JPH0197461A - Sterilizing method - Google Patents
Sterilizing methodInfo
- Publication number
- JPH0197461A JPH0197461A JP62254604A JP25460487A JPH0197461A JP H0197461 A JPH0197461 A JP H0197461A JP 62254604 A JP62254604 A JP 62254604A JP 25460487 A JP25460487 A JP 25460487A JP H0197461 A JPH0197461 A JP H0197461A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- bacteria
- ozone
- titanium
- floating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 241000894006 Bacteria Species 0.000 claims abstract description 27
- 238000004659 sterilization and disinfection Methods 0.000 claims description 19
- 239000010936 titanium Substances 0.000 abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052719 titanium Inorganic materials 0.000 abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052710 silicon Inorganic materials 0.000 abstract description 15
- 239000010703 silicon Substances 0.000 abstract description 15
- 239000007789 gas Substances 0.000 abstract description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 abstract description 12
- 239000011218 binary composite Substances 0.000 abstract description 11
- 238000007667 floating Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000011206 ternary composite Substances 0.000 abstract description 5
- 239000007792 gaseous phase Substances 0.000 abstract 4
- 230000001590 oxidative effect Effects 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000010948 rhodium Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 229910052703 rhodium Inorganic materials 0.000 description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 244000052616 bacterial pathogen Species 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical class Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- 150000003755 zirconium compounds Chemical class 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- -1 inorganic acid salts Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 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 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- CSPVUHYZUZZRGF-RNFRBKRXSA-N (4R,6R)-hydroxy-2,2,6-trimethylcyclohexanone Chemical compound C[C@@H]1C[C@@H](O)CC(C)(C)C1=O CSPVUHYZUZZRGF-RNFRBKRXSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 241000589220 Acetobacter Species 0.000 description 1
- 241000186361 Actinobacteria <class> Species 0.000 description 1
- 229930185327 Actinol Natural products 0.000 description 1
- 241000186046 Actinomyces Species 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241001478240 Coccus Species 0.000 description 1
- 241000588722 Escherichia Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000186660 Lactobacillus Species 0.000 description 1
- 241000192041 Micrococcus Species 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 241000702670 Rotavirus Species 0.000 description 1
- NAORJVVMBQZCPF-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[N+](=O)([O-])[O-].[Mn+3] Chemical compound S(=O)(=O)([O-])[O-].[N+](=O)([O-])[O-].[Mn+3] NAORJVVMBQZCPF-UHFFFAOYSA-L 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 241000194017 Streptococcus Species 0.000 description 1
- 241000187747 Streptomyces Species 0.000 description 1
- 241000607598 Vibrio Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 241000589634 Xanthomonas Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021331 inorganic silicon compound Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229940039696 lactobacillus Drugs 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- VBLQNYINPWASGP-UHFFFAOYSA-M oxygen(2-) titanium(3+) chloride Chemical compound [O-2].[Ti+3].[Cl-] VBLQNYINPWASGP-UHFFFAOYSA-M 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 241000701161 unidentified adenovirus Species 0.000 description 1
- 241000712461 unidentified influenza virus Species 0.000 description 1
- 241001430294 unidentified retrovirus Species 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は気相中に浮遊する菌をオゾンにより接触的に酸
化分解し無菌化する殺菌方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a sterilization method in which bacteria floating in a gas phase are catalytically oxidized and decomposed with ozone to render them sterilized.
〈従来技術とその問題点〉
従来から、室内に浮遊する菌を殺菌する方法として、（
１）薬液法、（２）紫外線法、（３）ガス法が上げられ
るが、薬液法においては、薬液の散布により、室内や諸
設備への液滴の付着などの問題があり、又紫外線法にお
いては、紫外線の透過力が弱いので、陰になる箇所の殺
菌ができないという欠点を有する故にガスによる殺菌が
一般的に好ましい。<Prior art and its problems> Traditionally, as a method of sterilizing bacteria floating indoors, (
1) Chemical liquid method, (2) Ultraviolet light method, and (3) Gas method. However, with chemical liquid method, there are problems such as droplets adhering to rooms and various equipment due to spraying of chemical liquid, and ultraviolet light method , gas sterilization is generally preferable because it has the disadvantage that it is not possible to sterilize shaded areas due to the weak penetrating power of ultraviolet rays.
ガスによる殺菌方法では、各種のガスの使用が可能であ
るが、残留性の問題、発ガン性の問題、排気処理設備の
必要性などを考慮すると、オゾンガスを使用するのが最
も好ましい。In the gas sterilization method, various gases can be used, but it is most preferable to use ozone gas in consideration of the problem of persistence, carcinogenicity, and the need for exhaust treatment equipment.
オゾンが強力な殺菌力を有していることはよく知られて
いるが、気相で殺菌を実施する場合には、長時間オゾン
と菌を接触させることが必要であるという欠点を有する
。Although it is well known that ozone has a strong sterilizing effect, when sterilizing in the gas phase, it has the disadvantage that ozone and bacteria must be brought into contact for a long period of time.
〈発明の目的〉
本発明の目的は、オゾンを導入し、気相中に浮遊する菌
を殺菌するにあたり、長期にわたり安定した効率のよい
殺菌効果が得られ、かつ、未反応オゾンの排出を実質的
になくした殺菌方法を提供することにある。<Objective of the Invention> The object of the present invention is to introduce ozone to sterilize bacteria floating in the gas phase, to obtain a stable and efficient sterilizing effect over a long period of time, and to substantially eliminate the emission of unreacted ozone. The objective is to provide a sterilization method that eliminates the need for sterilization.
