurement of the catalyst before and after the evaluation. The particle size is unknown, and it is clear from the TEM measurement that the aggregate is in an amorphous state. On the other hand, the catalytic activity of some other V compounds was evaluated, but it had a certain catalytic activity except for V 2 O 5 which did not show any catalytic activity. The reason why V 2 O 5 does not show catalytic activity is that it has no solubility in ionic liquid, and it was supported in the form of a slurry without dissolving completely in methanol during catalyst preparation. This is considered to be caused by the fact that it is not finely dispersed. Since the state analysis about other metals (Examples 15-18) was not performed, it is unknown whether it is an oxide. In the heteropolyacid catalysts shown in Examples 19 and 20, the catalytic activity was low regardless of the presence or absence of V.

<Effect of loading amount>

  The preparation of the catalyst will be described.

Example 21
Other than using N-butyl-N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and acetylacetone vanadyl (VO (acac) 2 , 54.2 mg, 0.20 mmol) Preparation was carried out in the same manner as in Example 1 to obtain 0.98 g of a green catalyst.

Example 22
Other than using N-butyl-N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and acetylacetone vanadyl (VO (acac) 2 , 103 mg, 0.40 mmol) Preparation was carried out in the same manner as in Example 1 to obtain 0.98 g of a green catalyst.

Example 23
Other than using N-butyl-N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and acetylacetone vanadyl (VO (acac) 2 275 mg, 1.00 mmol) Preparation was carried out in the same manner as in Example 1 to obtain 0.98 g of a green catalyst.

  The evaluation method will be described. The evaluation of the catalytic activity was performed using styrene as VOC by the same method as that performed in “Effect of ionic liquid”. )

The evaluation result will be described. Using [BuMeIm] BF 4 as the ionic liquid, the ability to remove styrene was examined using a catalyst in which the supported amount of VO (acac) 2 was changed. As is apparent from Table 3 and FIG. 4, as the amount of V catalyst supported increases, the conversion of styrene increases. As shown in Example 22, when VO (acac) 2 was supported at 0.04 mmol, The styrene conversion reached 36%.

<Effect of temperature>

  The preparation of the catalyst will be described.

Examples 24-28
The catalyst prepared in Example 2 was used.

The evaluation method will be described.
The evaluation of the catalytic activity was performed using styrene as VOC by the same method as that performed in “Effect of ionic liquid”.

  Thermal analysis was performed as follows. Thermogravimetric / differential thermal analysis was carried out using a DTG-60 manufactured by Shimadzu Corporation under an air stream of 100 mL / min from room temperature to 400 ° C at a rate of 2 ° C / min.

The evaluation result will be described.
The evaluation results of catalyst activity will be described. Table 4 and FIG. 5 show the effect of reaction temperature on the catalytic oxidation removal of styrene. Using the VO (acac) 2 / [BuMeIm] BF 4 / SiO 2 catalyst prepared in Example 2, the reaction of styrene at each temperature revealed that the reaction temperature was 200 ° C. and the styrene conversion was 30%. After that, it gradually began to decrease. From the result of thermal analysis shown below, it is known that the ionic liquid itself decomposes at 260 as a boundary.

The thermal analysis result will be described. Using the VO (acac) 2 / [BuMeIm] BF 4 / SiO 2 catalyst prepared in Example 2, the thermal stability of the catalyst in an air stream was examined. The weight ratio of ionic liquid: SiO 2 in the catalyst is approximately 1: 2, and if the ionic liquid starts to decompose and volatilize as heating proceeds, the weight loss should decrease to 66% weight ratio of SiO 2. is there. As is clear from FIG. 6, the catalyst weight started to decrease at 260 ° C., and a complete decrease in the weight of the ionic liquid was observed near 400 ° C. Originally, the decomposition point of the ionic liquid [BuMeIm] BF 4 in this catalyst is 300 ° C., and it is considered that the oxidation catalyst V 2 O 5 promoted the decomposition of the ionic liquid. Therefore, it is considered that the present catalyst is preferably operated at a relatively low temperature (from room temperature to hundreds of degrees Celsius) rather than being operated in a high temperature region. The decomposition point of this catalyst is considered to vary depending on the type of metal used, the amount supported, and the type of ionic liquid.

<Effects of volatile organic compounds>

  The preparation of the catalyst will be described. The catalyst prepared in Example 2 and the catalyst described in the following examples were used.

Examples 29-34
The catalyst prepared in Example 2 was used.

Examples 35 and 36
Other than using N-butyl-N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as ionic liquid and acetylacetone copper (Cu (acac) 2 , 26.1 mg, 0.10 mmol) Preparation was carried out in the same manner as in Example 1 to obtain 0.89 g of a blue catalyst.

