JP4711012B2 - Ozonolysis agent - Google Patents
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- JP4711012B2 JP4711012B2 JP2009232232A JP2009232232A JP4711012B2 JP 4711012 B2 JP4711012 B2 JP 4711012B2 JP 2009232232 A JP2009232232 A JP 2009232232A JP 2009232232 A JP2009232232 A JP 2009232232A JP 4711012 B2 JP4711012 B2 JP 4711012B2
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- iron compound
- iron
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- ozonolysis
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- 238000005949 ozonolysis reaction Methods 0.000 title description 19
- 150000002506 iron compounds Chemical class 0.000 claims description 45
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 229910052596 spinel Inorganic materials 0.000 claims description 20
- 239000011029 spinel Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910003321 CoFe Inorganic materials 0.000 claims description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 5
- 239000001099 ammonium carbonate Substances 0.000 description 5
- 235000012501 ammonium carbonate Nutrition 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910000358 iron sulfate Inorganic materials 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 159000000014 iron salts Chemical class 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 208000013220 shortness of breath Diseases 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910006540 α-FeOOH Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
本発明は、空気中に存在するオゾン（Ｏ３）を分解除去するオゾン分解触媒に関する。 The present invention relates to an ozone decomposition catalyst that decomposes and removes ozone (O 3 ) present in the air.
コロナ放電による帯電方式を採用した電気集塵式空気清浄機や電子写真複写機などにおいては、コロナ放電が機内の空気中で行われるために、機内に多量のオゾンが発生する。そしてこのオゾンは、非常に臭いが強く、酸化性の高い気体であり、例えば空気中に０．１ｐｐｍの濃度が存在するだけで、息切れやめまい、吐き気、頭痛などの生理作用を生じさせるものであるため、各機器からこのようなオゾンを機外に漏洩させることは回避しなければならない。 In an electrostatic precipitator type air cleaner or an electrophotographic copying machine adopting a charging method by corona discharge, a large amount of ozone is generated in the apparatus because corona discharge is performed in the air in the apparatus. This ozone is a very odorous and highly oxidative gas that, for example, has a concentration of 0.1 ppm in the air, causing physiological effects such as shortness of breath, dizziness, nausea and headache. For this reason, it is necessary to avoid leakage of ozone from each device.
このような問題を克服するために、オゾンを分解するフィルタが各種提案されている。形態も様々であるが、オゾン分解剤に着眼すると次のようになる。 In order to overcome such problems, various filters for decomposing ozone have been proposed. There are various forms, but when focusing on the ozonolysis agent, it is as follows.
まず、活性炭の細孔容積を制御したオゾン分解剤が開示されている（例えば特許文献１参照）。 First, an ozonolysis agent in which the pore volume of activated carbon is controlled is disclosed (for example, see Patent Document 1).
しかしながら、活性炭の細孔容積を制御しても、炭素の消失反応であるため、経時的に劣化率が大きくなり、長期間に渡って、高効率を維持することができないという問題がある。 However, even if the pore volume of the activated carbon is controlled, there is a problem that since it is a carbon disappearance reaction, the deterioration rate increases with time, and high efficiency cannot be maintained over a long period of time.
更に、活性炭の表面にα−ＦｅＯＯＨと５Ｆｅ2Ｏ3・Ｈ2Ｏとを担持されたオゾン分解剤が開示されている（例えば特許文献２参照）。 Additionally, alpha-FeOOH and 5Fe 2 O 3 · H 2 O and ozonolysis agent carried on the surface of the activated carbon has been disclosed (for example, see Patent Document 2).
しかしながら、かかる手法は、活性炭依存の分解反応であり、活性炭単体よりは高効率を維持する事が可能であるが、やはり経時的に劣化率が大きくなり、長期間に渡って、高効率を維持することができないという問題がある。 However, this method is an activated carbon-dependent decomposition reaction, and it is possible to maintain a higher efficiency than that of the activated carbon alone, but the deterioration rate increases with time, and the high efficiency is maintained over a long period of time. There is a problem that you can not.