〈問題点を解決するための手段〉
本発明者らは上記目的を達成するために、種々検討した
結果、本発明を完成するに至ったものである。すなわち
、本発明になる殺菌方法は、気相中の浮遊菌を触媒上に
捕捉し、触媒で活性化されたオゾンにより速やかに酸化
分解し、なおかつ未反応オゾンを触媒上で分解すること
を特徴とする。<Means for Solving the Problems> In order to achieve the above object, the present inventors have conducted various studies and have completed the present invention. That is, the sterilization method of the present invention is characterized in that airborne bacteria in the gas phase are captured on a catalyst, rapidly oxidized and decomposed by ozone activated by the catalyst, and unreacted ozone is decomposed on the catalyst. shall be.
上記触媒としては、浮遊菌を効率よく吸着捕集する能力
と捕集された菌をオゾン導入により効率よく酸化分解す
る能力と、未反応オゾンを分解する能力を兼ね備えるこ
とが必要である。The catalyst needs to have the ability to efficiently adsorb and collect airborne bacteria, the ability to efficiently oxidize and decompose the collected bacteria by introducing ozone, and the ability to decompose unreacted ozone.
本発明者らは、浮遊菌の捕捉能力を有し、かつ、捕捉さ
れた菌がオゾンにより効率よく分解し、なおかつ、未反
応オゾンを分解する好ましい触媒として、チタンおよび
ケイ素からなる二元系複合酸化物、チタンおよびジルコ
ニウムからなる二元系複合酸化物、またはチタン、ケイ
素およびジルコニウムからなる三元系複合酸化物が優れ
たオゾン殺菌用触媒であることを見い出し、さらに、上
記二元系複合酸化物または三元系複合酸化物にマンガン
（Ｍｎ ） 、鉄（Ｆｅ）、コバルト（ＣＯ）、ニッケ
ル（Ｎｉ）、亜鉛（Ｚ ｎ）、銀（Ａｇ）、白金（Ｐｔ
）、パラジウム（Ｐｄ）およびロジウム（Ｒｈ）よりな
る群から選ばれた少なくとも一種の元素またはその化合
物を添加してなるものは、より優れたオゾン殺菌用触媒
であることを見い出した。The present inventors have developed a binary composite consisting of titanium and silicon as a preferred catalyst that has the ability to capture airborne bacteria, efficiently decomposes the trapped bacteria by ozone, and decomposes unreacted ozone. It has been discovered that a binary composite oxide consisting of oxide, titanium and zirconium, or a ternary composite oxide consisting of titanium, silicon and zirconium is an excellent catalyst for ozone sterilization. manganese (Mn), iron (Fe), cobalt (CO), nickel (Ni), zinc (Zn), silver (Ag), platinum (Pt),
), palladium (Pd), and rhodium (Rh), or a compound thereof, has been found to be a more excellent ozone sterilization catalyst.
すなわち、本発明は菌の浮遊する気相中にオゾンを導入
し、菌を分解殺菌する方法において、該ガス流路に触媒
を設置し、オゾンを導入することを特徴とする殺菌方法
であり、また実施の態様として好ましい触媒がチタンお
よびケイ素からなる二元系複合酸化物、チタンおよびジ
ルコニウムからなる二元系複合酸化物および／またはチ
タン、ケイ素およびジルコニウムからなる三元系複合酸
化物をＡ成分とし、マンガン（Ｍｎ）、鉄（Ｆｅ）、コ
バルト（Ｃｏ）、ニッケル（Ｎｉ）、亜鉛（Ｚ ｎ）、
銀（Ａｇ）、白金（Ｐｔ）、パラジウム（Ｐｄ）および
ロジウム（Ｒｈ ）よりなる群から選ばれた少なくとも
一種の元素を８成分としてなるものであって、かつ該触
媒の組成がＡ成分が酸化物の重量％で４０〜１００重量
％、Ｂ成分はＭｎＸＦｅ、Ｃｏ、Ｎｉ １ＺｎおよびＡ
ｇにツイテは酸化物としての重量％で０〜６０重量％、
Ｐｔ１ｐｄ 、 Ｒｈについては金属元素として０〜１
０重量％の範囲よりなることを特徴とするものである。That is, the present invention is a sterilization method for decomposing and sterilizing bacteria by introducing ozone into a gas phase in which bacteria are suspended, which is characterized by installing a catalyst in the gas flow path and introducing ozone, In addition, as a preferred embodiment, a preferred catalyst is a binary composite oxide consisting of titanium and silicon, a binary composite oxide consisting of titanium and zirconium, and/or a ternary composite oxide consisting of titanium, silicon, and zirconium as the component A. Manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn),
The catalyst is composed of eight components consisting of at least one element selected from the group consisting of silver (Ag), platinum (Pt), palladium (Pd) and rhodium (Rh), and the composition of the catalyst is such that component A is oxidized. 40 to 100% by weight, component B is MnXFe, Co, Ni 1Zn and A
g is 0 to 60% by weight as an oxide,
For Pt1pd and Rh, the metal element is 0 to 1.
It is characterized by being in the range of 0% by weight.
〈作 用〉
本発明にかかる前記の好適な触媒の特徴はチタンおよび
ケイ素からなる二元系複合酸化物（以下、ＴｉＯ２−８
ｉＯ２とする）、チタンおよびジルコニウムからなる二
元系複合酸化物（以下、Ｔ ｉ ０２−Ｚｒ ０２とす
る）、チタン、ケイ素およびジルコニウムからなる三元
系複合酸化物（以下、Ｔ １ｏ２−８１ｏ２−ＺｒＯ２
とする）を触媒成分として用いている点にある。<Function> The above-mentioned preferred catalyst according to the present invention is characterized by a binary composite oxide (hereinafter referred to as TiO2-8) consisting of titanium and silicon.
iO2), a binary composite oxide consisting of titanium and zirconium (hereinafter referred to as T i 02-Zr 02), and a ternary composite oxide consisting of titanium, silicon and zirconium (hereinafter referred to as T 1o2-81o2- ZrO2
) is used as a catalyst component.
