TWI361719B - - Google Patents

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TWI361719B
TWI361719B TW96118851A TW96118851A TWI361719B TW I361719 B TWI361719 B TW I361719B TW 96118851 A TW96118851 A TW 96118851A TW 96118851 A TW96118851 A TW 96118851A TW I361719 B TWI361719 B TW I361719B
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catalyst
sulfur
containing compound
adsorption
unit
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TW96118851A
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TW200734034A (en
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Kou Ching Wu
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1.361719 九、發明說明: 【發明所屬之技術領域】 本發明係關於一種含硫化合物之氣體淨化濾材裝置與 方法及其所使用之觸媒吸附材,特別是關於一種針對例如 二曱基硫(DMS)、二曱基二硫(DMDS)、硫化氫(H2S)等空 氣中含硫化合物之氣體淨化濾材裝置與方法及其所使用之 觸媒吸附材。 胃 【先前技術】 近來,國際間對於環保議題及工業安全衛生及高科技 廠潔淨室分子污染物淨化之日益重視,考量工業廢氣對環 境及勞工以至於一般大眾身體產生之危害,對於工業廢氣 ,排放標準日趨嚴格,國内外法規都制定出濃度及臭味的排 放標準;另一方面,近來高科技廠之高階製程對於含硫化 合物等難處理之分子污染物,在外氣引入潔淨室前的淨化 φ 程度要求愈為嚴苛。 、 例如在半導體晶圓製造廠及TFT-LCD面板光電製造 ' 業面板製程中’去光阻程序(stripping process)所使用之去 光阻剝離液(stripper)主要成分為高沸點且幾乎全溶於水的 有機化合物,包括單乙醇胺(MEA)、二曱基亞砜(DMS〇)以 及乙二醇單丁謎(BDG)等。在去光阻製程中,去光阻劑中 的-甲基亞礙雖然是—種高沸點水溶性而且揮發性低的液 體,但在處理過程中’極容易形成惡臭的二f基硫邮 sulfide,DMS)和一甲基二硫(dimethyl disu腕dMDS)的 1361719 =態污染物。然而’以傳統冷凝法及吸收錢I法〜 除低_及低會溶性的巧基硫與 ^ :濃度下即會產生惡臭,極易影響礙房周圍生活:= 發民眾抗議,同時$田境而引 程之產品良率。房圍其他高科技礙高階製 二氣中S硫化合物氣體之淨化技術可運用物 化學方法及。物理方法係將空氣通過採用吸收、分物 理步驟之淨化設如除去空含硫化合物 :法有機械分離法、過渡法'吸附法、洗條法:=理 吊用的化學方法有熱氧化法和催化燃燒法等。_目前最 常採用的淨化設備仙抽風與㈣綱或-般吸附或水洗 洗滌處理,此傳統設備及方法無法有效淨化如二甲基硫與 二曱基二硫等含硫化合物之氣體,是造成空氣污染臭味陳 情的主因;同時,也是造成被污染之外氣導引進入如半導 體晶圓製造薇及TFT_LCD面板光電製造廄等高階製程潔 淨室’影響產品良率之分子污染物主要來源之一。 此外’尚有運用觸媒催化法來淨化處理空氣中含硫化 合物氣體,觸媒催化法之優點為含硫化合物之脫除效率 咼、反應溫度低、能源消耗低、避免生成二次污染物等, 疋種壤境友好的催化淨化技術。然而·’.此項技術目前最 需要突破的是開發低溫氧化觸媒,由於含硫化合物的處理 效率不佳,所以開發之觸媒必需具有以下特點: 1.具低溫氧化活性之奈米觸媒負載技術 利用奈米觸媒特有的催化特性,小晶粒觸媒載體粒 1361719 徑小、孔道短、晶内擴散阻力小、暴露在外的 ,)、含有眾多的晶_ (二次_、具有 附此力’對於A分子或液相反應有利。反^及 於多孔性—賴孔㈣速擴散,減纽穑^物能 降低觸媒的失活速率,延長觸媒壽命。—積石灭’而 2·具中孔洞特性之吸附/催化基材合成技術 利用中孔洞的高表面積與孔洞特性, 物的吸附去除效率,由於孔容積和孔隙率=:硫化合 :增加三成的吸附量,且因晶間空隙增大可;= -子,總體觸媒效率可提升30%以上。 刀 3.提升氧化活性的助劑辅助技術 無論吸附劑或觸媒,均會隨使用時間而呈現 蓋的現^設計以低電壓激發系統中的氧氣或錢^ 生具較咼氧化活性的氧化助劑,如:〇/、〇 ·、Η〇1.361719 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a gas purification filter device and method for a sulfur-containing compound and a catalyst adsorbing material therefor, and more particularly to a method for, for example, dimercaptosulfur (DMS) A gas purification filter device and method for containing sulfur compounds in air such as dimercapto disulfide (DMDS) or hydrogen sulfide (H2S), and a catalyst adsorbing material used therefor. Stomach [Prior Art] Recently, the international community has paid more and more attention to environmental issues, industrial safety and hygiene, and purification of molecular pollutants in clean rooms of high-tech factories. Considering the harmful effects of industrial waste gas on the environment and labor and the general public, for industrial waste gas, Emission standards are becoming more and more strict, and domestic and foreign regulations have formulated emission standards for concentration and odor; on the other hand, high-end processes of high-tech plants have recently purified toxic compounds such as sulfur compounds before they are introduced into clean rooms. The degree of φ is more stringent. For example, in semiconductor wafer fabrication plants and TFT-LCD panel optoelectronic manufacturing's industrial panel process, the stripper used in the stripping process is mainly composed of a high-boiling point and almost completely soluble. Organic compounds of