一方、鉄、銅複合酸化物から各種オゾン分解剤も開示されている（例えば特許文献３、特許文献４参照）。 On the other hand, various ozone decomposing agents are also disclosed from iron and copper complex oxides (see, for example, Patent Document 3 and Patent Document 4).
しかしながら、鉄酸化物、銅酸化物の複合化合物では、オゾン分解性能が不十分であるため、貴金属を併用することによりオゾン分解性能を向上させるもので、極めて高価な触媒となり、産業上広く利用するには困難なものであった。 However, the complex compound of iron oxide and copper oxide has insufficient ozonolysis performance, so it improves ozonolysis performance by using a noble metal in combination, and becomes an extremely expensive catalyst and widely used in industry. It was difficult.
本発明は上記従来技術の課題を背景になされたものであり、本発明の目的は、オゾンを初めとする人体に有害なガスの除去性能が高く、長寿命で、安価であるオゾン分解剤を提供することを目的とする。 The present invention has been made against the background of the problems of the prior art described above, and the object of the present invention is to provide an ozone decomposing agent that has a high performance for removing gases harmful to the human body including ozone, has a long life, and is inexpensive. The purpose is to provide.
上記課題を解決するため、鋭意研究した結果、遂に本発明を完成するに到った。すなわち本発明は、鉄化合物とスピネル構造の鉄化合物を含有するオゾン分解剤である。 As a result of intensive studies to solve the above problems, the present invention has finally been completed. That is, the present invention is an ozonolysis agent containing an iron compound and an iron compound having a spinel structure.
前記鉄化合物がＦｅ2Ｏ3、ＦｅＯ（ＯＨ）、Ｆｅ（ＯＨ）3の少なくとも一種の酸化物を含み、前記スピネル構造の鉄化合物がＭｎＦｅ2Ｏ4、ＺｎＦｅ2Ｏ4、ＮｉＦｅ2Ｏ4、ＣｕＦｅ2Ｏ4、ＣｏＦｅ2Ｏ4の少なくとも一種の酸化物を含むオゾン分解剤が上記目的に適する。 The iron compound includes at least one oxide of Fe 2 O 3 , FeO (OH), and Fe (OH) 3 , and the spinel structure iron compound is MnFe 2 O 4 , ZnFe 2 O 4 , NiFe 2 O 4 , An ozone decomposing agent containing at least one oxide of CuFe 2 O 4 and CoFe 2 O 4 is suitable for the above purpose.
鉄化合物とスピネル構造の鉄化合物を含有するオゾン分解剤により、低価格で、長期にわたって満足すべきオゾン除去性能を発現することが可能となる。 An ozone decomposing agent containing an iron compound and an iron compound having a spinel structure can exhibit satisfactory ozone removal performance over a long period of time at a low price.
本発明は、鉄化合物とスピネル構造の鉄化合物の両者を含むオゾン分解剤であることが好ましい。鉄化合物とスピネル構造の鉄化合物両者を含むことにより、優れたオゾン分解性能が得られるからである。かかる組み合わせにより優れたオゾン分解性能が得られる原因については定かではないが、両者を含むことをオゾンの酸素原子の取込、及び放出がスムーズを行われるためと推測する。 The present invention is preferably an ozonolysis agent containing both an iron compound and an iron compound having a spinel structure. It is because excellent ozonolysis performance can be obtained by including both an iron compound and an iron compound having a spinel structure. Although it is not certain about the reason that such combination provides excellent ozonolysis performance, it is assumed that the inclusion of both causes smooth incorporation and release of ozone oxygen atoms.