Examples 37, 38
Other than using N-butyl-N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and acetylacetone manganese (Mn (acac) 2 , 25.3 mg, 0.10 mmol) Preparation was carried out in the same manner as in Example 1 to obtain 0.96 g of an orange catalyst.

Examples 39, 40
Other than using N-butyl-N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and acetylacetone cobalt (Co (acac) 3 , 35.6 mg, 0.10 mmol) Preparation was carried out in the same manner as in Example 1 to obtain 0.80 g of a dark green catalyst.

Examples 41 and 42
The catalyst prepared in Example 18 was used.

Example 43
Other than using N-butyl-N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and nickel acetylacetone (Ni (acac) 2 , 29.3 mg, 0.10 mmol) Preparation was carried out in the same manner as in Example 1 to obtain 0.73 g of a light blue catalyst.

Comparative Example 3
The catalyst prepared in Comparative Example 2 was used.
Example 44
The catalyst prepared in Example 22 was used.
Example 45
The catalyst prepared in Example 23 was used.

  The evaluation method will be described. Evaluation of the catalytic activity was carried out using various VOCs described in Table 5 in the same manner as in the section “Effect of ionic liquid”.

The evaluation result will be described. Table 5 shows the results of catalytic oxidation removal using various catalysts for various VOC reactions. The reactivity of various VOCs when VO (acac) 2 / [BuMeIm] BF 4 / SiO 2 catalyst is used as the catalyst is in the order of styrene>ethylbenzene>p-xylene>trichloroethane>trichloroethylene>toluene> benzene (Examples) 2, 29-33, 44).

Among VOCs that have been examined for reactivity, halogen-based organic solvents are considered to be difficult to decompose due to their low reactivity. Even in this experiment, the reactivity of trichlorethylene is low (Example 33). Therefore, as a result of searching for a catalyst having higher activity for trichlorethylene, the catalytic activity of Mn (acac) 2 was high, and a conversion rate of 5% was shown at 100 ° C. (Example 37).

  From the above, according to this example, it was confirmed that various organic compounds were easily oxidized by air in the catalyst system using ionic liquid as a reaction medium.

  Next, a second embodiment according to the present invention will be specifically described. However, it goes without saying that the present invention is not limited to these examples.

<Effect of ionic liquid>

  The preparation of the antibacterial agent will be described.

Comparative Example 4
Ampicillin, sodium salt (Ampicilline, Sodium Salt, manufactured by Nacalai Tesque) 50 μg (0.134 μmol) was used as it was.

Comparative Example 5
Prepared in the same manner as in Example 1 except that spherical silica (0.66 g) and VO (acac) 2 (26.7 mg, 0.10 mmol) were used as a catalyst and [[BuMeIm) CF 3 COO] was not added. 0.63 g of a sample was obtained.

Comparative Example 6
Prepared in the same manner as in Example 1 except that spherical silica (0.66 g) and Mn (acac) 2 (25.4 mg, 0.10 mmol) were used as a catalyst and [[BuMeIm) CF 3 COO] was not added. A sample of 0.65 g was obtained.

Comparative Example 7
Spherical silica itself was used.

Example 46
Prepared in the same manner as in Example 1 except that N-butyl-N′-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) was used as the ionic liquid, and VO (acac) 2 was not added. And 0.87 g of a white sample was obtained.

Example 47
The same procedure as in Example 1 was carried out except that N-butyl-N′-methylimidazolium trifluoromethanesulfonate [(BuMeIm) CF 3 SO 3 ] (0.34 g) was used as the ionic liquid, and 0.97 g of a gray sample was obtained. Obtained.

Comparative Example 8
The same as Example 1 except that N-butyl-N'-methylimidazolium trifluoromethanesulfonate [(BuMeIm) CF 3 SO 3 ] (0.33 g) was used as the ionic liquid, and VO (acac) 2 was not added. And 0.89 g of a white sample was obtained.

Example 48
Example 1 except that N-butyl-N′-methylimidazolium hexafluorophosphate [(BuMeIm) PF 6 ] (0.33 g) is used as the ionic liquid and Mn (acac) 2 (24.7 mg, 0.10 mmol) is used as the catalyst. The same preparation was performed to obtain 0.98 g of an orange sample.

Comparative Example 9
Prepared in the same manner as in Example 1 except that N-butyl-N′-methylimidazolium hexafluorophosphate [(BuMeIm) PF 6 ] (0.33 g) was used as the ionic liquid and VO (acac) 2 was not added. And 0.98 g of a white sample was obtained.

Example 49
N-butyl-N'-methylimidazolium bis (trifluoromethanesulfonyl) imide [(BuMeIm) (CF 3 SO 2 ) 2 N] (0.33 g) as ionic liquid and VO (acac) 2 (31.0 mg, 0.10 In the same manner as in Example 1 except that mmol) was used, 0.97 g of a green sample was obtained.