water, including monoethanolamine (MEA), dimercaptosulfoxide (DMS), and ethylene glycol monobutyl (BDG). In the photoresist-removing process, the -methyl sub-blocking agent in the photoresist is a liquid with high boiling point water solubility and low volatility, but it is very easy to form malodorous bis-sulfur sulfide during the treatment process. , DMS) and monomethyl disulfide (dimethyl disu wrist dMDS) 1361719 = state pollutants. However, 'Traditional condensation method and absorption method I ~ In addition to low _ and low solubility, the sulphur-based sulphur and ^: concentration will produce stench, it is easy to affect the living around the house: = public protest, while the field And the product yield of the lead. Other high-tech systems in the room surrounding the high-order system The purification technology of S-sulfur compound gas in the second gas can be applied by chemical methods. The physical method is to remove the empty sulfur-containing compound by using the absorption and physical separation steps: the mechanical separation method, the transition method, the adsorption method, the washing method: the chemical method for the lifting method, the thermal oxidation method, and Catalytic combustion method, etc. _The most commonly used purification equipment is the extraction of wind and (4) or general adsorption or washing and washing. This traditional equipment and method cannot effectively purify gases such as dimethyl sulfide and dimercapto disulfide. The main cause of air pollution odors; at the same time, it is also one of the main sources of molecular pollutants that affect the product yield, such as the high-order process clean room such as semiconductor wafer fabrication and TFT_LCD panel optoelectronic manufacturing. . In addition, the catalyst catalyst is used to purify the sulfur-containing compound gas in the air. The catalytic catalyst has the advantages of high removal efficiency of sulfur-containing compounds, low reaction temperature, low energy consumption, and avoidance of secondary pollutants. , a kind of soil-friendly catalytic purification technology. However, the most important breakthrough in this technology is the development of low-temperature oxidation catalysts. Due to the poor processing efficiency of sulfur-containing compounds, the catalysts developed must have the following characteristics: 1. Nanocatalysts with low-temperature oxidation activity. The load technology utilizes the unique catalytic properties of the nanocatalyst. The small-grain catalyst carrier particles 1361719 have small diameter, short pores, small intra-crystal diffusion resistance, and are exposed, and contain many crystals _ (secondary _, with attached This force 'is favorable for the reaction of A molecule or liquid phase. In contrast to the porosity-Lyphoon (4) rapid diffusion, the reduction of the amount of catalyst can reduce the rate of catalyst deactivation and prolong the life of the catalyst. 2. Adsorption/catalytic substrate synthesis technology with mesoporous properties utilizes the high surface area and pore characteristics of the mesopores, the adsorption removal efficiency of the material, due to pore volume and porosity =: sulfide: increase the adsorption capacity by 30%, and The interstitial space can be increased; = -, the overall catalyst efficiency can be increased by more than 30%. Knife 3. Auxiliary technology for the promotion of oxidation activity, regardless of the adsorbent or catalyst, will present the cover with the use of time At low voltage Hair money system or oxygen ^ born with oxidation activity than 咼 oxidation auxiliary agent, such as: square / square ·, Η〇