本発明にかかる鉄化合物は、Ｆｅ2Ｏ3、ＦｅＯ（ＯＨ）、Ｆｅ（ＯＨ）3の少なくとも一種の酸化物を含むことが好ましい。これらの鉄化合物を採用することにより、スピネル構造の鉄化合物の存在と相まって、より優れたオゾン分解性能を発揮するからである。鉄化合物の製法は、水溶性鉄塩を炭酸アンモニウム、炭酸水素ナトリウム、炭酸ナトリウム等で中和後に高温で焼成する方法や、水溶性鉄塩を炭酸アンモニウム、炭酸水素ナトリウム、炭酸ナトリウム等で中和し、その後、ペルオキソ二硫酸カリウム、次亜塩素酸ナトリウム、過酸化水素水等の酸化剤で水中酸化する方法や、水溶性鉄塩を炭酸アンモニウム、炭酸水素ナトリウム、炭酸ナトリウム等で中和し、その後、液中に空気を通気して、溶存酸素で水中酸化する方法や、水溶性鉄塩を高温で焼成する方法などにより作製することが可能である。 The iron compound according to the present invention preferably contains at least one oxide of Fe 2 O 3 , FeO (OH), and Fe (OH) 3 . This is because by adopting these iron compounds, combined with the presence of iron compounds having a spinel structure, it exhibits better ozonolysis performance. The iron compound can be produced by neutralizing water-soluble iron salts with ammonium carbonate, sodium hydrogen carbonate, sodium carbonate, etc., and then firing the water-soluble iron salts with ammonium carbonate, sodium hydrogen carbonate, sodium carbonate, etc. Then, the method of oxidizing in water with an oxidizing agent such as potassium peroxodisulfate, sodium hypochlorite, and hydrogen peroxide water, and neutralizing the water-soluble iron salt with ammonium carbonate, sodium bicarbonate, sodium carbonate, etc. Then, it can be produced by a method in which air is passed through the liquid and oxidized in water with dissolved oxygen, or a method in which a water-soluble iron salt is baked at a high temperature.
一方、スピネル構造の鉄化合物は、ＭｎＦｅ2Ｏ4、ＺｎＦｅ2Ｏ4、ＮｉＦｅ2Ｏ4、ＣｕＦｅ2Ｏ4、ＣｏＦｅ2Ｏ4の少なくとも一種の酸化物を含むことが好ましい。スピネル構造の鉄化合物の製法は、各金属の酸化物、炭酸塩の粉末を混合し、８００℃以上の高温で加熱合成する方法や、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｎは各金属をシュウ酸塩として共沈して、６００〜８００℃で加熱する方法や、水溶性金属塩を炭酸アンモニウム、炭酸水素ナトリウム、炭酸ナトリウム等で中和後、反応液に窒素ガスを通気しながら４０〜８０℃まで加熱し、一定温度に保持した後、窒素ガスを空気に変えて、撹拌しながら溶存酸素で酸化する方法などにより作製することが可能である。 On the other hand, the iron compound having a spinel structure preferably contains at least one oxide of MnFe 2 O 4 , ZnFe 2 O 4 , NiFe 2 O 4 , CuFe 2 O 4 , and CoFe 2 O 4 . The spinel-structured iron compound is manufactured by mixing each metal oxide and carbonate powder and heating and synthesizing it at a high temperature of 800 ° C. or higher. Fe, Ni, Co, and Mn are used as oxalate for each metal. Co-precipitated and heated at 600-800 ° C, or neutralized water-soluble metal salt with ammonium carbonate, sodium bicarbonate, sodium carbonate, etc., then heated to 40-80 ° C with nitrogen gas flowing through the reaction solution Then, after maintaining at a constant temperature, it can be produced by a method of changing nitrogen gas to air and oxidizing with dissolved oxygen while stirring.
前記の方法により、鉄化合物とスピネル構造の鉄化合物を個別に作製して混合する方法が挙げられる。しかし、合理的に鉄化合物とスピネル構造の鉄化合物を作製するには、鉄化合物とスピネル構造の鉄化合物を共沈法で作製する方法が好ましい。 A method of individually preparing and mixing an iron compound and an iron compound having a spinel structure by the above-described method is mentioned. However, in order to rationally produce an iron compound and an iron compound having a spinel structure, a method of producing an iron compound and an iron compound having a spinel structure by a coprecipitation method is preferable.