Example 50
N-butyl-N'-methylimidazolium bis (trifluoromethanesulfonyl) imide [(BuMeIm) (CF 3 SO 2 ) 2 N] (0.33 g) as ionic liquid and Mn (acac) 2 (25.4 mg, 0.10 as catalyst) In the same manner as in Example 1 except that mmol) was used, 0.98 g of an orange sample was obtained.

Comparative Example 10
Use N-butyl-N'-methylimidazolium bis (trifluoromethanesulfonyl) imide [(BuMeIm) (CF 3 SO 2 ) 2 N] (0.33 g) as ionic liquid, without adding VO (acac) 2 The others were prepared in the same manner as in Example 1 to obtain 0.91 g of a white sample.

Example 51
Example using N-hexyl-N'-methylimidazolium trifluoroacetate [(HexMeIm) CF 3 COO] (0.33 g) as ionic liquid and VO (acac) 2 (26.5 mg, 0.10 mmol) as catalyst The same preparation as in 1 was performed to obtain 0.97 g of a green sample.

Example 52
As in Example 1, except that N-hexyl-N'-methylimidazolium trifluoroacetate [(HexMeIm) CF 3 COO] (0.33 g) was used as the ionic liquid, and VO (acac) 2 was not added. A white sample of 0.90 g was obtained.

Example 53
As in Example 1, except that N-octyl-N′-methylimidazolium trifluoroacetate [(OctMeIm) CF 3 COO] (0.33 g) was used as the ionic liquid and VO (acac) 2 was not added. A white sample of 0.91 g was obtained.

Comparative Example 11
A white sample was prepared in the same manner as in Example 1, except that N-butylpyridinium tetrafluoroborate [(BuPy) BF 4 ] (0.33 g) was used as the ionic liquid and VO (acac) 2 was not added. 0.89 g was obtained.

Example 54
The preparation was carried out in the same manner as in Example 1 except that N-hexylpyridinium trifluoroacetate [(HexPy) CF 3 COO] (0.33 g) was used as the ionic liquid, and VO (acac) 2 was not added. A sample of 0.96 g was obtained.

Example 55
The preparation was carried out in the same manner as in Example 1 except that N-octylpyridinium trifluoroacetate [(OctPy) CF 3 COO] (0.33 g) was used as the ionic liquid, and VO (acac) 2 was not added. A sample of 0.90 g was obtained.

  In addition, samples were obtained according to Examples 2, 3, 4, 6, 7, 8, and 37.

The evaluation method will be described.
A method for measuring the antibacterial activity (Positive Control) will be described. Purified agar powder (manufactured by Nacalai Tesque) 15 g and LB medium (Lennox) (manufactured by Nacalai Tesque) 20 g were added to purified water 1000 mL, and heat sterilized (autoclave) at 130 ° C. for 1 hour. This warm solution was added to a petri dish having a diameter of 10 cm to a depth of about 5 mm, covered with a lid and allowed to stand for 1 day. To this agar medium, 100 μL of an Escherichia coli DH5α (manufactured by Wako Pure Chemical Industries, Ltd.) solution was added, and the bacteria were spread on the entire surface of the medium with a conage rod. In the center of this medium, 10 mg of the sample powder was placed so that the diameter was within 8 mm, and cultured at 37 ° C. for 18 hours. After culturing, the growth of fungal moss is inhibited around the sample, and a blocking circle is formed. This diameter (mm) was measured and the antibacterial activity was evaluated.

The evaluation result will be described.
The effects of various ionic liquids were investigated using VO (acac) 2 and Mn (acac) 2 . The results are shown in Table 6 and FIG. First, none of the silica impregnated with only a metal compound without using an ionic liquid showed antibacterial activity. Many ionic liquids exhibit antibacterial activity, but the water-soluble ionic liquids of Examples 46, 52, 53, 54, and 55 themselves exhibited antibacterial activity even when no metal compound was present. Furthermore, it turned out that the antimicrobial activity increases by adding a metal compound (Example 2, 37, 47, 3, 48, 49, 50, 51, 4, 8, 6, 7). In particular, in the case of an ionic liquid having no water solubility (Comparative Examples 9 and 10), although there is no antibacterial activity of its own, antibacterial activity is expressed by adding a metal compound (Example 3, 48, 49, 50). Even when the ionic liquid is water-soluble, it does not show antibacterial activity (Comparative Examples 8 and 11), and it can be seen that the antibacterial activity is increased by adding a metal compound.