〇3等,加速觸媒表面的氧化還原循環進行,加速觸媒表 面污染物的降解’以達到降低積碳的目的,預計、 提升觸媒的壽命。 W 【發明内容】 為了改善上述習知技術所面臨的問題,本發明之目的 在提供一種含硫化合物之氣體淨化濾材裝置,立包含: 至少一個觸媒吸脫附單元,其以並聯及/或串聯設置; 及 -臭氧產生單7L ’其可提供臭氧於該觸媒吸脫附單 7 1361719 元為加強觸媒吸附功能或低溫氧化分解反應之用。 可=發^含魏合物之氣體淨倾材裝置中,該裝置 1料步包含一水氣或蒸氣產生單元,其可提供水氣或塞 乳於該觸媒吸賴單元,與綠產生單元所提供之臭氧1 併作為觸媒吸附活化再生還原反應之用。 本發明之含硫化合物之氣體淨化濾材裝置中,可於該 裝置之下游端進一步設置空氣淨化處理設備,以作為氣流 終處理之用。該空氣淨化處理設備並無特別限制,較佳為 臭氧分解觸媒或濕式洗滌塔或吸附床。 , 、本發明之含硫化合物之氣體淨化濾材裝置中,可包含 複數個觸媒吸贿單元,其巾該裝置關吸贿單元型式 可為固定床式、轉輪式、轉塔式或、淨動床式、流體化床 式,各觸媒吸脫附單元可同時進行吸附反應或觸媒氧化分 解反應。或者是,該吸附觸媒單元可部分進行吸附反應, 同時部分進行觸媒氧化分解反應。 此外本發明另一目的在提供一種含硫化合物之氣體 淨化方法,其包含下列步驟: (1) 提供一種上述之空氣中含硫化合物之氣體淨化濾材 裝置,其中該觸媒吸脫附單元中充塡有觸媒吸附材; (2) 經由風機將欲處理之含硫化合物之空氣導入該裝 置’開啟及/或關閉相關閥組,同時可導入臭氧產生 單元所產生之臭氧,使充填觸媒吸附材之觸媒吸脫附 單元進一步進行化學性吸附反應或低溫氧化分解反 應’同時排出經吸附後之乾淨氣流; 1361719 (3 )開啟及/或關閉 ._ . ^ ]相關閥組,將已吸附飽和之觸媒吸脫 附旱兀導人身、$女, 塞一 、、虱產生單元所產生之臭氧及/或進一步 入一7 .氣或蒸氣產生單元產生之 行觸媒吸附材之再生還原反應。U 乂進 =發月之3破化合物之氣體淨化方法 硫化合物之氣體淨务驻罢^3 呈之Φ丨·+·、,& & 裝置可包含一水氣或蒸氣產生單元, ^ ^ …、、別限制,較佳可為噴霧加濕器、超音波加〇3, etc., accelerate the redox cycle of the catalyst surface and accelerate the degradation of the surface of the catalyst to reduce the carbon deposit, and predict and improve the life of the catalyst. In order to improve the problems faced by the above-mentioned prior art, it is an object of the present invention to provide a gas purification filter device containing a sulfur compound, comprising: at least one catalyst suction and desorption unit, which is connected in parallel and/or The series arrangement; and - the ozone generation unit 7L' can provide ozone to the catalyst adsorption and release unit 7 1361719 yuan for strengthening the catalyst adsorption function or low temperature oxidative decomposition reaction. In the gas purifying device for the gas containing the Wei compound, the device 1 step comprises a water vapor or steam generating unit, which can provide water vapor or milk to the catalyst absorbing unit, and the green generating unit The provided ozone 1 is used as a catalyst to activate the regeneration reduction reaction. In the gas purifying filter device of the sulfur-containing compound of the present invention, an air purifying treatment device may be further provided at the downstream end of the device for the final treatment of the gas flow. The air purification treatment equipment is not particularly limited, and is preferably an ozone decomposition catalyst or a wet scrubber or an adsorption bed. The gas purification filter device of the sulfur-containing compound of the present invention may comprise a plurality of catalyst-absorbing bribe units, and the device may be a fixed bed type, a rotary type, a turret type or a net. In the movable bed type and the fluidized bed type, each of the catalyst adsorption and desorption units can simultaneously perform an adsorption reaction or a catalytic decomposition reaction of the catalyst. Alternatively, the adsorption catalyst unit may partially perform an adsorption reaction while partially performing a catalytic oxidation decomposition reaction. In addition, another object of the present invention is to provide a gas purification method for a sulfur-containing compound, comprising the steps of: (1) providing a gas purification filter device of the above-mentioned sulfur-containing compound in the air, wherein the catalyst absorption and desorption unit is charged塡The catalyst adsorbs the material; (2) Introduce the air of