JP2006026194A - Organic matter removing apparatus - Google Patents
Organic matter removing apparatus Download PDFInfo
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- JP2006026194A JP2006026194A JP2004211207A JP2004211207A JP2006026194A JP 2006026194 A JP2006026194 A JP 2006026194A JP 2004211207 A JP2004211207 A JP 2004211207A JP 2004211207 A JP2004211207 A JP 2004211207A JP 2006026194 A JP2006026194 A JP 2006026194A
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- 239000005416 organic matter Substances 0.000 title abstract description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000011941 photocatalyst Substances 0.000 claims description 36
- 239000000126 substance Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 22
- 238000012545 processing Methods 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 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 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 230000009471 action Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 244000144972 livestock Species 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
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Abstract
Description
本発明は、空気や水の処理に関し、特に限定されるものではないが、主に大気中に含まれる揮発性有機物（ＶＯＣ）、臭気成分、細菌類等の人体に有害な成分を分解して清浄な空気に浄化する目的や、上下水道や、スイミングプール、し尿、産業排水、農畜産排水、ゴミ埋立地浸出水等の排水に含まれる、臭気、着色物質、環境ホルモン等の有害有機物や細菌類の処理方法として有用な有機物除去装置に関するものである。 The present invention relates to the treatment of air and water, but is not particularly limited, but mainly decomposes components harmful to the human body such as volatile organic substances (VOC), odorous components and bacteria contained in the atmosphere. Harmful organic substances such as odors, coloring substances, environmental hormones, and bacteria contained in wastewater such as water and sewage, swimming pools, human waste, industrial wastewater, agricultural and livestock wastewater, landfill leachate, etc. The present invention relates to an organic substance removing apparatus useful as a processing method for a kind.
従来の有機物除去装置は、例えば下水二次処理水や工場排水等の処理において、被処理水中の難分解性有機物の除去を行う場合、強力な酸化力を有するＯＨラジカルを生成してこれを効果的に活用する手段としてオゾンと紫外線を併用した処理法が知られている（例えば、特許文献１参照）。この処理装置の概略を図５に示す。図５において、１はオゾン発生装置、２はオゾン、３はエゼクタ、４は被処理水、５は反応塔、６は紫外線照射装置、７は処理水である。
オゾン発生装置１で生成されたオゾン２はエゼクタ３により被処理水中４に注入され、オゾンが溶解した気泡混合状態の被処理水は反応塔５に送られる。反応塔内では紫外線照射装置６から照射された紫外線によって生成されたＯＨラジカルにより被処理水中の有機物質が酸化分解され、清浄な処理水７が得られるといったものである。
また、有機物を分解・除去する目的として前例と同様ではあるが、液体または気体中の有機物を除去する方法として、紫外線照射により光触媒表面で活性化して生じるＯＨラジカルの作用を有効に利用した処理法がある。さらに光触媒の反応機構については、ＯＨラジカルの生成と同時に過酸化水素が生成し、これも有機物との反応に寄与しているとの報告もある。
このような光触媒反応装置については中空管の内部に光触媒活性を有する材料を担持させた立体的な網目構造を有する多孔質セラミックを充填し、これに紫外線を照射するものがある（例えば、特許文献２参照）。
この装置の概略を図６に示す。図６において、８は中空管、９は触媒担持体である。触媒担持体には酸化チタン等の光触媒がコーティングされている。なお、共通する符号については、同じ機能を示すため説明を省略する。
浄化の機構について説明する。被処理水４は、中空管８内に固定された触媒担持体９を通過する際、紫外線照射装置６により照射された紫外線と光触媒の作用により、被処理水中の有機物が分解され、清浄な処理水７が得られるといったものである。
このように、従来の有機物除去装置は、オゾンと紫外線または光触媒の作用を利用した構成となっていた。
The ozone 2 generated by the ozone generator 1 is injected into the water to be treated 4 by the ejector 3, and the water to be treated in a bubble mixed state in which ozone is dissolved is sent to the reaction tower 5. In the reaction tower, organic substances in the water to be treated are oxidatively decomposed by OH radicals generated by the ultraviolet rays irradiated from the
In addition, as the method of decomposing / removing organic matter, the same as the previous example, but as a method of removing organic matter in liquid or gas, a treatment method that effectively utilizes the action of OH radicals generated by activation on the photocatalyst surface by ultraviolet irradiation. There is. Furthermore, as for the reaction mechanism of the photocatalyst, there is a report that hydrogen peroxide is generated simultaneously with the generation of OH radicals, which also contributes to the reaction with organic matter.