  From the above, the mechanism of antibacterial action can be considered as follows. First, for ionic liquids that exhibit antibacterial activity, when the ionic liquid adsorbed on the silica gel surface touches the agar medium, only the water-soluble ionic liquid is eluted into the agar medium and exhibits antibacterial activity. It is believed that there is.

  In the case of an ionic liquid containing a metal compound, regardless of whether the ionic liquid is water-soluble or not, the metal compound dissolved in the ionic liquid gradually becomes fine oxide particles on the silica gel surface by the action of air and humidity. This is considered to exhibit antibacterial activity by inhibiting the growth of moss by moving to an agar medium.

<Effect of metal compound>

The preparation of the antibacterial agent will be described.
Samples were obtained according to Examples 2, 12, 14, 16, 17, 18, 37, 39, 43, and 46.

The evaluation method will be described.
Antibacterial activity (Positive Control) was measured by the method described above.

The evaluation result will be described.
Using [BuMeIm] BF 4 as the ionic liquid, the effects of various metal compounds were investigated. The results are shown in Table 7 and FIG. Although the ionic liquid itself has antibacterial activity (Example 46), the addition of all metal compounds shown in the table increased its inhibition circle diameter.

  As described in the effect of the ionic liquid, the mechanism showing the antibacterial action is considered to be that the water-soluble ionic liquid and the metal compound are dissolved in the agar medium, thereby inhibiting the growth of fungi and exhibiting the antibacterial activity. In addition, although the mechanism is unknown about the difference by the kind of metal, the strength of the antibacterial activity was the order of Ni = Co> Mn> V = Mo = Fe> Pd.

<Effect of loading amount>

  The preparation of the antibacterial agent will be described.

Example 56
Other than using N-butyl-N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and acetylacetone vanadyl (VO (acac) 2 , 82.4 mg, 0.30 mmol) Preparation was carried out in the same manner as in Example 1 to obtain 0.99 g of a green sample.

Example 57
Other than using N-butyl-N'-methylimidazolium tetrafluoroborate [(BuMeIm) BF 4 ] (0.33 g) as the ionic liquid and acetylacetone vanadyl (VO (acac) 2 , 160.4 mg, 0.60 mmol) Preparation was carried out in the same manner as in Example 1 to obtain 0.99 g of a green sample.

  In addition, samples were obtained according to Examples 2, 21, 22, 23, and 46.

The evaluation method will be described.
Antibacterial activity (Positive Control) was measured by the method described above.

The evaluation result will be described.
Using [BuMeIm] BF 4 as the ionic liquid, the effect of the loading amount of VO (acac) 2 was examined. The results are shown in Table 8 and FIG. Although the ionic liquid itself has antibacterial activity (Example 46), the antibacterial activity was increased by increasing the amount of VO (acac) 2 supported. This can be understood as an increase in the amount of the metal compound that moves to the agar medium.

  From the above, according to this example, a novel antibacterial agent having high antibacterial activity could be obtained.

It is a figure which shows the outline | summary of the catalytic oxidation catalyst evaluation apparatus of VOCs by the pulse injection method. FIG. 3 is a diagram showing a V 2p spectrum in XPS measurement at the time of preparing a VO (acac) 2 / [BuMeIm] BF 4 / SiO 2 catalyst. (A) Transmission electron microscope image of a catalyst in which V 2 O 5 is dispersed in an ionic liquid, (B) Elemental analysis results at point a in the transmission electron microscope image (without V), (C) Transmission electron It is a figure which shows the elemental-analysis result (with V) in b point of a microscope observation image, respectively. FIG. 3 is a graph showing the effect of the amount of VO (acac) 2 catalyst supported on the catalytic oxidation removal of styrene. It is a figure which shows the effect of the reaction temperature on the catalytic oxidation removal of styrene. VO (acac) 2 / [BuMeIm ] thermal analysis results for BF 4 / SiO 2 catalyst is a diagram showing a. In V / Mn-Ionic Liquid / SiO 2 of antimicrobial activity against E. coli (E. coli), shows the effect of various ionic liquids. In Metal- [BuMeIm] BF 4 / SiO 2 of antimicrobial activity against E. coli (E. coli), a diagram showing various metal type effect. E. VO for (E. coli) (acac) 2 - In [BuMeIm] BF 4 / SiO 2 of antimicrobial activity, shows the effect of metal loading amount.