the sulfur-containing compound to be treated into the device via the fan to 'turn on and/or close the relevant valve group, and at the same time introduce the ozone generated by the ozone generating unit to make the filling catalyst adsorb The catalyst-absorbing and desorbing unit of the material further performs a chemical adsorption reaction or a low-temperature oxidative decomposition reaction while discharging the cleaned air stream after adsorption; 1361719 (3) opening and/or closing the ._. ^] related valve group, which has been adsorbed The saturated catalyst absorbs and desorbs the ozone generated by the unit, the female, the plug, and the enthalpy, and/or further enters into a 7. gas or vapor generating unit to produce a catalytic reductive reaction . U 乂 = = = 发 之 破 化合物 化合物 化合物 化合物 气体 气体 气体 硫 硫 硫 硫 硫 硫 硫 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 丨 + + + + + + + + + + + + + + + + + ...,, not limited, preferably spray humidifier, ultrasonic plus

濕态、蒸氣加濕器。 本發明之含硫化合物之氣體淨化方法中,可進一步包 3 ,步驟(4) ’係為設置—空氣淨化處理設備於下游端, 可簡易.地終處理步驟⑶所可能生成之新污染物1於該 空氣淨化處理設備之型式並無制聞,較佳可為臭氧分 解觸媒或濕式洗蘇塔或吸附床。 本發明之含硫化合物之氣體淨化方法中,.該裝置可包 含複數個觸媒吸脫附單元,其可同時進行步驟(2)。戋者 是,該複數個觸媒吸脫附單元可部分進行步驟(2),同時 部分進行步驟(3)。亦或是,該觸媒吸脫附單元可於線上 進行步驟(1)或步驟(1)及(2),線外進行步驟(2\ 或步驟(3)。 ^ 本發明之含硫化合物之氣體淨化方法中,該觸媒 材係由觸媒載體與觸媒組成,其中該觸媒载體係選自活性 碳、沸石、氧化鋁、其他多孔性物質或其之混合物;該= 媒之活性部分為N-orbit金屬,其係選自Mn、Fe、c。、'Wet, steam humidifier. In the gas purification method of the sulfur-containing compound of the present invention, the package 3 can be further provided, and the step (4) is set as the air purification treatment device at the downstream end, and the new pollutants which may be generated in the step (3) can be easily processed. The type of the air purification treatment apparatus is not smear, and is preferably an ozone decomposition catalyst or a wet scrubber or an adsorption bed. In the gas purifying method of the sulfur-containing compound of the present invention, the apparatus may comprise a plurality of catalyst adsorption and desorption units which can perform step (2) simultaneously. The latter is that the plurality of catalyst suction and removal units can partially perform step (2) while partially performing step (3). Alternatively, the catalyst adsorption and desorption unit may perform step (1) or steps (1) and (2) on the line, and perform the step (2\ or step (3) off-line. ^ The sulfur-containing compound of the present invention In the gas purification method, the catalyst medium is composed of a catalyst carrier and a catalyst, wherein the catalyst carrier is selected from the group consisting of activated carbon, zeolite, alumina, other porous substances or a mixture thereof; the active part of the medium Is an N-orbit metal selected from the group consisting of Mn, Fe, c., '

Cu、Pb或Zn。而觸媒吸附材成形之形狀並無特別限:1,' 較佳可為圓柱狀或 狀或發泡狀等形式 顆教狀或真球狀或蜂巢狀或多層次堆疊 本發明另一目、 體淨化裝置與方法的在提供一種用於上述含硫化合物之氣 紐成,姐之觸媒吸附材’其係由觸媒載體與觸媒 N-orbit 而觸媒吸附 較佳可為圓柱狀或顆粒狀或 上=裁體係選自活性碳 金屬,其係選自合物;該觸媒之活性部分為 :成形之形狀並無特:限:,、:=ΓΖη 真球狀或蜂巢狀或多 二:: 泡狀等形式。 層"人堆豎狀(Multl Layers Media)或發 介風t ^本發明之觸媒吸附材,其可進行化學性吸附並可 y予生再生還原。例如以DMS之有機廢氣為例4單獨進 行化學性吸_之_: M + DMS $ Ma+ --S(CH3)2 @線上以臭氧加強還原吸附之機制(其可延長吸附劑之 壽命):Cu, Pb or Zn. The shape of the catalyst adsorbing material is not particularly limited: 1. 