With respect to such a photocatalytic reaction device, there is one in which a hollow ceramic is filled with a porous ceramic having a three-dimensional network structure in which a material having photocatalytic activity is supported, and this is irradiated with ultraviolet rays (for example, patents) Reference 2).
An outline of this apparatus is shown in FIG. In FIG. 6, 8 is a hollow tube and 9 is a catalyst carrier. The catalyst carrier is coated with a photocatalyst such as titanium oxide. In addition, about a common code | symbol, since it shows the same function, description is abbreviate | omitted.
The purification mechanism will be described. When the water to be treated 4 passes through the catalyst carrier 9 fixed in the hollow tube 8, the organic matter in the water to be treated is decomposed by the action of the ultraviolet rays and the photocatalyst irradiated by the
Thus, the conventional organic substance removing apparatus has a configuration using the action of ozone and ultraviolet light or a photocatalyst.
従来のオゾンと紫外線を併用した装置は、強力な処理性能を有するものの、オゾン発生時には原料ガスの生成工程も含めると大きな電力を要するため、汚染度合が比較的軽微または強力な処理が不要である場合は、オゾン処理を停止し別の手法で代替できることが望ましい。ところが、従来のオゾンと紫外線とを組み合わせた促進酸化手法では、オゾンの発生を停止した際、紫外線による殺菌効果はあるものの、脱臭や有機物分解等の効果はほとんど期待できないものであった。
一方、光触媒装置による反応は、紫外線が照射された光触媒表面でのみ起こるので、反応効率は接触面積に対する依存率が高い。三次元空間で効率良く処理を行うためには透過性の良好な触媒担持体の採用や、空隙を小さくし接触効率を向上させる等の措置が必要であるが、諸々の課題があるため未だこれらを満足できるような材料の開発には至っていない。このため光触媒における除去効率はあまり高くなく、処理には時間を要する問題があった。
本発明はこのような問題点に鑑みてなされたものであり、オゾン、紫外線、光触媒、オゾン反応触媒のそれぞれの作用を効果的に併用することにより、処理効率が高く、かつオゾン発生装置もしくは紫外線照射装置を停止した場合においても、一定の浄化機能を維持できる低コストの有機物除去装置を提供することを目的とする。
Although conventional ozone / ultraviolet combined devices have powerful processing performance, they require a large amount of power when ozone is generated, including the raw material gas generation process, so that the degree of contamination is relatively light or does not require powerful processing. In this case, it is desirable that the ozone treatment can be stopped and replaced by another method. However, in the conventional accelerated oxidation method combining ozone and ultraviolet rays, when ozone generation is stopped, there are sterilization effects by ultraviolet rays, but effects such as deodorization and organic matter decomposition can hardly be expected.
On the other hand, since the reaction by the photocatalyst device occurs only on the surface of the photocatalyst irradiated with ultraviolet rays, the reaction efficiency is highly dependent on the contact area. In order to perform the treatment efficiently in a three-dimensional space, measures such as the use of a catalyst carrier with good permeability and the reduction of voids to improve contact efficiency are necessary. Development of materials that can satisfy the requirements has not been achieved. For this reason, the removal efficiency in the photocatalyst is not so high, and there is a problem that it takes time for the treatment.
The present invention has been made in view of such problems. By effectively using ozone, ultraviolet rays, a photocatalyst, and an ozone reaction catalyst in combination, the treatment efficiency is high, and an ozone generator or ultraviolet ray is used. An object of the present invention is to provide a low-cost organic substance removing device capable of maintaining a certain purification function even when the irradiation device is stopped.