Claims (46)

  1. In oxidation catalysts that oxidize target substances,
    An oxidation catalyst characterized in that an ionic liquid containing a metal compound is supported on a carrier.
  2. The oxidation catalyst according to claim 1, wherein the target substance is a volatile organic compound.
  3. 2. The oxidation catalyst according to claim 1, wherein the target substance is one selected from styrene, benzene, ethylbenzene, p-xylene, trichloroethane, toluene, and trichloroethylene, or a mixture of any two or more thereof.
  4. The ionic liquid is composed of one kind selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, and phosphonium-based ionic liquid, or a mixture of any two or more thereof. Oxidation catalyst.
  5. The ionic liquids are N-butyl-N'-methylimidazolium trifluoroacetate, N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N'-methylimidazolium hexafluorophosphate, N- Octyl-N'-methylimidazolium trifluoroacetate, N-butylpyridinium trifluoroacetate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, N-butylpyridinium tetrafluoroborate, tri 2. The oxidation catalyst according to claim 1, comprising one kind selected from hexyltetradecylphosphonium tetrafluoroborate and trihexyltetradecylphosphonium chloride, or a mixture of any two or more thereof.
  6. The metal compound is composed of one kind selected from metal salts, metal complexes, metal oxides, metal hydroxides, metal sulfides, and metal fine particles, or a mixture of any two or more thereof. Oxidation catalyst.
  7. Metal compounds include VO (acac) 2 , V (acac) 3 , NaVO 3 , Na 3 VO 4 , VOSO 4 , Cu (OAc) 2 , Fe (acac) 3 , Pd (acac) 2 , MoO 2 (acac) 2 , ( n Bu 4 N) 4 PVMo 11 O 40 , ( n Bu 4 N) 3 PMo 12 O 40 , or one or a mixture of two or more thereof. Oxidation catalyst.
  8. The carrier is one selected from granular silica, alumina, activated carbon, molecular sieves, fibers, glass plates, glass fine beads, glass beads, metal plates, metal fine beads, sawdust, paper, sponge, or any two or more of them. The oxidation catalyst according to claim 1, comprising a mixture.
  9. The oxidation catalyst according to claim 1, wherein the carrier is made of granular silica.
  10. The target substance consists of one or a mixture of two or more selected from styrene, benzene, ethylbenzene, p-xylene, trichloroethane, toluene, trichloroethylene,
    The ionic liquids are N-butyl-N'-methylimidazolium trifluoroacetate, N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N'-methylimidazolium hexafluorophosphate, N- Octyl-N'-methylimidazolium trifluoroacetate, N-butylpyridinium trifluoroacetate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, N-butylpyridinium tetrafluoroborate, tri One kind selected from hexyltetradecylphosphonium tetrafluoroborate and trihexyltetradecylphosphonium chloride, or a mixture of any two or more thereof,
    Metal compounds include VO (acac) 2 , V (acac) 3 , NaVO 3 , Na 3 VO 4 , VOSO 4 , Cu (OAc) 2 , Fe (acac) 3 , Pd (acac) 2 , MoO 2 (acac) 2 , ( n Bu 4 N) 4 PVMo 11 O 40 , ( n Bu 4 N) 3 PMo 12 O 40 selected from one or a mixture of two or more,
    The oxidation catalyst according to claim 1, wherein the carrier is made of granular silica.
  11. In an oxidation method of oxidizing a target substance using an oxidation catalyst,
    The oxidation method is characterized in that an ionic liquid containing a metal compound is supported on a carrier.
  12. The oxidation method according to claim 11, wherein the target substance is a volatile organic compound.
  13. 12. The oxidation method according to claim 11, wherein the target substance is one selected from styrene, benzene, ethylbenzene, p-xylene, trichloroethane, toluene, trichloroethylene, or a mixture of any two or more thereof.
  14. The ionic liquid is composed of one kind selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, and phosphonium-based ionic liquid, or a mixture of any two or more thereof. Oxidation method.
  15. The ionic liquids are N-butyl-N'-methylimidazolium trifluoroacetate, N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N'-methylimidazolium hexafluorophosphate, N- Octyl-N'-methylimidazolium trifluoroacetate, N-butylpyridinium trifluoroacetate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, N-butylpyridinium tetrafluoroborate, tri 12. The oxidation method according to claim 11, comprising one kind selected from hexyltetradecylphosphonium tetrafluoroborate and trihexyltetradecylphosphonium chloride, or a mixture of any two or more thereof.
  16. The metal compound is composed of one kind selected from metal salts, metal complexes, metal oxides, metal hydroxides, metal sulfides, and metal fine particles, or a mixture of any two or more thereof. Oxidation method.
  17. Metal compounds include VO (acac) 2 , V (acac) 3 , NaVO 3 , Na 3 VO 4 , VOSO 4 , Cu (OAc) 2 , Fe (acac) 3 , Pd (acac) 2 , MoO 2 (acac) 2, (n Bu 4 n) 4 PVMo 11 O 40, claim 11, wherein the consist (n Bu 4 n) 3 PMo 12 O 1 kind selected from 40, or any two or more thereof Oxidation method.
  18. The carrier is one selected from granular silica, alumina, activated carbon, molecular sieves, fibers, glass plates, glass fine beads, glass beads, metal plates, metal fine beads, sawdust, paper, sponge, or any two or more of them. It consists of a mixture. The oxidation method of Claim 11 characterized by the above-mentioned.
  19. The oxidation method according to claim 11, wherein the support is made of granular silica.