より具体的には、水溶性金属塩を炭酸アンモニウム、炭酸水素ナトリウム、炭酸ナトリウム等で中和後、窒素を通気しないで反応液に空気を通気しながら４０〜８０℃まで加熱し、一定温度に保持し、撹拌しながら溶存酸素で酸化する方法である。更に、２００〜４００℃で焼成することでＦｅＯＯＨ、Ｆｅ（ＯＨ）3等の酸化を進行させることも可能である。この方法で行うことにより、４０℃以下の低温側で鉄化合物を生成し、４０℃以上の温度でスピネル構造の鉄化合物が生成していると考えられる。 More specifically, after neutralizing the water-soluble metal salt with ammonium carbonate, sodium hydrogen carbonate, sodium carbonate or the like, the mixture is heated to 40 to 80 ° C. while aerating air to the reaction solution without aeration of nitrogen, and kept at a constant temperature. This is a method of holding and oxidizing with dissolved oxygen while stirring. Furthermore, it is possible to advance oxidation of FeOOH, Fe (OH) 3, etc. by firing at 200 to 400 ° C. By carrying out by this method, it is considered that an iron compound is generated on the low temperature side of 40 ° C. or lower, and an iron compound having a spinel structure is generated at a temperature of 40 ° C. or higher.
オゾン分解触媒に含有するマンガン、亜鉛、ニッケル、銅、コバルトは、マンガン、亜鉛、ニッケル、銅、コバルトの含有率は、オゾン分解触媒の鉄元素に対して３〜５０モル％で配合することが好ましく、１０〜３０モル％がより好ましい。３モル％未満の場合は、スピネル構造の生成率が低くなり、オゾン分解性能が低くなる。一方、５０モル％を超える場合は、マンガン、亜鉛、ニッケル、銅、コバルト由来の化合物の生成が多くなり、オゾン分解性能が低くなる。 Manganese, zinc, nickel, copper, and cobalt contained in the ozonolysis catalyst may be blended at 3 to 50 mol% of manganese, zinc, nickel, copper, and cobalt with respect to the iron element of the ozonolysis catalyst. Preferably, 10-30 mol% is more preferable. When the amount is less than 3 mol%, the rate of formation of the spinel structure is lowered, and the ozonolysis performance is lowered. On the other hand, when it exceeds 50 mol%, the production | generation of the compound derived from manganese, zinc, nickel, copper, and cobalt increases and ozonolysis performance becomes low.
鉄化合物、スピネル構造の鉄化合物の構造は、Ｘ線回折により確認することができる。一方、オゾン分解触媒に含有する鉄、マンガン、亜鉛、ニッケル、銅、コバルトは、マンガン、亜鉛、ニッケル、銅、コバルトの金属元素の含有率は、蛍光Ｘ線により確認することができる。 The structure of the iron compound and the iron compound having a spinel structure can be confirmed by X-ray diffraction. On the other hand, for iron, manganese, zinc, nickel, copper, and cobalt contained in the ozone decomposition catalyst, the content of metal elements of manganese, zinc, nickel, copper, and cobalt can be confirmed by fluorescent X-rays.
前記の鉄化合物とスピネル構造の鉄化合物を含有するオゾン分解触媒を粉末またはペレット状に成形して単独で充填層などに使用するだけでなく、他の脱臭剤や分解剤と混合したり併用したりして使用することができる。また、不織布、織物、シート基材に添着してプリーツ形状、ハニカム形状に成形加工して使用することができる。さらに、シート、アルミ箔からなるハニカム基材、ウレタンに添着して使用することができる。 The ozone decomposition catalyst containing the iron compound and spinel structure iron compound is molded into powder or pellets and used alone for a packed bed, etc., but also mixed with other deodorizers and decomposers. Can be used. Further, it can be used after being formed into a pleated shape or a honeycomb shape by being attached to a nonwoven fabric, a woven fabric, or a sheet base material. Furthermore, it can be used by being attached to a sheet, a honeycomb substrate made of aluminum foil, or urethane.