上記問題を解決するため、本発明は次のように構成したものである。
請求項１に記載の発明は、オゾン発生装置と、前記オゾン発生装置より発生したオゾンと被処理流体とを混合するオゾン混合装置と、前記被処理流体とオゾンとを反応処理させる反応塔と、前記反応塔内に設けられ前記被処理流体に紫外線を照射する紫外線照射装置とから構成される有機物除去装置において、前記反応塔内に三次元網目構造または多孔質構造の光触媒層およびオゾン反応触媒層の二層からなる触媒担持体を設けるとともに、前記被処理流体の除去対象物の濃度または強度を計測するセンサを設け、前記センサの計測値により前記オゾン発生装置と前記紫外線照射装置を同時あるいは一方だけの運転に切り替えて制御するものである。
請求項２に記載の発明は、前記光触媒の材料が、酸化チタン、酸化タングステン、酸化亜鉛、酸化スズおよび酸化タンタルの少なくとも一種から選択されるものである。
前記光触媒において、光触媒機能を有する材料が、酸化チタン、酸化タングステン、酸化亜鉛、酸化スズおよび酸化タンタルの一種または二種以上から選択されるものである。
請求項３に記載の発明は、前記オゾン反応触媒の材料が、マンガン、鉄、コバルト、ニッケル、セリウム、タングステン、銅、銀、金、白金、パラジウム、ロジウム、ルテニウムおよびイリジウムの少なくとも一種またはその化合物から選択されるものである。
請求項４に記載の発明は、前記紫外線照射装置と前記触媒担持体からなる構成を１ユニットとし、処理量や負荷に適応してこれを複数組み合わせたものである。
In order to solve the above problems, the present invention is configured as follows.
The invention according to claim 1 is an ozone generator, an ozone mixing device that mixes ozone generated from the ozone generator and a fluid to be treated, a reaction tower that reacts the fluid to be treated and ozone, In the organic substance removing apparatus, which is provided in the reaction tower and configured to irradiate the fluid to be treated with ultraviolet rays, a photocatalyst layer having a three-dimensional network structure or a porous structure and an ozone reaction catalyst layer in the reaction tower And a sensor for measuring the concentration or strength of the object to be removed of the fluid to be treated, and the ozone generator and the ultraviolet irradiation device can be used simultaneously or in accordance with the measured value of the sensor. The control is switched to only driving.
In the invention described in claim 2, the material of the photocatalyst is selected from at least one of titanium oxide, tungsten oxide, zinc oxide, tin oxide and tantalum oxide.
In the photocatalyst, the material having a photocatalytic function is selected from one or more of titanium oxide, tungsten oxide, zinc oxide, tin oxide and tantalum oxide.
The invention according to claim 3 is that the material of the ozone reaction catalyst is at least one of manganese, iron, cobalt, nickel, cerium, tungsten, copper, silver, gold, platinum, palladium, rhodium, ruthenium and iridium or a compound thereof Is selected from.
In a fourth aspect of the present invention, the unit composed of the ultraviolet irradiation device and the catalyst carrier is made into one unit, and a plurality of these are combined in accordance with the processing amount and load.
請求項１記載の発明によれば、反応塔内に三次元網目構造または多孔質構造の光触媒層およびオゾン反応触媒層の二層からなる触媒担持体を設けたので、触媒の表面において有機物の酸化分解反応が早まり処理効率が向上する。また、触媒担持体は三次元網目構造または多孔質構造状であるため、紫外線、被処理流体およびオゾンとの接触効率が高く、効果的に光触媒反応やオゾン反応が行われる。また、オゾンと紫外線、オゾンとオゾン反応触媒および光触媒による全ての反応工程を１槽で行うため、付帯設備が削減されコンパクトな構造になる。また、触媒の清掃作業を同時に行えるため、作業が容易かつ短時間にでき、ランニングコストを低減化できる。
請求項２記載の発明によれば、光触媒の材料が通常使用される酸化チタン以外のものも選択できるので、触媒性能の向上、性能の長期安定化、成形性の向上、原料コストの低減等が可能である。また、異種特性を利用することにより、複数の種類からなる除去対象物質に対して選択的に反応を行う等の手段をとることができる。
請求項３記載の発明によれば、オゾン反応触媒の材料を、通常使用されるマンガン酸化物以外のものにも選択できるので、触媒性能の向上、性能の長期安定化、成形性の向上、原料コストの低減等ができる。
請求項４記載の発明によれば、紫外線照射装置と触媒担持体からなる構成を１ユニットにしているので、設計または構造上、処理量や負荷量への対応が容易になり、コンパクトになるとともにコストの低減にもつながる。
According to the first aspect of the present invention, since the catalyst carrier comprising two layers of the photocatalyst layer having a three-dimensional network structure or a porous structure and the ozone reaction catalyst layer is provided in the reaction tower, the oxidation of organic substances on the surface of the catalyst is performed. The decomposition reaction is accelerated and the processing efficiency is improved. Further, since the catalyst carrier has a three-dimensional network structure or a porous structure, the contact efficiency with ultraviolet rays, a fluid to be treated and ozone is high, and a photocatalytic reaction and an ozone reaction are effectively performed. In addition, since all reaction steps using ozone and ultraviolet light, ozone and ozone reaction catalyst, and photocatalyst are performed in one tank, the incidental facilities are reduced and the structure becomes compact. In addition, since the catalyst can be cleaned simultaneously, the operation can be performed easily and in a short time, and the running cost can be reduced.