一般に、チタンおよびケイ素からなる二元系複合酸化物
は例えば田部浩三（触媒、第１７巻、ぬ３．７２頁（１
９７５年））によっても周知のように、固体酸として知
られ、構成するおのおの単独の酸化物には見られない顕
著な酸性を示し、また高表面積を有する。In general, binary composite oxides consisting of titanium and silicon are used, for example, by Kozo Tabe (Catalysts, Vol. 17, p. 3.72 (1)
975)), it is known as a solid acid, exhibits remarkable acidity that is not found in the constituent oxides alone, and has a high surface area.
すなわち、ＴｉＯ２−８ｉＯ２は酸化チタンおよび酸化
ケイ素を単に混合したものではなく、チタンおよびケイ
素がいわゆる二元系複合酸化物を形成することによりそ
の特異な物性が発現するものと認めることのできるもの
である。また、チタン、ジルコニウムからなる二元系複
合酸化物およびチタン、ジルコニウムおよびケイ素から
なる三元系複合酸化物もＴｉＯ２−８＋０２と同じよう
な性質を有する複合酸化物として特定される。In other words, TiO2-8iO2 is not simply a mixture of titanium oxide and silicon oxide, but it can be recognized that titanium and silicon form a so-called binary composite oxide, resulting in its unique physical properties. be. Furthermore, binary composite oxides consisting of titanium and zirconium and ternary composite oxides consisting of titanium, zirconium and silicon are also specified as composite oxides having properties similar to TiO2-8+02.
さらに、上記複合酸化物はＸ線回折による分析の結果、
非晶質もしくはほぼ非晶質に近い微細構造を有している
。Furthermore, as a result of analysis by X-ray diffraction, the above composite oxide
It has an amorphous or almost amorphous microstructure.
本発明になる殺菌方法において、前記触媒の特異な性能
、すなわち、菌をオゾンによって分解除去する機構につ
いては確かではないが、上記複合酸化物の諸性質が菌の
吸着及び吸着された物質とオゾンとの酸化反応に対して
好ましい影響を与えるものと考えられ、さらに、上記複
合酸化物にマンガン、鉄、ニッケル、コバルト、亜鉛、
銀、白金、パラジウム、ロジウム等の元素またはその化
合物の添加が、より一層効果的に作用しオゾン殺菌反応
を速める役割を果していると考えられる。In the sterilization method of the present invention, although the unique performance of the catalyst, that is, the mechanism for decomposing and removing bacteria by ozone, is not certain, the various properties of the composite oxide are such that the adsorption of bacteria and the adsorbed substances and ozone It is thought to have a favorable effect on the oxidation reaction with manganese, iron, nickel, cobalt, zinc,
It is believed that the addition of elements such as silver, platinum, palladium, and rhodium or their compounds acts more effectively and plays a role in accelerating the ozone sterilization reaction.
触ｍＡｔｔ分テアルＴ ｉ ０２−８ ｉ ０２ 、Ｔ
ｉＯ２−ＺｒＯ２およびＴ ｉ ０２−８ ｉ ０２−
ＺｒＯ２はいずれもその表面積が３０７ｙＬ２７ｇ以上
であることが好ましい。T i 02-8 i 02 , T
iO2-ZrO2 and T i 02-8 i 02-
It is preferable that the surface area of ZrO2 is 307yL27g or more.
触ｍＡ成分の組成は酸化物に換算してＴｉＯ２が２０〜
９５モル％、５ｉＯｚもしくはＺＪ’０２またはＳ ｉ
０２とＺｒＯ２の和が５〜８０モル％（いずれもＴｉ
Ｏ２＋ＺｒＯ２＋Ｓ １ｏ２＝１００モル％に対して）
の範囲にあることが好ましい結果を与える。The composition of the contact mA component is TiO2 of 20~20 in terms of oxide.
95 mol%, 5iOz or ZJ'02 or Si
The sum of 02 and ZrO2 is 5 to 80 mol% (both Ti
O2 + ZrO2 + S 1o2 = 100 mol%)
range gives preferable results.
本発明にかかる触媒の組成は酸化物としての重量百分率
でＡ成分が４０〜１００％、Ｂ成分はマンガン（Ｍｎ）
、銀（Ａ！Ｉ＋）、鉄（Ｆｅ ）、コバルト（Ｇｏ）、
亜鉛（Ｚｎ ）およびニッケル（Ｎｉ ）については酸
化物としての重量百分率で０〜６０％、白金（Ｐｔ）、
パラジウム（Ｐｄ ）およびロジウム（Ｒｈ ）につい
ては金属元素として０〜１０重量％の範囲よりなること
が好ましい。The composition of the catalyst according to the present invention is that component A is 40 to 100% by weight as an oxide, and component B is manganese (Mn).
, silver (A!I+), iron (Fe), cobalt (Go),
Zinc (Zn) and nickel (Ni) have a weight percentage of 0 to 60% as oxides, platinum (Pt),
Palladium (Pd) and rhodium (Rh) are preferably contained in a range of 0 to 10% by weight as metal elements.