  20. The target substance consists of one or a mixture of two or more selected from styrene, benzene, ethylbenzene, p-xylene, trichloroethane, toluene, trichloroethylene,
    The ionic liquids are N-butyl-N'-methylimidazolium trifluoroacetate, N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N'-methylimidazolium hexafluorophosphate, N- Octyl-N'-methylimidazolium trifluoroacetate, N-butylpyridinium trifluoroacetate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, N-butylpyridinium tetrafluoroborate, tri One kind selected from hexyltetradecylphosphonium tetrafluoroborate and trihexyltetradecylphosphonium chloride, or a mixture of any two or more thereof,
    Metal compounds include VO (acac) 2 , V (acac) 3 , NaVO 3 , Na 3 VO 4 , VOSO 4 , Cu (OAc) 2 , Fe (acac) 3 , Pd (acac) 2 , MoO 2 (acac) 2 , ( n Bu 4 N) 4 PVMo 11 O 40 , ( n Bu 4 N) 3 PMo 12 O 40 selected from one or a mixture of two or more,
    The oxidation method according to claim 11, wherein the support is made of granular silica.
  21. In an oxidizer that oxidizes a target substance using an oxidation catalyst,
    The oxidation catalyst is characterized in that an ionic liquid containing a metal compound is supported on a carrier.
  22. The oxidizer according to claim 21, wherein the target substance is a volatile organic compound.
  23. The oxidizer according to claim 21, wherein the target substance is one selected from styrene, benzene, ethylbenzene, p-xylene, trichloroethane, toluene, and trichloroethylene, or a mixture of any two or more thereof.
  24. The ionic liquid comprises one or a mixture of two or more selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, and phosphonium-based ionic liquid. Oxidation equipment.
  25. The ionic liquids are N-butyl-N'-methylimidazolium trifluoroacetate, N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N'-methylimidazolium hexafluorophosphate, N- Octyl-N'-methylimidazolium trifluoroacetate, N-butylpyridinium trifluoroacetate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, N-butylpyridinium tetrafluoroborate, tri The oxidizer according to claim 21, wherein the oxidizer is composed of one kind selected from hexyltetradecylphosphonium tetrafluoroborate and trihexyltetradecylphosphonium chloride, or a mixture of any two or more thereof.
  26. The metal compound is composed of one kind selected from metal salts, metal complexes, metal oxides, metal hydroxides, metal sulfides, and metal fine particles, or a mixture of any two or more thereof. Oxidation equipment.
  27. Metal compounds include VO (acac) 2 , V (acac) 3 , NaVO 3 , Na 3 VO 4 , VOSO 4 , Cu (OAc) 2 , Fe (acac) 3 , Pd (acac) 2 , MoO 2 (acac) 23. One type selected from 2 , ( n Bu 4 N) 4 PVMo 11 O 40 , ( n Bu 4 N) 3 PMo 12 O 40 , or a mixture of two or more types thereof. Oxidation equipment.
  28. The carrier is one selected from granular silica, alumina, activated carbon, molecular sieves, fibers, glass plates, glass fine beads, glass beads, metal plates, metal fine beads, sawdust, paper, sponge, or any two or more of them. The oxidizer according to claim 21, comprising a mixture.
  29. The oxidizer according to claim 21, wherein the carrier is made of granular silica.
  30. The target substance consists of one or a mixture of two or more selected from styrene, benzene, ethylbenzene, p-xylene, trichloroethane, toluene, trichloroethylene,
    The ionic liquids are N-butyl-N'-methylimidazolium trifluoroacetate, N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N'-methylimidazolium hexafluorophosphate, N- Octyl-N'-methylimidazolium trifluoroacetate, N-butylpyridinium trifluoroacetate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, N-butylpyridinium tetrafluoroborate, tri One kind selected from hexyltetradecylphosphonium tetrafluoroborate and trihexyltetradecylphosphonium chloride, or a mixture of any two or more thereof,
    Metal compounds include VO (acac) 2 , V (acac) 3 , NaVO 3 , Na 3 VO 4 , VOSO 4 , Cu (OAc) 2 , Fe (acac) 3 , Pd (acac) 2 , MoO 2 (acac) 2 , ( n Bu 4 N) 4 PVMo 11 O 40 , ( n Bu 4 N) 3 PMo 12 O 40 selected from one or a mixture of two or more,
    The oxidizer according to claim 21, wherein the carrier is made of granular silica.
  31. An antibacterial agent characterized in that an ionic liquid containing a metal compound is supported on a carrier.
  32. 32. The ionic liquid comprises one or a mixture of two or more selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, and phosphonium-based ionic liquid. Antibacterial agent.
  33. Ionic liquids include imidazolium tetrafluoroborate derivatives, imidazolium trifluoromethanesulfonate derivatives, imidazolium hexafluorophosphate derivatives, imidazolium bis (trifluoromethanesulfonyl) imide derivatives, imidazolium trifluoroacetate derivatives, imidazolium alkylsulfurates. Fate derivatives, imidazolium hydrogen sulfate derivatives, imidazolium dialkyl phosphate derivatives, imidazolium chloride derivatives, imidazolium bromide derivatives, imidazolium iodide derivatives, imidazolium thiocyanide derivatives, imidazolium carboxylate derivatives, imidazolium bisoxa Satoborate derivatives, imidazolium dicyanamide derivatives, pyridinium tetrafluoroborate derivatives , Pyridinium trifluoroacetate derivative, pyridinium trifluoromethanesulfonate derivative, pyridinium chloride derivative, pyridinium bromide derivative, pyridinium iodide derivative, pyridinium thiocyanate derivative, pyridinium dicyanamide derivative, pyridinium alkyl sulfate derivative, pyridinium hydrogen sulfate 32. One type selected from a fete derivative, a pyridinium dialkyl phosphate derivative, a pyridinium carboxylate derivative, a pyridinium bisoxalatoborate derivative, and a pyridinium dicyanamide derivative, or a mixture of any two or more thereof. Antibacterial agent.