According to the invention of claim 2, since the photocatalyst material can be selected other than the titanium oxide which is usually used, the catalyst performance is improved, the performance is stabilized for a long time, the moldability is improved, the raw material cost is reduced, etc. Is possible. Further, by utilizing different characteristics, it is possible to take measures such as selectively reacting with a plurality of types of substances to be removed.
According to the invention described in claim 3, since the material of the ozone reaction catalyst can be selected from those other than the manganese oxide that is usually used, the catalyst performance is improved, the performance is stabilized for a long time, the moldability is improved, and the raw material Cost can be reduced.
According to the invention described in claim 4, since the configuration including the ultraviolet irradiation device and the catalyst carrier is made into one unit, it is easy to cope with the processing amount and the load amount in terms of design or structure, and it becomes compact. It also leads to cost reduction.
以下、本発明の実施の形態について図を参照して説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
図１は、本発明の有機物除去装置の概略図である。図において、10は被処理空気、11はオゾン混合装置、12は光触媒層、13はオゾン反応触媒層、14は処理空気、15は隔壁、16は除去対象物計測センサである。なお、同じ機能のものは、同じ符号を付しているため、前出のものは説明を省略する。
本発明が特許文献１と異なる部分は、紫外線照射装置６の外周に光触媒層１２とオゾン反応触媒層１３の性質の異なる二層の触媒で形成した三次元網目または多孔質構造状からなるセラミックス触媒担持体を設置したことであり、特許文献２と異なる部分は、光触媒とオゾン反応触媒層１３の性質の異なる二層の触媒で形成したことである。なお、光触媒層１２を紫外線照射側に、オゾン反応触媒層１３はその反対側になるように配置している。
また、双方とも異なる点は除去対象物の濃度または強度を計測するセンサを設け、計測値によりオゾン発生装置１と紫外線照射装置６を同時あるいは一方だけの運転に切り替えて制御するように構成している点である。
同触媒担時体９に酸化チタン等の光触媒層１２や酸化マンガン等のオゾン反応触媒層１３の異性質の触媒をコーティングしている。この場合、スパッタリングや、ガスの燃焼炎やプラズマ炎を利用した被覆法等がある。本構成においては触媒担持体９の内部までコーティングする必要があるため、触媒に浸漬して添着後、焼付け時の温度差を利用して焼付け温度が高い触媒から順に焼付けて被覆する。
異性質触媒層の構成は、図２のような構造や、図３のように接触効率を高めるために隔壁15を設けて流路を延長している。触媒層の厚みについては任意に変更することができる。
水処理においてオゾン混合装置１１を選択する場合は、オゾン混合直後のオゾン溶解量を高める手段として、ディフューザよりもエゼクタ等のインラインによるオゾン混合装置を採用する方が有効である。その後段にスタティックミキサ等の混合手段を付加すればさらなる混合効率の向上を図ることができる。
FIG. 1 is a schematic view of an organic matter removing apparatus of the present invention. In the figure, 10 is air to be treated, 11 is an ozone mixing device, 12 is a photocatalyst layer, 13 is an ozone reaction catalyst layer, 14 is treatment air, 15 is a partition, and 16 is an object measurement sensor. In addition, since the thing with the same function attaches | subjects the same code | symbol, description of the previous thing is abbreviate | omitted.
The portion where the present invention is different from Patent Document 1 is a ceramic catalyst having a three-dimensional network or porous structure formed by two layers of catalysts having different properties of the
Also, the difference between the two is that a sensor for measuring the concentration or intensity of the object to be removed is provided, and the ozone generator 1 and the
The catalyst carrier 9 is coated with an isomer catalyst such as a
The structure of the isomer catalyst layer has a structure as shown in FIG. 2 and a partition 15 for extending the flow path in order to increase the contact efficiency as shown in FIG. The thickness of the catalyst layer can be arbitrarily changed.