以下、実施例によって本発明の作用効果をより具体的に示す。下記実施例は本発明方法を限定する性質のものではなく、前・後記の趣旨に沿って設計変更することはいずれも本発明の技術的範囲に含まれるものである。 Hereinafter, the effects of the present invention will be described more specifically by way of examples. The following examples are not intended to limit the method of the present invention, and any design changes in accordance with the gist of the preceding and following descriptions are included in the technical scope of the present invention.
まず、本実施例で用いたオゾン分解剤の試験方法を以下に示す。 First, the test method of the ozonolysis agent used in this example is shown below.
（スピネル構造）
鉄化合物、スピネル構造の鉄化合物は、Ｘ線回折による格子面間隔（ｄ値）を測定することにより確認することができる。測定条件は、ＣｕＫα線源、電圧４０ＫＶ、電流３７．５ｍＡ、走査範囲１５〜７５°、走査速度０．１２４°／ｍｉｎで実施した。測定結果をＪＣＰＤＳ（Ｊｏｉｎｔ Ｃｏｍｍｉｔｔｅｅ ｏｆ Ｐｏｗｄｅｒ Ｄｉｆｆｒａｃｔｉｏｎ Ｓｔａｎｄａｒｔｓ）カードと比較し、格子面間隔から確認できる。例えば、ＭｎＦｅ2Ｏ4のｄ値は、相対強度が高い順に、２．５６、１．５０、３．０１、１．６４等である。
(Spinel structure)
The iron compound and the iron compound having a spinel structure can be confirmed by measuring the lattice spacing (d value) by X-ray diffraction. The measurement conditions were a CuKα radiation source, a voltage of 40 KV, a current of 37.5 mA, a scanning range of 15 to 75 °, and a scanning speed of 0.124 ° / min. The measurement result can be confirmed from the lattice plane spacing by comparing with a JCPDS (Joint Committee of Powder Diffraction Standards) card. For example, the d value of MnFe 2 O 4 is 2.56, 1.50, 3.01, 1.64, etc. in descending order of relative strength.
（オゾン除去率）
オゾン分解剤を０．１ｇ計量して内径１２．５ｍｍのガラス製カラムに充填した。温度２５℃、相対湿度５０％ＲＨに調整した８ｐｐｍのオゾンを含む空気を、風量２Ｌ／ｍｉｎでカラムに供給した。カラムの入口、出口のオゾン濃度を測定し、除去率を次式から算出した。オゾン濃度は紫外線吸収法オゾン濃度測定器で測定した。
(Ozone removal rate)
0.1 g of ozonolysis agent was weighed and packed into a glass column having an inner diameter of 12.5 mm. Air containing 8 ppm of ozone adjusted to a temperature of 25 ° C. and a relative humidity of 50% RH was supplied to the column at a flow rate of 2 L / min. The ozone concentration at the inlet and outlet of the column was measured, and the removal rate was calculated from the following equation. The ozone concentration was measured with an ultraviolet absorption method ozone concentration measuring device.