'It is preferably a cylindrical shape or a foamed shape, or a spherical shape or a honeycomb shape or a multi-layer stack. The purification apparatus and method provide a gas-forming compound for the above-mentioned sulfur-containing compound, and the catalyst adsorbent material of the sister is adsorbed by the catalyst carrier and the catalyst N-orbit, and the catalyst may preferably be cylindrical or granular. The shape or upper = cutting system is selected from the group consisting of activated carbon metal, which is selected from the compound; the active part of the catalyst is: the shape of the forming is not special: limit:,::=ΓΖη true spherical or honeycomb or more than two :: Bubbles and other forms. Layer "Multl Layers Media or Mediation The catalyst adsorbent of the present invention is chemically adsorbable and can be regenerated by regeneration. For example, the organic exhaust gas of DMS is used as an example of chemical adsorption alone. _: M + DMS $ Ma+ --S(CH3)2 @ Online strengthens the adsorption mechanism by ozone (which can prolong the life of the adsorbent):

Ma+ + DMS -> Ma+ -S(CH3)2 5〇z ^Ma+ + DMS -> Ma+ -S(CH3)2 5〇z ^

Ma+ -S(CH3)2 + 03 + Ma+ 卞C02 + H20 +CH4 以臭氧化學性再生還原機制:Ma+ -S(CH3)2 + 03 + Ma+ 卞C02 + H20 +CH4 Ozone chemical regeneration reduction mechanism:

Ma+ -S(CH3)2 + 〇3 + Ma+ + S02 + C02 + H20 +CH4 或者是以臭氧、水氣或蒸汽化學性再生還原機制: M'+ -s(CH3)2 + 〇3 +H20^ Ma+ + S02 + C〇2 + H2〇 +ch4 因此本發明之觸媒吸附材可搭配所設計之裝置使用 1361719 置化學性再生還原 吸附後之觸媒吸附材可取出以其他t 或者是於線上直接化學性再生還原。 限制本發明之範疇,合 者顯而易見為合理者, •下列實驗設計係為說明,不應 理的變化’諸如對於熟習此項技藝 可於不脫離本發明之範疇下進行。 【實施方式】 實施例1 _ 帛-圖為本發明之含硫化合物之氣體淨化裝置較佳具 體例的示意圖。該襞置包含二個觸媒吸脫附單元丨丨及u、 ’其中充塡有觸媒吸附材,其係由觸媒載體與觸媒組成, 其中該觸媒載體係選自活性碳、沸石、氧化鋁、其他多孔 ,性物質或其之混合物;該觸媒之活性部分為N_〇rbit金屬, 其係選自Mn、Fe、Co、Ni、Cu、Pb或Zn。且其以並聯設 置;一風機30’設置於觸媒吸脫附單元u及12之上游端, • 其可抽送欲處理之空氣至該觸媒吸脫附單元11及/或12 ; ' 及二個臭氧產生單元20及21,其可提供臭氧於該觸媒吸 . 脫附單元11及/或丨2,作為也^觸—媒農原'吸'附功能或隻溫/ 氧化分解反應之用;—水氣產生單元40,可提供水氣或蒸 氣至該觸媒吸脫附單元u及/或12 ^以下各閥組除另有說 明外,皆為關閉狀態。 首先’開啟風機3〇、閥51、52、57及58,經由風機 30可將空氣入口 a之欲處理之含硫化合物氣體導入觸媒吸 脫附單元11及12 ’其中所充塡之觸媒吸附材可將空氣中 11 1361719 含硫化合物之氣體吸附,而吸附處理後之乾淨氣流在經由 煙囪(圖未示)排放。 ·. 而吸附完成之觸媒吸附材可取出還原處理,另充填新 品於觸媒吸脫附單元11及12。 實施例2 如實施例1之裝置及方法,但於觸媒吸脫附單元11及 12吸附飽和後,開啟閥53、54、55及56,以臭氧產生單 元20所提供之臭氧及水氣產生單元40所提供之水氣或蒸 氣,進行低溫氧化分解反應,將觸媒吸脫附單元11及12 内之觸媒吸附材再生還原。而所產生之廢氣由廢氣出口 C 排出,經由後端所設置之終處理裝置(圖未示)處理。 實施例3 如實施例1及2之裝置及方法,但於經由風機30將空 氣入口 A之欲處理之有機廢氣導入觸媒吸脫附單元11及 12時,同時以臭氧產生單元21提供臭氧於該觸媒吸脫附 單元11及/或12,以加強觸媒還原吸附功能。 實施例4 使用如實施例1所述之裝置,開啟風機30、閥51、57、 56及54,經由風機30可將空氣入口 A之欲處理之含硫化 合物之氣體導入觸媒吸脫附單元11,進行化學性吸附反 應,吸附後之乾淨氣流經由煙自排放。同時導入臭氧產生 12 136.1719 單元20所產生之臭氧及水氣產生單元40所產生之水氣或 蒸氣,使先也已吸附飽和之觸媒吸脫附單元12進行低温軋 化分解反應,以再生還原内部所充填之觸媒吸附材’而所 ' 產生之廢氣由廢氣出口 C排出,經由後端所設置之終處理 . 裝置(圖未示)處理。 於觸媒吸脫附單元U吸附飽和後,開啟闕52、58、 55及53 ’將已再生還原之觸媒吸脫附單元12進行化學性 吸附反應,而將已吸附飽和之觸媒吸脫附單元n導入臭氧 產生早7C所產生之臭氧,以進行觸媒吸附材之再生還原反 應'。依次循環,可連續進行線上含硫化合物氣體之淨化。 實施例5 第-圖為本發明之含硫化合物之氣體淨化裳置 體例的示㈣。該裝置包含_轉輪式觸媒吸脫附 ” 其包含有觸媒吸附材;一風機3〇 ’ 附單元η之上游端,其可抽送欲處理之空脱 媒吸脫附單元13;及二個臭氧產生單元2〇及2;, 別提供臭氧於該轉輪式觸媒吸脫附單元13之化學^可刀 還原脫附區m及化學性吸附區m,作為加強 吸附功能或低溫氧化分解反狀用。、 明外’皆為關狀態。 首先’開啟風機3G及轉輪之驅動裝置(圖未 由風機3G可將空氣人σ A之欲處理之含硫化合物氣體= 入轉輪式觸媒吸脫附單元13之化學性吸附區ΐ3ι,其中= 13 1361719 3之觸媒吸附材可將空氣中含硫化合物之氣體吸附,而吸 附處理後之乾淨氣流在經由煙自(圖未示)排放。 經由驅動裝置驅動轉輪式觸媒吸脫附單元13轉動,將 吸附完成之觸媒吸脫附單元轉移至化學性再生還原脫附區 132。導入臭氧產生單元2〇所產生之臭氧或及水氣產生單 兀40所產生之水氣或蒸氣,使化學性再生還原脫附區132 之觸媒吸脫附單元進行低溫氧化分解反應,以再生還原内 所含之觸媒吸附材,而所產生之廢氣由廢氣出口 c排 出’經由後端所設置之終處理裝置(圖未示)處理。 實施例6-8 實施例6-8為分別以DMS、DMDS及H2S作為含硫化 合物之氣體,測試本發明裝置所充填之觸媒吸之處理 效能,實施例6、7所使用之觸媒吸附材組成為含有銅之活 性碳及γ型沸石,實施例8所使用之觸媒吸附材組成為含 有Μη之鹼性活性碳,各實施例結果如下。 