When the ozone mixing device 11 is selected in water treatment, it is more effective to adopt an in-line ozone mixing device such as an ejector than a diffuser as means for increasing the amount of ozone dissolved immediately after ozone mixing. If mixing means such as a static mixer is added to the subsequent stage, the mixing efficiency can be further improved.
つぎに、本実施例の動作について説明する。
本実施例は、水等の液体または空気等の気体ともに同様の効果を有するが、空気中のＶＯＣ、臭気物質、細菌類を除去対象物質とし、これらを分解・除去する。
被処理空気10はオゾン混合装置11において、オゾン発生装置１から供給されるオゾン２と混合し、反応塔５の触媒担持体９の内方に送られる。紫外線照射装置６と触媒担持体間の三次元空間中において紫外線を浴びることにより混合気体中のオゾンが分解してＯＨラジカルが生成する。このときオゾン、ＯＨラジカル等の活性種により被処理空気中の除去対象物質が効果的に分解される。この空間で一定時間滞留した被処理空気は三次元網目状の触媒担持体９の細孔を抜けて外方に移動する。そのとき光触媒層12表面に接触あるいは吸着した除去対象物は、光触媒層表面に生成するＯＨラジカルの作用によりさらに分解が進行する。
紫外線の届かないオゾン反応触媒層13を通過する際、この触媒と接触したオゾンは分解すると同時に、ＯＨラジカル等の活性種が生成する。ここでさらに除去対象物質は酸化分解反応が進行するとともに、残存したオゾンは完全に酸素に分解するため、処理空気中14に有害な濃度のオゾンが残存することを防止することができる。
なお、予め処理の前段で被処理空気中の水分量を任意に維持するような手段を付設することにより、オゾン発生装置運転時や光触媒におけるＯＨラジカルの生成効率を向上させることができる。
また、被処理空気中に存在する除去対象物質の濃度や強度を計測する除去対象物計測センサ16を設け、これを計測することにより所要処理条件を算出してオゾンの発生量や紫外線照射量を調節することが可能である。しかしながらオゾンの発生には原料ガスのコストを伴うため、気中の汚染量が比較的少ない場合においてはオゾン発生装置を停止すれば良い。この場合でも光触媒による一定の浄化機能は維持することができる。
付着物により触媒機能が低下した際は、触媒担持体を取り外して表面を洗浄することにより、両触媒の機能を回復させることができる。
本発明の作用・効果を整理するとつぎのようになる。
（１）〔オゾン＋紫外線〕処理
先に触れたように、紫外線照射装置と中空体間の空間において、オゾンと紫外線（低圧水銀ランプによる２５４ｎｍ波長の紫外線）との併用により、オゾンが分解し過酸化水素の生成を経てＯＨラジカルが生成する。このとき水中へのオゾン溶解量が大きく紫外線による分解率が大きいほどＯＨラジカルの生成量は大きい。ＯＨラジカルの作用は前述したように酸化還元電位が２．８５Ｖ（酸性下）とオゾンの２．０７（酸性下）よりも高く、強い酸化力により有機物を最終的には二酸化炭素と水にまで分解することができる。
（２）〔オゾン＋オゾン反応触媒〕処理
オゾンがこの触媒と接触するとオゾンが分解すると同時に、ＯＨラジカル等の活性種が生成し、触媒の表面において有機物の酸化分解反応が進行する。
（３）光触媒処理
光照射により光触媒表面では周辺に存在する水の水酸イオンから電子を引き抜き、ＯＨラジカルを生成する。このため光触媒表面に有機物が接触するとＯＨラジカルの作用により分解される。また、光触媒面からは紫外線照射により過酸化水素が生成することが知られており、オゾンとの相乗効果が期待できる。
また、処理の状況によりオゾン発生装置を停止しても、上記(3)の作用は維持することができる。もしくは紫外線照射装置を停止しても上記(2)の作用は維持することができる。
さらに、触媒担持体を光触媒とオゾン反応触媒の別々の特性を有する二層の触媒体で形成することにより、次の効果が得られる。
・オゾン＋紫外線、オゾン＋オゾン反応触媒、光触媒による全ての反応工程を１槽で行うため、付帯設備が削減されシンプルな構造になる。
・触媒担持体が同一構造体の場合においては製造工程が短縮できる。
・触媒の清掃作業を同時に行えるため、作業が容易かつ短時間にできる。
なお、本発明における触媒担体は三次元網目構造または多孔質構造状であるため、紫外線、被処理流体およびオゾンとの接触効率が高く、効果的に光触媒反応やオゾン反応が行われる。
Next, the operation of this embodiment will be described.