Ｂ成分が上記範囲外ではオゾンによる殺菌能力が不十分
であり、また、白金、パラジウムおよびロジウムの場合
、原料コストが高くなり十分な効果が発揮できない。If the B component is outside the above range, the bactericidal ability of ozone will be insufficient, and in the case of platinum, palladium, and rhodium, the raw material cost will be high and sufficient effects will not be exhibited.
本発明において用いられるＴｉＯ２−８ｉＯ＋を調製す
るには、まずチタン源として塩化チタン類、硫酸チタン
などの無機性チタン化合物および修酸チタン、テトライ
ソプロピルチタネートなどの有機性チタン化合物などか
ら選ぶことができ、またケイ素源としてはコロイド状シ
リカ、水ガラス、四塩化ケイ素など無機性のケイ素化合
物およびテトラエチルシリケートなど有機ケイ素化合物
などから選ぶことができる。そしてこれら原料中には、
微量の不純物、混入物のあるものがあるが、えられるＴ
ｉＯ２−３ｉＯ２の物性に大きく影響を与えるものでな
い限り問題とならない。To prepare TiO2-8iO+ used in the present invention, first, a titanium source can be selected from inorganic titanium compounds such as titanium chlorides and titanium sulfate, and organic titanium compounds such as titanium oxalate and tetraisopropyl titanate. The silicon source can be selected from inorganic silicon compounds such as colloidal silica, water glass, silicon tetrachloride, and organic silicon compounds such as tetraethyl silicate. And among these raw materials,
Although there may be trace amounts of impurities and contaminants, the T obtained
There is no problem as long as it does not significantly affect the physical properties of iO2-3iO2.
好ましいＴｉＯ＋−８ｉＯ２の調製法としては、以下の
方法が挙げられる。A preferred method for preparing TiO+-8iO2 includes the following method.
■ 四塩化チタンをシリカゾルと共に混合し、アンモニ
アを添加して沈殿を生成せしめ、この沈殿を洗浄、乾燥
後３００〜６５０℃で焼成せしめる方法。(2) A method in which titanium tetrachloride is mixed with silica sol, ammonia is added to form a precipitate, the precipitate is washed, dried, and then calcined at 300 to 650°C.
■ 四塩化チタンにケイ酸ナトリウム水溶液を添加し、
反応せしめて沈殿を生成させ、これを洗浄、乾燥後３０
０〜６５０℃で焼成せしめる方法。■ Add sodium silicate aqueous solution to titanium tetrachloride,
The reaction was carried out to form a precipitate, which was washed and dried for 30 minutes.
A method of firing at 0 to 650°C.
■ 四塩化チタンの水−アルコール溶液にエチルシリケ
ート（（Ｃｚ）−１ｓＯ＞４８ｉ）を添加し加水分解反
応せしめ沈殿を形成させ、これを洗浄、乾燥後３００〜
６５０℃で焼成せしめる方法。■ Add ethyl silicate ((Cz)-1sO>48i) to a water-alcohol solution of titanium tetrachloride to cause a hydrolysis reaction to form a precipitate, which is washed and dried for 300~
A method of firing at 650℃.
■ 酸化塩化チタン（Ｔ ｉ ０ＣＪ２ ）とエチルシ
リケートの水−アルコール溶液にアンモニアを加えて沈
殿を形成せしめ、これを洗浄、乾燥後３００〜６５０℃
で焼成せしめる方法。■ Ammonia is added to a water-alcohol solution of titanium oxide chloride (T i 0CJ2 ) and ethyl silicate to form a precipitate, which is washed and dried at 300-650°C.
A method of firing.
以上の好ましい方法のうちでもとくに■の方法が好まし
く、この方法は具体的には以下のごと〈実施される。す
なわち、上記チタン源およびケイ素源の化合物をＴｉＯ
２とＳｉＯ２のモル比が所定量になるようにとり、酸性
の水溶液状態またはゾル状態でチタンおよびケイ素を酸
化物換算して１〜１ ｏｏｏ ／１の濃度として１０〜
１００℃に保つ。その中へ撹拌上中和剤としてアンモニ
ア水を滴下し、１０分間ないし３時間ｐｔ−１２〜１０
にてチタンおよびケイ素よりなる共沈化合物を生成せし
め、濾別しよく洗浄したのち８０〜１４０℃で１〜１０
時間乾燥し、３００〜６５０℃で１〜１０時間焼成して
ＴｉＯ２−８ｉＯ＋をえることができる。Among the above preferred methods, method (2) is particularly preferred, and this method is specifically carried out as follows. That is, the titanium source and silicon source compounds are replaced by TiO
The molar ratio of 2 and SiO2 is set to a predetermined amount, and the concentration of titanium and silicon in terms of oxides is 10 to 100/1 in an acidic aqueous solution or sol state.
Keep at 100℃. Aqueous ammonia was added dropwise as a neutralizing agent into the solution while stirring, and the mixture was stirred for 10 minutes to 3 hours at pt-12 to 10.
A coprecipitated compound consisting of titanium and silicon was produced at 80-140°C after being filtered and thoroughly washed.
TiO2-8iO+ can be obtained by drying for hours and firing at 300-650°C for 1-10 hours.
また、ＴｉＯ２−８ｉＯ２−Ｚｒ０２にツいテは、Ｔｉ
Ｏ２−８ｉＯ２同様の方法で調製されるものであり、ジ
ルコニウム源として、塩化ジルコニウム、硫酸ジルコニ
ウムなどの無機性ジルコニウム化合物および修酸ジルコ
ニウムなど有機性ジルコニウム化合物のなかから選ぶこ
とができる。Also, regarding TiO2-8iO2-Zr02, Ti
It is prepared in the same manner as O2-8iO2, and the zirconium source can be selected from inorganic zirconium compounds such as zirconium chloride and zirconium sulfate, and organic zirconium compounds such as zirconium oxalate.