實施例6 觸媒線速度 DMS 入 σ DMS 出口 去除效率(%) 觸媒壽命(hrs) 臭氧加入 —(m/s) 濃度(ppb) 濃度(PPb) (致率>95%) 濃度 0.5 900 15 98.3% > 1440 6.8gpm 0.5 3600 20 99.4% ___^720 6.8ppm 1 u---— 1800 18 99.0% >720 3.4ppm 136.1719 實施例、7 觸媒線速度 DMDS 入口 DMDS 出口 去除效率 觸媒壽命(hrs) 臭氧加入 (m/s) 濃度(ppb) 濃度(ppb) (%) (效率>95%) 濃度 0.5 900 8 99.1% >2160 6.8ppm 0.5 3600 12 99.7% > 1080 6.8ppm 1 1800 15 99.2% > 1080 3.4ppm 實施例8 觸媒線速度 H2S入口濃度 H2S出口濃度 去除效率 觸媒壽命(hrs) 臭氧加入 (m/s) (ppb) (ppb) (%) (效率>95%) 濃度 0.5 900 10 98.9% >2880 6.8ppm 0.5 3600 15 99.6% > 1440 6.8ppm 1 1800 13 99.3% > 1440 3.4ppmMa+ -S(CH3)2 + 〇3 + Ma+ + S02 + C02 + H20 +CH4 Or chemically regenerated by ozone, water vapor or steam: M'+ -s(CH3)2 + 〇3 +H20^ Ma+ + S02 + C〇2 + H2〇+ch4 Therefore, the catalyst adsorbent of the present invention can be used with the designed device to use 1361719. The catalytic adsorbent after chemical regeneration reduction adsorption can be taken out to other t or directly on the line. Chemical regeneration reduction. The scope of the present invention is intended to be limited, and the following experimental design is intended to be illustrative, and undeniable changes may be made without departing from the scope of the invention. [Embodiment] Embodiment 1 _ 帛-Fig. is a schematic view showing a preferred embodiment of a gas purifying apparatus containing a sulfur compound of the present invention. The device comprises two catalyst adsorption and desorption units u and u, which are filled with a catalyst adsorption material, which is composed of a catalyst carrier and a catalyst, wherein the catalyst carrier is selected from the group consisting of activated carbon and zeolite. Alumina, other porous, sexual substances or mixtures thereof; the active portion of the catalyst is a N_〇rbit metal selected from the group consisting of Mn, Fe, Co, Ni, Cu, Pb or Zn. And arranged in parallel; a fan 30' is disposed at the upstream end of the catalyst suction and removal units u and 12, and • can pump the air to be treated to the catalyst suction and removal unit 11 and/or 12; 'and two Ozone generating units 20 and 21, which can provide ozone to the catalyst absorbing and desorbing unit 11 and/or 丨2, as a function of absorbing or oxidizing decomposition reaction The water vapor generation unit 40 can supply moisture or steam to the catalyst suction and release unit u and/or 12 ^. The valve groups are all closed unless otherwise stated. Firstly, the fan 3〇 and the valves 51, 52, 57 and 58 are turned on, and the sulfur-containing compound gas to be treated of the air inlet a can be introduced into the catalyst suction and removal unit 11 and 12' via the blower 30. The adsorbent material adsorbs the gas of the 11 1361719 sulfur-containing compound in the air, and the cleaned air stream after the adsorption treatment is discharged through the chimney (not shown). · The adsorbent adsorbent material which has been adsorbed can be taken out and reduced, and the new product is filled in the catalyst suction and release unit 11 and 12. Embodiment 2 The apparatus and method of Embodiment 1, but after the catalyst adsorption and desorption units 11 and 12 are saturated and saturated, the valves 53, 54, 55 and 56 are opened to generate ozone and moisture generated by the ozone generating unit 20. The water vapor or vapor supplied from the unit 40 undergoes a low-temperature oxidative decomposition reaction to regenerate and reduce the catalyst adsorbing materials in the catalyst adsorption/desorption units 11 and 12. The generated exhaust gas is discharged from the exhaust gas outlet C and processed through a final processing device (not shown) provided at the rear end. Embodiment 3 The apparatus and method of Embodiments 1 and 2, but when the organic waste gas to be treated of the air inlet A is introduced into the catalyst suction and removal units 11 and 12 via the blower 30, ozone is simultaneously supplied by the ozone generating unit 21. The catalyst adsorbs the desorption unit 11 and/or 12 to enhance the catalytic reduction adsorption function. Embodiment 4 Using the apparatus as described in Embodiment 1, the fan 30, the valves 51, 57, 56 and 54 are turned on, and the gas of the sulfur-containing compound to be treated of the air inlet A can be introduced into the catalyst-absorbing and desorbing unit via the blower 30. 