（数式１）
除去率（％）＝［１−（オゾン出口濃度）／（オゾン入口濃度）×１００］
(Formula 1)
Removal rate (%) = [1- (ozone outlet concentration) / (ozone inlet concentration) × 100]
（実施例１）
硫酸鉄［ＦｅＳＯ4・７Ｈ2Ｏ］５．５ｇ、硫酸マンガン［ＭｎＳＯ4・５Ｈ2Ｏ］１．２ｇを５００ｍｌ、２０℃のイオン交換水に溶解させてＡ液を得た。一方、炭酸ナトリウム［Ｎａ2ＣＯ3］８ｇを５００ｍｌ、２０℃のイオン交換水に溶解させてＢ液を得た。Ａ液にＢ液をゆっくり添加して鉄化合物が含むＣ液を得た。このＣ液中に空気を通気しながら１時間撹拌した。その後、５０℃まで昇温して６時間撹拌した。Ｃ液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、１００℃の空気中で１０時間乾燥した。得られた触媒は、Ｆｅ2Ｏ3、ＦｅＯ（ＯＨ）の鉄化合物とＭｎＦｅ2Ｏ4のスピネル構造の鉄化合物を含有しており、Ｍｎ元素比率は２０モル％であった。
Example 1
Liquid A was obtained by dissolving 5.5 g of iron sulfate [FeSO 4 .7H 2 O] and 1.2 g of manganese sulfate [MnSO 4 .5H 2 O] in 500 ml of ion-exchanged water at 20 ° C. On the other hand, 8 g of sodium carbonate [Na 2 CO 3 ] was dissolved in 500 ml of ion exchange water at 20 ° C. to obtain a liquid B. Liquid B was slowly added to liquid A to obtain liquid C containing an iron compound. It stirred for 1 hour, ventilating air in this C liquid. Then, it heated up to 50 degreeC and stirred for 6 hours. Liquid C was filtered off, washed with ion exchange water until the filtrate became neutral, and then dried in air at 100 ° C. for 10 hours. The obtained catalyst contained an iron compound of Fe 2 O 3 and FeO (OH) and an iron compound having a spinel structure of MnFe 2 O 4 , and the Mn element ratio was 20 mol%.
（実施例２）
硫酸鉄［ＦｅＳＯ4・７Ｈ2Ｏ］５．５ｇ、硫酸銅［ＣｕＳＯ4・５Ｈ2Ｏ］１．２ｇを５００ｍｌ、２０℃のイオン交換水に溶解させてＡ液を得た。一方、炭酸ナトリウム［Ｎａ2ＣＯ3］８ｇを５００ｍｌ、２０℃のイオン交換水に溶解させてＢ液を得た。Ａ液にＢ液をゆっくり添加して鉄化合物が含むＣ液を得た。このＣ液中に空気を通気しながら１時間撹拌した。その後、５０℃まで昇温して６時間撹拌した。Ｃ液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、１００℃の空気中１０時間乾燥した。得られた触媒は、Ｆｅ2Ｏ3、ＦｅＯ（ＯＨ）の鉄化合物とＣｕＦｅ2Ｏ4のスピネル構造の鉄化合物を含有しており、Ｃｕ元素比率は２０モル％であった。
(Example 2)
Liquid A was obtained by dissolving 5.5 g of iron sulfate [FeSO 4 .7H 2 O] and 1.2 g of copper sulfate [CuSO 4 .5H 2 O] in 500 ml of ion-exchanged water at 20 ° C. On the other hand, 8 g of sodium carbonate [Na 2 CO 3 ] was dissolved in 500 ml of ion exchange water at 20 ° C. to obtain a liquid B. Liquid B was slowly added to liquid A to obtain liquid C containing an iron compound. It stirred for 1 hour, ventilating air in this C liquid. Then, it heated up to 50 degreeC and stirred for 6 hours. Liquid C was filtered off, washed with ion exchange water until the filtrate was neutral, and then dried in air at 100 ° C. for 10 hours. The obtained catalyst contained an iron compound of Fe 2 O 3 and FeO (OH) and an iron compound of a spinel structure of CuFe 2 O 4 , and the Cu element ratio was 20 mol%.