すなわち、ジルコニウム化合物をチタン化合物と共に上
述の方法と同様に扱うことによりＴｉＯ２−８ｉ ０２
−Ｚ ｒ０２は容易に調製しうるものである。そして、
このジルコニウムの存在量は、ＴｉＯ２＋Ｓ ｉ０２＋
ＺｒＯ２の合計量に対しＺｒＯ２に換算して３０重量％
までの範囲内にあるのが好ましい。ＴｉＯ２−ＺｒＯ２
の調製法も同様にして行なうことができる。That is, by treating the zirconium compound together with the titanium compound in the same manner as described above, TiO2-8i 02
-Z r02 can be easily prepared. and,
The amount of zirconium present is TiO2+S i02+
30% by weight converted to ZrO2 based on the total amount of ZrO2
It is preferable that it be within the range of . TiO2-ZrO2
can be prepared in the same manner.
上記の方法で調製されたＴｉＯ２−８ｉ０２、Ｔ ｉ
０２−Ｚ ｒｏ２およびＴｉＯ２−８１ｏ２−７ｒＯ２
を用いて、以下に示す方法により完成触媒がえられる。TiO2-8i02 prepared by the above method, Ti
02-Z ro2 and TiO2-81o2-7rO2
A finished catalyst can be obtained by the method shown below.
−例を示せばＴｉＯ＋−８ｉＯ２粉体を成型助剤と共に
加え、適量の水を添加しつつ混合、混練し、押し出し成
型機でペレット状またはハニカム状等に成型する。- For example, TiO+-8iO2 powder is added together with a molding aid, mixed and kneaded while adding an appropriate amount of water, and molded into a pellet or honeycomb shape using an extrusion molding machine.
成型物を５０〜１２０℃で乾燥後３００〜８００℃、好
ましくは３５０〜６００℃で１〜１０時間、好ましくは
２〜６時間空気流通下で焼成して触媒を得ることができ
る。The catalyst can be obtained by drying the molded product at 50 to 120°C and then calcining it at 300 to 800°C, preferably 350 to 600°C, for 1 to 10 hours, preferably 2 to 6 hours under air circulation.
また、ＴｉＯ２−８ｉＯ２にマンガン、鉄、ニッケル、
コバルト、亜鉛、銀、白金、パラジウム、ロジウムを添
加して触媒化する場合、上記金属塩の水溶液をＴｉＯ２
−８ｉＯ２成型体に含浸させて担持した後、乾燥、焼成
することにより触媒とすることができる。In addition, manganese, iron, nickel,
When catalyzing by adding cobalt, zinc, silver, platinum, palladium, or rhodium, the aqueous solution of the above metal salt is TiO2
A catalyst can be obtained by impregnating and supporting a -8iO2 molded body, followed by drying and firing.
一方、別法としてＴｉＯ２−８ｉＯ２粉体に上記金属塩
の水溶液を成型助剤と共に加え、混練成型する方法も採
用できる。On the other hand, as an alternative method, an aqueous solution of the above metal salt may be added to the TiO2-8iO2 powder together with a molding aid, and the mixture may be kneaded and molded.
形状としては上記のペレット状およびハニカム状にとど
まらず円柱状、円筒状、板状、リボン状、波板状、パイ
プ状、ドーナツ状、格子状、その他一体化成型されたも
のが適宜選ばれる。The shape is not limited to the above-mentioned pellet shape and honeycomb shape, but may be suitably selected from columnar, cylindrical, plate, ribbon, corrugated, pipe, donut, lattice, and other integrally molded shapes.
次に、触媒にＡ成分と共に用いられているＢ成分の出発
原料としては、酸化物、水酸化物、無機酸塩、有機酸塩
など、特にアンモニウム塩、修酸塩、硝ｍｓ、硫Ｍ塩ま
たはハロゲン化物などから適宜選ばれる。Next, the starting materials for component B used together with component A in the catalyst include oxides, hydroxides, inorganic acid salts, organic acid salts, etc., especially ammonium salts, oxalates, nitric acid salts, and sulfuric acid salts. or halides, etc., as appropriate.
本発明の方法において、気相中に浮遊する菌を処理する
際、反応条件を適宜選択することにより、実質的に菌の
浮遊しない気相をえることができる。In the method of the present invention, when treating bacteria floating in the gas phase, by appropriately selecting reaction conditions, it is possible to obtain a gas phase in which substantially no bacteria are suspended.
本発明の殺菌方法は、反応温度−１０°〜１６０℃、空
間速度１０００〜１００，０００Ｈｒ−１、オゾン濃度
０．０１１）Ｅｌｌｌｌ 〜１０．０００１）ｌ）ＩＩ
Ｉという条件で実施されるのが好ましい。The sterilization method of the present invention includes a reaction temperature of -10° to 160°C, a space velocity of 1000 to 100,000 Hr-1, and an ozone concentration of 0.011) to 10.0001) l) II
It is preferable to carry out under the conditions of I.
本発明による殺菌方法は、対象として広汎に使用できる
が、例えば食品工場、製薬工場、給食センター、調理室
、病院等の空気中の浮遊菌の処理に使用できるとともに
、一般家庭、ビルディングのあらゆる空間の空気清浄に
有効である。The sterilization method according to the present invention can be used in a wide range of applications, including for treating airborne bacteria in food factories, pharmaceutical factories, school lunch centers, kitchens, hospitals, etc. It is effective for air purification.