11. A chemical adsorption reaction is carried out, and the cleaned air stream after adsorption is discharged through the smoke. At the same time, ozone is introduced to generate water or steam generated by the ozone and water gas generating unit 40 generated by the unit 12 136.1719 unit 20, so that the catalyst adsorbing and desorbing unit 12 which has also been adsorbed and saturated is subjected to low temperature rolling decomposition reaction for regeneration and reduction. The exhaust gas generated by the internal catalyst adsorbent material is discharged from the exhaust gas outlet C and processed through a final process (not shown) provided at the rear end. After the catalyst adsorption and desorption unit U is saturated and saturated, the 阙52, 58, 55, and 53' are opened, and the reductively reduced catalyst adsorption and desorption unit 12 is subjected to a chemical adsorption reaction, and the adsorbed saturated catalyst is removed. The unit n is introduced into the ozone to generate ozone generated by the early 7C to carry out the regeneration reduction reaction of the catalyst adsorbing material. The cycle is repeated to continuously purify the sulfur-containing compound gas on the line. [Embodiment 5] Fig. 4 is a view showing the gas purifying skirt of the present invention (4). The device comprises a _rotary-type catalyst absorbing and desorbing, which comprises a catalyst adsorbing material; a fan 3〇' is attached to the upstream end of the unit η, which can pump the empty desorption and desorption unit 13 to be processed; Ozone generating units 2 and 2; respectively, providing ozone to the chemically-removable desorption zone m and the chemical adsorption zone m of the rotary-type catalyst adsorption and desorption unit 13 as a strengthening adsorption function or low-temperature oxidative decomposition In the opposite direction, the outside of the 'all are closed. First of all' turn on the fan 3G and the drive of the runner (the figure is not the fan 3G can be used to treat the sulfur compound gas of the air σ A = into the wheel touch The chemical adsorption zone of the sorption unit 13 is ΐ3ι, wherein the catalyst adsorbing material of 13 1361719 3 can adsorb the gas of the sulfur compound in the air, and the clean gas flow after the adsorption treatment is via the smoke (not shown). Discharge. The drive-type catalyst suction and release unit 13 is driven to rotate, and the adsorbed catalyst absorption and desorption unit is transferred to the chemical regeneration reduction desorption zone 132. The ozone generated by the ozone generation unit 2 is introduced or And water vapor produces water produced by single 兀40 The gas or vapor causes the catalytic absorption and desorption unit of the chemical regeneration reduction desorption zone 132 to perform a low temperature oxidative decomposition reaction to regenerate the catalytic adsorbent contained in the reduction, and the generated exhaust gas is discharged from the exhaust gas outlet c. The final processing device (not shown) disposed at the back end is processed. Embodiments 6-8 Embodiments 6-8 test the catalyst absorption of