The present embodiment has the same effect with a liquid such as water or a gas such as air, but decomposes and removes VOC, odorous substances, and bacteria in the air as substances to be removed.
The air 10 to be treated is mixed with the ozone 2 supplied from the ozone generator 1 in the ozone mixing device 11 and sent to the inside of the catalyst carrier 9 of the reaction tower 5. When ultraviolet rays are exposed in a three-dimensional space between the
When passing through the ozone
It should be noted that the provision of means for arbitrarily maintaining the amount of moisture in the air to be treated in advance of the treatment can improve the generation efficiency of OH radicals during operation of the ozone generator or in the photocatalyst.
In addition, a removal object measurement sensor 16 that measures the concentration and intensity of the removal target substance present in the air to be treated is provided, and by measuring this, the required treatment conditions are calculated to calculate the amount of ozone generated and the amount of ultraviolet irradiation. It is possible to adjust. However, since the generation of ozone involves the cost of the raw material gas, the ozone generator may be stopped when the amount of contamination in the air is relatively small. Even in this case, a certain purification function by the photocatalyst can be maintained.
When the catalyst function is reduced by the deposit, the functions of both catalysts can be recovered by removing the catalyst carrier and washing the surface.
The actions and effects of the present invention are summarized as follows.
(1) [Ozone + UV] treatment As mentioned earlier, in the space between the UV irradiation device and the hollow body, ozone is decomposed and excessively combined with ozone and UV (254 nm wavelength UV from a low-pressure mercury lamp). OH radicals are generated through the generation of hydrogen oxide. At this time, the greater the amount of ozone dissolved in water and the greater the decomposition rate by ultraviolet rays, the greater the amount of OH radicals produced. As described above, the action of the OH radical is higher than the oxidation-reduction potential of 2.85 V (under acidity) and 2.07 (under acidity) of ozone, and the organic matter is finally converted into carbon dioxide and water by strong oxidizing power. Can be disassembled.
(2) [Ozone + ozone reaction catalyst] treatment When ozone comes into contact with this catalyst, ozone decomposes and at the same time, active species such as OH radicals are generated, and an oxidative decomposition reaction of organic matter proceeds on the surface of the catalyst.
(3) Photocatalytic treatment Electrons are extracted from the hydroxyl ions of water present on the surface of the photocatalyst by light irradiation to generate OH radicals. For this reason, when an organic substance contacts the photocatalyst surface, it is decomposed by the action of OH radicals. In addition, it is known from the photocatalytic surface that hydrogen peroxide is generated by ultraviolet irradiation, and a synergistic effect with ozone can be expected.
In addition, even if the ozone generator is stopped depending on the state of treatment, the action (3) can be maintained. Alternatively, the function (2) can be maintained even when the ultraviolet irradiation device is stopped.
Furthermore, the following effects can be obtained by forming the catalyst carrier with a two-layer catalyst body having different characteristics of a photocatalyst and an ozone reaction catalyst.
・ Since all reaction processes using ozone + ultraviolet light, ozone + ozone reaction catalyst, and photocatalyst are performed in a single tank, incidental facilities are reduced, resulting in a simple structure.
-If the catalyst carrier has the same structure, the manufacturing process can be shortened.
-Since the catalyst can be cleaned at the same time, it can be done easily and in a short time.
In addition, since the catalyst carrier in the present invention has a three-dimensional network structure or a porous structure, contact efficiency with ultraviolet rays, a fluid to be treated, and ozone is high, and a photocatalytic reaction and an ozone reaction are effectively performed.
図４は、本発明の第２実施例の構成を示す概略図である。
実施例１で説明した任意の紫外線照射装置と、それを取り囲むように構成した光触媒層とオゾン反応触媒層の二層構造からなる触媒担持体を１ユニットとし、複数からなるユニットを１台の反応塔内に並列に収めている。このように処理空気の風量や汚染度合いに応じて収めるユニットの台数を決めることができる。
FIG. 4 is a schematic diagram showing the configuration of the second embodiment of the present invention.
One unit is a catalyst carrier having a two-layer structure of an arbitrary ultraviolet irradiation device described in Example 1 and a photocatalyst layer and an ozone reaction catalyst layer configured to surround the device, and one unit includes a plurality of units. They are stored in parallel in the tower. In this way, the number of units to be accommodated can be determined according to the air volume of the processing air and the degree of contamination.