本発明方法を用いれば空気中に浮遊する菌であればいず
れも殺菌することができる。具体的に示せば、シュード
モナス属（Ｐｓｅｕｄｏｍｏｎａｓ）、クサントモナス
属（Ｘａｎｔｈｏｍｏｎａｓ）、アセトバクター属（＾
ＣｅｔＯｂａＣｔｅｒ）等のダラム陰性好気性桿菌また
は球菌；エシェリキア属（Ｅｓｃｈｅｒｉｃｈｉａ）
、サルモネラ属（ＳａｌｌＯｎｅｌｌａ） 、ビブリオ
属（Ｖｉｂｒｉｏ）等のダラム陰性通性嫌気性桿菌：ミ
クロコツカス属（肛旺虹並図貝、スタヒロコツカス属（
５ｔａｐｈｙｌ。Using the method of the present invention, any bacteria floating in the air can be sterilized. Specifically, the genus Pseudomonas, the genus Xanthomonas, and the genus Acetobacter (^
Durham-negative aerobic bacilli or cocci such as CetObaCter; Escherichia spp.
Durham-negative facultative anaerobic bacilli such as , Salmonella , Vibrio , Micrococcus spp.
5taphyl.
ｃｏｃｃｕｓ） 、ストレプトコツカス属（５ｔｒｅｐ
ｔ。coccus), Streptococcus (5trep
t.
ｏｃｃｕｓ）等のグラム陽性球菌；バチルス属（Ｂａｃ
ｉｌｌｕｓ） 、クロストリブラム属（Ｃｌ０８ｔｒｉ
虹す）等の内生胞子形成桿菌：ラクトバチルス属（Ｌａ
ｃｔｏｂａｃ ｉ Ｉ １ｕｓ）等のダラム陽性内生胞
子非形成桿菌：アクチノマイセスｊＩ（ＡＣｔｉｎｏｌ
ｙＣｅＳ）、ストレプトマイセス属（Ｓｔｒｅｐｔｏｍ
ｙｃｅｓ）等の放線菌：カンディダ属（Ｃａｎｄｉｄａ
）、アスペルジルス属（Ａｓｐｅｒｇｉｌｌｕｓ）、ベ
ニシリウス属（Ｐｅｎｉｃｉｌｌｉｕｓ）等の真菌；ア
デノウィルス属（＾ｄｅｎｏｖｉｒｕｓ） 、ロタウィ
ルス属（ＲＯｔａＶ＋ｒＵ３）、インフルエンザウィル
スｉｌｊ （Ｉｎｆｌｕｅｎｚａｖｉｒｕｓ） 、レト
ロウィルス科（Ｒｅｔｒｏｖｉｒｕｓ）等のウィルスが
挙げられる。Gram-positive cocci such as Bacillus occus;
illus), Clostribram (Cl08tri
Endospore-forming bacilli such as Lactobacillus (La
Durum-positive non-endospore-forming bacilli such as ctobac i I 1us): Actinomyces jI (ACtinol
yCeS), Streptomyces spp.
yces) and other actinomycetes: Candida spp.
), fungi such as Aspergillus and Penicillius; adenovirus, rotavirus (ROtaV+rU3), influenza virus, and Retrovirus. Viruses such as .
〈実 施 例〉
以下に実施例を用いて本発明をさらに詳細に説明するが
、本発明はこれらの実施例のみに限定されるものではな
い。<Examples> The present invention will be explained in more detail using Examples below, but the present invention is not limited to these Examples.
実施例 １
チタンおよびケイ素からなる複合酸化物を以下に述べる
方法で調製した。チタン源として以下の組成を有する硫
酸チタニルの硫酸水溶液を用いた。Example 1 A composite oxide consisting of titanium and silicon was prepared by the method described below. A sulfuric acid aqueous solution of titanyl sulfate having the following composition was used as a titanium source.
Ｔ ｔ ０８０４ （ＴｉＯ２換算） ２５０ｕ／
ｊ！全Ｈ２ＳＯ４１１００ｏ／ｊ！
別に水４０Ｊにアンモニア水＜ＮＨｓ 、２５％）２８
ｊ！を添加し、これにスノーテックス−ＮＣ８−３０（
１産化学製シリカゾル、５ｉ０２として約３０重量％含
有＞２．４Ｋｇを加えた。得られた溶液中に、上記硫酸
チタニルの硫酸水溶液１５．３ｊ！を水３０１に添加し
て稀釈したチタン含硫酸水溶液を撹拌下体々に滴下し、
共沈ゲルを生成した。T t 0804 (TiO2 conversion) 250u/
j! All H2SO41100o/j! Separately, add 40 J of water to ammonia water <NHs, 25%) 28
j! and Snowtex-NC8-30 (
Silica sol manufactured by Ichisan Kagaku Co., Ltd., containing approximately 30% by weight of 5i02 (>2.4 kg) was added. In the obtained solution, 15.3j of the above sulfuric acid aqueous solution of titanyl sulfate was added! A titanium-containing sulfuric acid aqueous solution diluted by adding 301% of water was added dropwise to the body while stirring,
A coprecipitated gel was produced.
さらにそのまま１５時間放置して静置した。かくして得
られたＴｉＯ２−８ｉＯ２ゲルを濾過、水洗後２００℃
で１０時間乾燥した。Further, it was left as it was for 15 hours. The thus obtained TiO2-8iO2 gel was filtered and washed with water at 200°C.
It was dried for 10 hours.