  34. The ionic liquids are N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N'-methylimidazolium trifluoromethanesulfonate, N-butyl-N'-methylimidazolium hexafluorophosphate, N- Butyl-N'-methylimidazolium bis (trifluoromethanesulfonyl) imide, N-hexyl-N'-methylimidazolium trifluoroacetate, N-octyl-N'-methylimidazolium trifluoroacetate, N-butylpyridinium 32. The antibacterial agent according to claim 31, comprising one kind selected from tetrafluoroborate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, or a mixture of any two or more thereof. .
  35. 32. The metal compound is composed of one or a mixture of two or more selected from metal salts, metal complexes, metal oxides, metal hydroxides, metal sulfides, and metal fine particles. Antibacterial agent.
  36. Metal compounds include VO (acac) 2 , Mn (acac) 2 , Ni (acac) 2 , Co (acac) 3 , Fe (acac) 3 , MoO 2 (acac) 2 , Pd (acac) 2 , NaVO 3 , VOSO 4 (H 2 O) antimicrobial agent of claim 31, wherein the one or in that it consists of either a mixture of two or more selected from n.
  37. The carrier is one kind selected from granular silica, alumina, activated carbon, molecular sieves, ceramics, brick, wood, fiber, glass plate, glass fine rod, glass bead, metal plate, metal fine rod, sawdust, paper, sponge, or 32. The antibacterial agent according to claim 31, comprising any mixture of two or more.
  38. 32. The antibacterial agent according to claim 31, wherein the carrier is made of granular silica.
  39. The ionic liquids are N-butyl-N'-methylimidazolium tetrafluoroborate, N-butyl-N'-methylimidazolium trifluoromethanesulfonate, N-butyl-N'-methylimidazolium hexafluorophosphate, N- Butyl-N'-methylimidazolium bis (trifluoromethanesulfonyl) imide, N-hexyl-N'-methylimidazolium trifluoroacetate, N-octyl-N'-methylimidazolium trifluoroacetate, N-butylpyridinium One kind selected from tetrafluoroborate, N-hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, or a mixture of any two or more thereof,
    Metal compounds include VO (acac) 2 , Mn (acac) 2 , Ni (acac) 2 , Co (acac) 3 , Fe (acac) 3 , MoO 2 (acac) 2 , Pd (acac) 2 , NaVO 3 , 1 type selected from VOSO 4 (H 2 O) n , or a mixture of any 2 or more types,
    32. The antibacterial agent according to claim 31, wherein the carrier is made of granular silica.
  40. An antibacterial agent characterized by supporting an ionic liquid on a carrier.
  41. 41. The ionic liquid is one type selected from ammonium-based ionic liquid, pyridinium-based ionic liquid, imidazolium-based ionic liquid, and phosphonium-based ionic liquid, or a mixture of any two or more thereof. Antibacterial agent.
  42. Ionic liquids include imidazolium tetrafluoroborate derivatives, imidazolium trifluoroacetate derivatives, imidazolium alkyl sulfate derivatives, imidazolium hydrogen sulfate derivatives, imidazolium dialkyl phosphate derivatives, imidazolium chloride derivatives, imidazolium bromide Derivatives, imidazolium iodide derivatives, imidazolium thiocyanide derivatives, imidazolium carboxylate derivatives, imidazolium bisoxatotoborate derivatives, imidazolium dicyanamide derivatives, pyridinium trifluoroacetate derivatives, pyridinium trifluoromethanesulfonate derivatives, chloride Pyridinium derivatives, pyridinium bromide derivatives, pyridinium iodide derivatives, pyridinium thiocyanide derivatives, One selected from dinium dicyanamide derivatives, pyridinium alkyl sulfate derivatives, pyridinium hydrogen sulfate derivatives, pyridinium dialkyl phosphate derivatives, pyridinium carboxylate derivatives, pyridinium bisoxalatoborate derivatives, pyridinium dicyanamide derivatives, or any Consisting of a mixture of two or more,
    The antibacterial agent according to claim 40, wherein the ionic liquid is water-soluble.
  43. The ionic liquids are N-butyl-N'-methylimidazolium tetrafluoroborate, N-hexyl-N'-methylimidazolium trifluoroacetate, N-octyl-N'-methylimidazolium trifluoroacetate, N 41. The antibacterial agent according to claim 40, which comprises one kind selected from -hexylpyridinium trifluoroacetate and N-octylpyridinium trifluoroacetate, or a mixture of any two or more thereof.
  44. The carrier is one kind selected from granular silica, alumina, activated carbon, molecular sieves, ceramics, brick, wood, fiber, glass plate, glass fine rod, glass bead, metal plate, metal fine rod, sawdust, paper, sponge, or 41. The antibacterial agent according to claim 40, comprising any two or more mixtures.
  45. The antimicrobial agent according to claim 40, wherein the carrier is made of granular silica.
  46. The ionic liquids are N-butyl-N'-methylimidazolium tetrafluoroborate, N-hexyl-N'-methylimidazolium trifluoroacetate, N-octyl-N'-methylimidazolium trifluoroacetate, N 1 type selected from -hexylpyridinium trifluoroacetate, N-octylpyridinium trifluoroacetate, or a mixture of any 2 or more types,
    The antimicrobial agent according to claim 40, wherein the carrier is made of granular silica.
JP2008272709A 2008-02-15 2008-10-23 Oxidation catalyst, oxidizing method, oxidation apparatus, and antimicrobial agent Pending JP2009214094A (en)