（実施例３）
実施例１の触媒を２５０℃の空気中で３時間空気酸化した。得られた触媒は、Ｆｅ2Ｏ3の鉄化合物とＭｎＦｅ2Ｏ4のスピネル構造の鉄化合物を含有しており、Ｃｕ元素比率は２０モル％であった。
(Example 3)
The catalyst of Example 1 was air oxidized in air at 250 ° C. for 3 hours. The obtained catalyst contained an Fe 2 O 3 iron compound and an MnFe 2 O 4 spinel-structure iron compound, and the Cu element ratio was 20 mol%.
（実施例４）
実施例２の触媒を２５０℃の空気中で３時間空気酸化した。得られた触媒は、Ｆｅ2Ｏ3の鉄化合物とＣｕＦｅ2Ｏ4のスピネル構造の鉄化合物を含有しており、Ｃｕ元素比率は２０モル％であった。
Example 4
The catalyst of Example 2 was air oxidized in air at 250 ° C. for 3 hours. The obtained catalyst contained an iron compound of Fe 2 O 3 and an iron compound of a spinel structure of CuFe 2 O 4 , and the Cu element ratio was 20 mol%.
（比較例１）
硫酸鉄［ＦｅＳＯ4・７Ｈ2Ｏ］５．５ｇを５００ｍｌ、２０℃のイオン交換水に溶解させてＡ液を得た。一方、炭酸ナトリウム［Ｎａ2ＣＯ3］８ｇを５００ｍｌ、２０℃のイオン交換水に溶解させてＢ液を得た。Ａ液にＢ液をゆっくり添加して鉄化合物が含むＣ液を得た。このＣ液中に空気を通気しながら１時間撹拌した。その後、５０℃まで昇温して６時間撹拌した。Ｃ液を濾別し、イオン交換水で濾液が中性になるまで水洗した後、１００℃の空気中で１０時間乾燥した。得られた触媒は、Ｆｅ2Ｏ3、ＦｅＯ（ＯＨ）の鉄化合物であった。
(Comparative Example 1)
Liquid A was obtained by dissolving 5.5 g of iron sulfate [FeSO 4 .7H 2 O] in 500 ml of ion exchange water at 20 ° C. On the other hand, 8 g of sodium carbonate [Na 2 CO 3 ] was dissolved in 500 ml of ion exchange water at 20 ° C. to obtain a liquid B. Liquid B was slowly added to liquid A to obtain liquid C containing an iron compound. It stirred for 1 hour, ventilating air in this C liquid. Then, it heated up to 50 degreeC and stirred for 6 hours. Liquid C was filtered off, washed with ion exchange water until the filtrate became neutral, and then dried in air at 100 ° C. for 10 hours. The obtained catalyst was an iron compound of Fe 2 O 3 and FeO (OH).
（比較例２）
比較例１の触媒を２５０℃の空気中で３時間空気酸化した。得られた触媒は、Ｆｅ2Ｏ3の鉄化合物であった。
(Comparative Example 2)
The catalyst of Comparative Example 1 was air oxidized in air at 250 ° C. for 3 hours. The obtained catalyst was an iron compound of Fe 2 O 3 .
実施例１〜３に関して、初期のオゾン除去率、６０時間後のオゾン除去率が高く、経時的な劣化が小さいことが分かる。一方、比較例１〜２に関して、初期のオゾン除去率から低性能であることが分かる。 Regarding Examples 1 to 3, it can be seen that the initial ozone removal rate, the ozone removal rate after 60 hours are high, and the deterioration over time is small. On the other hand, regarding Comparative Examples 1-2, it turns out that it is low performance from the initial ozone removal rate.
本願発明にかかるオゾン分解剤は、初期から長期に渡って、高効率を維持することが可能であり、幅広いオゾン分解除去分野に利用することができ、産業界に寄与することが大である。 The ozonolysis agent according to the present invention can maintain high efficiency from the initial stage over a long period of time, can be used in a wide range of ozonolysis removal fields, and contributes to the industry.
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| JPS5727903A (en) * | 1980-07-24 | 1982-02-15 | Toshiba Mach Co Ltd | Method and apparatus for decomposing ozone |
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