このように、三次元網目または多孔質構造状からなる触媒担持体を光触媒とオゾン反応触媒の異特性を有する二層の触媒で形成することにより、オゾン＋紫外線、オゾン＋オゾン反応触媒、光触媒による全ての反応工程を１槽で行うことができるため、除去対象物質の除去効率が向上するのみでなく、付帯設備が削減されシンプルな構造になる。また、触媒担持体が同一構造体の場合においては製造工程が短縮できるとともに、触媒の清掃作業を同時に行えるため、作業が容易かつ短時間にできるようになる。
また、気中の汚染量に応じてオゾン発生装置と紫外線照射装置を同時あるいは一方だけの運転に切り替えて制御することができるので、処理の状況によりランニングコストが高いオゾン発生装置を停止しても、光触媒の作用により一定の浄化機能を維持することができる。もしくは紫外線照射装置を停止してもオゾン＋オゾン反応触媒の機能が存在する。
以上により、処理効率が向上するとともに、コンパクト化、イニシャルおよびランニングコストの低減を図ることができる。
Thus, by forming a catalyst carrier having a three-dimensional network or porous structure with a two-layer catalyst having different characteristics of a photocatalyst and an ozone reaction catalyst, ozone + ultraviolet, ozone + ozone reaction catalyst, and photocatalyst are used. Since all the reaction steps can be performed in one tank, not only the removal efficiency of the substance to be removed is improved, but also incidental facilities are reduced, resulting in a simple structure. Further, when the catalyst carrier has the same structure, the manufacturing process can be shortened and the catalyst cleaning operation can be performed simultaneously, so that the operation can be performed easily and in a short time.
In addition, the ozone generator and the ultraviolet irradiation device can be controlled by switching to the simultaneous or only operation according to the amount of pollution in the air, so even if the ozone generator with a high running cost is stopped depending on the processing situation A certain purification function can be maintained by the action of the photocatalyst. Or even if the ultraviolet irradiation device is stopped, the function of ozone + ozone reaction catalyst exists.
As described above, the processing efficiency can be improved, and the downsizing, the initial cost, and the running cost can be reduced.
本発明の有機物除去装置は、空気の処理のみでなく下水や上水等の分野において、水中の着色・臭気物質や細菌類、あるいはゴミ処理場の浸出水中に含まれるダイオキシン等の難分解性有機物の除去にも適用することができる。 The organic substance removing apparatus of the present invention is not only for treating air but also in fields such as sewage and clean water, coloring, odorous substances and bacteria in water, or persistent organic substances such as dioxin contained in leachate from garbage disposal sites It can also be applied to the removal of water.
１ オゾン発生装置
２ オゾン
３ エゼクタ
４ 被処理水
５ 反応塔
６ 紫外線照射装置
７ 処理水
８ 中空管
９ 触媒担持体
１０ 被処理空気
１１ オゾン混合装置
１２ 光触媒層
１３ オゾン反応触媒層
１４ 処理空気
１５ 隔壁
１６ 除去対象物計測センサ
DESCRIPTION OF SYMBOLS 1 Ozone generator 2 Ozone 3 Ejector 4 Water to be treated 5
Claims (4)
前記反応塔内に三次元網目構造または多孔質構造の光触媒層およびオゾン反応触媒層の二層からなる触媒担持体を設けるとともに、前記被処理流体の除去対象物の濃度または強度を計測するセンサを設け、前記センサの計測値により前記オゾン発生装置と前記紫外線照射装置を同時あるいは一方だけの運転に切り替えて制御することを特徴とする有機物除去装置。 An ozone generator, an ozone mixing device that mixes ozone generated from the ozone generator and a fluid to be treated, a reaction tower that reacts the fluid to be treated and ozone, and a reaction tower provided in the reaction tower. In the organic substance removing device composed of an ultraviolet irradiation device that irradiates the processing fluid with ultraviolet rays,
A sensor for measuring the concentration or strength of the removal target of the fluid to be treated is provided in the reaction tower with a catalyst carrier comprising two layers of a photocatalyst layer having a three-dimensional network structure or a porous structure and an ozone reaction catalyst layer. And an organic substance removing device that controls the ozone generator and the ultraviolet irradiation device by switching to the simultaneous or only operation according to the measured value of the sensor.
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