次いで５５０℃で６時間空気雰囲気下で焼成した。得ら
れた粉体の組成はＴｉＯ２：Ｓ １ｏ２＝４＝１（モル
比）で、ＢＥＴ表面積は１８５ＴｒＬ２／ｇであった。Then, it was fired at 550° C. for 6 hours in an air atmosphere. The composition of the obtained powder was TiO2:S 1o2=4=1 (molar ratio), and the BET surface area was 185TrL2/g.
ここで得られた粉体を以降ＴＳ−１と呼び、この粉体を
用いて以下に述べる方法で触媒を調製した。The powder thus obtained was hereinafter referred to as TS-1, and a catalyst was prepared using this powder by the method described below.
上記ＴＳ−１粉体１．ＯＫｓに微結晶性セルロース（旭
化成工業■製、商品名：アビセル）２０ｇを適当量の水
と共に加え、ニーダ−でよく混合、混練した後、押し出
し成型機で直径３．０ ｔｔｍ １長さ３、０１１１１
のベレットに成型し、１００℃で１０時間乾燥後５００
℃で６時間空気雰囲気下で焼成し、ＴｉＯ２−８ｉＯ２
からなる触媒を得た。Above TS-1 powder 1. Add 20 g of microcrystalline cellulose (manufactured by Asahi Kasei Kogyo ■, trade name: Avicel) to the OKs along with an appropriate amount of water, mix and knead well with a kneader, and then use an extrusion molding machine to form a mold with a diameter of 3.0 ttm and a length of 3. 01111
After molding into pellets and drying at 100℃ for 10 hours,
℃ under air atmosphere for 6 hours to obtain TiO2-8iO2
A catalyst consisting of
実施例 ２
Ｔ ｉ ０２−ＺｒＯ２を以下に述べる方法で調製した
。Example 2 T i 02-ZrO2 was prepared by the method described below.
水１００ｊ！にオキシ塩化ジルコニウム（ＺｒＯＣＪ１
２ ・８Ｈ２０）１．９３Ｋｙを溶解させ、実施例１で
用いたのと同じ組成の硫酸チタニルの硫酸水溶液７．８
ｊ！を添加しつつよく混合する。これを温度的３０℃に
維持しつつよく撹拌しながらアンモニア水を徐々に滴下
し、ｐＨが７になるまで加え、さらにそのまま放置して
１５時間静置した。Water 100j! Zirconium oxychloride (ZrOCJ1
2 ・8H20) 1.93Ky was dissolved in a sulfuric acid aqueous solution of titanyl sulfate having the same composition as used in Example 1.
j! Add and mix well. While maintaining the temperature at 30°C and stirring well, aqueous ammonia was gradually added dropwise to the mixture until the pH reached 7, and the mixture was left to stand still for 15 hours.
かくして得られたＴ ｉ ０２−Ｚ ｒｏ２グルを濾過
し水洗後２００℃で１０時間乾燥した。次いで空気雰囲
気下で５５０℃で６時間焼成した。得られた粉体の組成
はＴｉＯ２：Ｚｒ０２＝４：１（モル比）であり、ＢＥ
Ｔ表面積は１４０ｍ ／ｇであった。ここで得られた
粉体を以降ＴＺ−１と呼ぶ。The T i 02-Z ro2 gel thus obtained was filtered, washed with water, and then dried at 200° C. for 10 hours. Then, it was fired at 550° C. for 6 hours in an air atmosphere. The composition of the obtained powder was TiO2:Zr02=4:1 (molar ratio), and BE
The T surface area was 140 m /g. The powder obtained here is hereinafter referred to as TZ-1.
ＴＺ−１を用いて実施例１の記載の方法に準じてＴ ｉ
０２−Ｚ ｒｏ２からなる触媒を調製した。T i according to the method described in Example 1 using TZ-1
A catalyst consisting of 02-Z ro2 was prepared.
実施例 ３
実施例１及び２の方法に準じてＴｉＯ２−８ｉ０２−Ｚ
ｒ０２を調製した。得られた粉体の組成はＴｉＯ２：５
ｉ０２：Ｚｒ０２＝８０：１６：４（モル比）で、ＢＥ
Ｔ表面積は１８０ｍ ／（＋であった。これで得られ
た粉体を以降ＴＳＺ−１と呼ぶ。Example 3 TiO2-8i02-Z according to the method of Examples 1 and 2
r02 was prepared. The composition of the obtained powder was TiO2:5
i02:Zr02=80:16:4 (molar ratio), BE
The T surface area was 180 m 2 /(+). The powder thus obtained was hereinafter referred to as TSZ-1.
ＴＳＺ−１を用いて実施例１の記載の方法に準じｒＴ
ｉ ０２−８ ｉ ０２−Ｚ ｒｏ２からなる触媒を調
製した。rT according to the method described in Example 1 using TSZ-1
A catalyst consisting of i 02-8 i 02-Z ro2 was prepared.
実施例 ４
実施例１で用いたのと同じＴＳ−１粉体１．ＯＫｇに硝
硫マンガンＭｎ （ＮＯ３）２−６８２００、３６６
Ｋ９を含む水溶液を加え、ニーダ−で適当量の水を添加
しつつよく混合、混練した後、実施例１と同様にしてペ
レット状に成型し、乾燥、焼成して、酸化物としての重
量比でＴＳ−１：Ｍｎ０２＝９０：１０の組成を有する
触媒を得た。Example 4 The same TS-1 powder 1 as used in Example 1. Manganese nitrate sulfate Mn (NO3)2-68200, 366 in OKg
After adding an aqueous solution containing K9 and thoroughly mixing and kneading it with a kneader while adding an appropriate amount of water, it was formed into pellets in the same manner as in Example 1, dried and fired, and the weight ratio as an oxide was determined. A catalyst having a composition of TS-1:Mn02=90:10 was obtained.