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CN102267685A (en) * 2010-06-07 2011-12-07 广西博世科环保科技股份有限公司 Methanol vanadium sulfate and sodium chlorate acid prepared by reacting chlorine dioxide method
CN101928394B (en) 2010-07-21 2012-08-08 天津大学 Activated carbon-supported nitrile group ionic liquid-palladium catalyst for synthesizing polyketone and preparation method thereof
CN101928394A (en) * 2010-07-21 2010-12-29 天津大学 Activated carbon-supported nitrile group ionic liquid-palladium catalyst for synthesizing polyketone and preparation method thereof
JP2012148242A (en) * 2011-01-19 2012-08-09 Niigata Univ Palladium catalyst for catalytic reduction
JP2013013864A (en) * 2011-07-05 2013-01-24 Toyota Motor Corp Method for manufacturing metal cluster supported catalyst
DE102011114132A1 (en) * 2011-08-14 2013-02-14 BLüCHER GMBH Filter material useful e.g. in or as filter for gas treatment and in filters for removing pollutants, comprises activated carbon, which is present in form of discrete activated carbon particles, preferably in spherical or granular shape
KR101618289B1 (en) * 2011-08-14 2016-05-04 블뤼허 게엠베하 Filter materials for treating and purifying gas
JP2014529490A (en) * 2011-08-14 2014-11-13 ブリュッヒャー ゲーエムベーハー Filter material for processing and purifying gas
US9440219B2 (en) 2011-08-14 2016-09-13 BLüCHER GMBH Filter materials for treating and purifying gas
US9409162B2 (en) 2011-08-14 2016-08-09 Blucher Gmbh Activated carbon with a metal based component
US10531665B2 (en) 2013-02-06 2020-01-14 Pom Patentverwaltungs Gbr Heteropolyoxometalates
JP2016511241A (en) * 2013-02-06 2016-04-14 ペーオーエム パテントフェルヴァルトゥングス ゲゼルシャフト ビュルゲルリッフェン レヒツPom Patentverwaltungs Gbr Heteropolyoxometalates
CN104588111A (en) * 2014-12-24 2015-05-06 东华大学 Preparation method and application of silicon oxide/palladium hybridized material with surface grafted with ionic liquid
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