実施例 ５
実施例１で得られたＴｉＯ２−８ｉＯｓ＋からなる触媒
（３ｓφＸ３ｓＬ）５００ｚにパラジウム（Ｐｄ ）と
して３．５ｇを含む硝酸パラジウム水溶液１４０ａ：を
蒸発皿にとり充分混合して含浸させ湯浴上で濃縮乾固し
１２０℃で５時間乾燥した。Example 5 A palladium nitrate aqueous solution 140a containing 3.5 g of palladium (Pd) was placed in an evaporating dish and thoroughly mixed to impregnate the catalyst (3sφX3sL) 500z made of TiO2-8iOs+ obtained in Example 1, and then heated on a hot water bath. It was concentrated to dryness and dried at 120°C for 5 hours.
次いで空気雰囲気下で４００℃、３時間電気炉で焼成し
た。Then, it was fired in an electric furnace at 400° C. for 3 hours in an air atmosphere.
得られた触媒の組成はＴＳ−１：ｐｄ ＝９９ ：１、
Ｏ（重量比）であった。The composition of the obtained catalyst was TS-1:pd =99:1,
O (weight ratio).
実施例 ６
実施例１〜５で得られた各触媒について次のような方法
で殺菌率を求めた。Example 6 The sterilization rate was determined for each catalyst obtained in Examples 1 to 5 using the following method.
内径２０履の反応管に直径３．０ ａｍ、長さ３．０Ｍ
のベレット状触媒１０．５ ａ：を充填し、大腸菌を３
６２０個／ｊ！含有する空気を０．１０１０５Ｎ／Ｈｒ
の流速（空間速度１０．０００Ｈｒ−１）で触媒層に導
入した。触媒層入口側にオゾンを３０ ｐｐｍ導入し、
反応温度２５℃での殺菌率を求めた。A reaction tube with an inner diameter of 20 mm has a diameter of 3.0 am and a length of 3.0 m.
of pellet-shaped catalyst 10.5 a: and E. coli 3
620 pieces/j! Containing air 0.10105N/Hr
was introduced into the catalyst layer at a flow rate of (space velocity 10.000 Hr-1). Introducing 30 ppm of ozone to the inlet side of the catalyst layer,
The sterilization rate was determined at a reaction temperature of 25°C.
殺菌率は次式により求めた。The sterilization rate was calculated using the following formula.
殺菌率（Ｘ）＝ 但し生菌数の測定はコロニー形成数で行った。Sterilization rate (X) = However, the number of viable bacteria was measured by the number of colonies formed.
得られた結果を表−１に示す。The results obtained are shown in Table-1.
表 −１
１９一
実施例 ７
実施例６において大腸菌を含有する空気の代わりに、ア
スベルジルス・ニガーの胞子を３５００個／１含有する
空気を用いた以外は実施例６におけると同様にして殺菌
率を求めた。得られた結果を表−２に示す。Table 1 19-Example 7 The sterilization rate was determined in the same manner as in Example 6 except that air containing 3500 Asbergilus niger spores/1 was used instead of the air containing Escherichia coli in Example 6. I asked for it. The results obtained are shown in Table-2.
表 −２Table-2
Claims (1)
殺菌する方法において、該ガス流路に触媒を設置し、オ
ゾンを導入すること を特徴とする殺菌方法。(1) A sterilization method for decomposing and sterilizing bacteria by introducing ozone into a gas phase in which bacteria are suspended, which is characterized by installing a catalyst in the gas flow path and introducing ozone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62254604A JPH0197461A (en) | 1987-10-12 | 1987-10-12 | Sterilizing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62254604A JPH0197461A (en) | 1987-10-12 | 1987-10-12 | Sterilizing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0197461A true JPH0197461A (en) | 1989-04-14 |
| JPH0556984B2 JPH0556984B2 (en) | 1993-08-20 |
Family
ID=17267341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62254604A Granted JPH0197461A (en) | 1987-10-12 | 1987-10-12 | Sterilizing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0197461A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2485546A (en) * | 2010-11-17 | 2012-05-23 | Steritrox Ltd | Catalyst for use in a sterilisation and/or decontamination process |
| US8867258B2 (en) | 2010-03-22 | 2014-10-21 | Qualcomm Incorporated | Memory cell that includes multiple non-volatile memories |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56113327A (en) * | 1980-02-14 | 1981-09-07 | Mitsubishi Electric Corp | Odorous gas treatment apparatus |
| JPS56130209A (en) * | 1980-03-17 | 1981-10-13 | Mitsubishi Heavy Ind Ltd | Malodor removing method |
| JPS60155503A (en) * | 1984-01-20 | 1985-08-15 | Shinryo Air Conditioning Co Ltd | Decomposition of ozone |
-
1987
- 1987-10-12 JP JP62254604A patent/JPH0197461A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56113327A (en) * | 1980-02-14 | 1981-09-07 | Mitsubishi Electric Corp | Odorous gas treatment apparatus |
| JPS56130209A (en) * | 1980-03-17 | 1981-10-13 | Mitsubishi Heavy Ind Ltd | Malodor removing method |
| JPS60155503A (en) * | 1984-01-20 | 1985-08-15 | Shinryo Air Conditioning Co Ltd | Decomposition of ozone |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8867258B2 (en) | 2010-03-22 | 2014-10-21 | Qualcomm Incorporated | Memory cell that includes multiple non-volatile memories |
| GB2485546A (en) * | 2010-11-17 | 2012-05-23 | Steritrox Ltd | Catalyst for use in a sterilisation and/or decontamination process |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0556984B2 (en) | 1993-08-20 |
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