the device of the present invention by using DMS, DMDS and H2S as gases containing sulfur compounds, respectively. The treatment efficiency of the catalyst adsorbing materials used in Examples 6 and 7 is composed of copper-containing activated carbon and γ-type zeolite, and the catalyst adsorbing material used in Example 8 is composed of 活性η-containing alkaline activated carbon. The results are as follows. Example 6 Catalytic linear velocity DMS into σ DMS outlet removal efficiency (%) Catalyst lifetime (hrs) Ozone addition—(m/s) Concentration (ppb) Concentration (PPb) (rate > 95%) Concentration 0.5 900 15 98.3% > 1440 6.8gpm 0.5 3600 20 99.4% ___^720 6.8ppm 1 u---- 1800 18 99.0% >720 3.4ppm 136.1719 Example, 7 Catalytic Linear Velocity DMDS Inlet DMDS Outlet Removal efficiency catalyst life (hrs) ozone addition (m/s) concentration (ppb) Concentration (ppb) (%) (Efficiency > 95%) Concentration 0.5 900 8 99.1% > 2160 6.8 ppm 0.5 3600 12 99.7% > 1080 6.8 ppm 1 1800 15 99.2% > 1080 3.4 ppm Example 8 Catalyst Line speed H2S inlet concentration H2S outlet concentration removal efficiency Catalyst life (hrs) Ozone addition (m/s) (ppb) (ppb) (%) (efficiency > 95%) Concentration 0.5 900 10 98.9% > 2880 6.8 ppm 0.5 3600 15 99.6% > 1440 6.8ppm 1 1800 13 99.3% > 1440 3.4ppm

產業可利用性 本發明之含硫化合物之氣體淨化裝置與方法及其所使 用之觸媒吸附材可處理較難處理之含硫化合物之氣體,例 如DMS或DMDS,可解決傳統處理裝置不能或不適處理某 些含硫化合物之氣體的問題,並可增加觸媒效率,延長觸 媒壽命,為相當符合環保及能源需求之優良技術,值得應 用於高風量低濃度排放之高科技晶圓製造、光電面板製造 業、塗裝印刷業及相關化工業。 【圖式簡單說明】 15 1361719 第一圖為本發明之含硫化合物之氣體淨化裝置較佳具 體例的示意圖。 第二圖為本發明之含硫化合物之氣體淨化裝置較佳具 體例的示意圖。 【主要元件符號說明】 1 卜 12、13 觸媒吸脫附單元 131 化學性吸附區 132 化學性再生還原脫附區 20 ' 21 臭氧產生單元 30 風機 40 水氣產生單元 51 > 52 > 53 、54 、 55 、 56 、 57 、 58 、 A 空氣入口 B 空氣出口 C 廢氣出口 閥 16INDUSTRIAL APPLICABILITY The gas purifying apparatus and method of the sulfur-containing compound of the present invention and the catalyst adsorbing material used therefor can process a gas of a sulfur-containing compound which is difficult to handle, such as DMS or DMDS, which can solve the problem that the conventional processing apparatus cannot or is uncomfortable. The problem of treating some gases containing sulfur compounds, and increasing the efficiency of the catalyst and prolonging the life of the catalyst. It is an excellent technology that is quite compatible with environmental protection and energy demand. It is worthy of being applied to high-tech wafer fabrication and optoelectronics with high air volume and low concentration emission. Panel manufacturing, coating and printing, and related industries. BRIEF DESCRIPTION OF THE DRAWINGS 15 1361719 The first figure is a schematic view showing a preferred embodiment of the gas purifying apparatus containing a sulfur compound of the present invention. The second drawing is a schematic view showing a preferred embodiment of the gas purifying apparatus of the sulfur-containing compound of the present invention. [Explanation of main component symbols] 1 Bu 12, 13 Catalyst absorption and desorption unit 131 Chemical adsorption zone 132 Chemical regeneration reduction desorption zone 20 ' 21 Ozone generation unit 30 Fan 40 Water gas generation unit 51 > 52 > 53 , 54, 55, 56, 57, 58 , A air inlet B air outlet C exhaust gas outlet valve 16

Claims (1)

1361719 __ 修正版修正日期:2011/Ί1/4 f 月/日晗(避)正替換頁 十、申請專利範圍〜一 1. -種含魏合物之氣體淨傾材U,該含硫化合物不 包含二氧化硫,其包含: 至少一個觸媒吸脫附單元,其以並聯及/或串聯設 置,其中該觸媒吸附單元中充塡有觸媒吸附材;及 一臭氧產生單元,其可提供臭氧於該觸媒吸脫附單 元’作為加強觸媒吸附功能及低溫氧化分解反應之用。 2. 如申請專利範圍第1項之含硫化合物之氣體淨化遽材裝 置’其中該觸媒吸附材係由觸媒載體與觸媒組成。 3·如申清專利範圍第2項之含硫化合物之氣體淨化遽材裝 置,其中該觸媒載體係選自活性碳、沸石、氧化銘、其 他多孔性物質或其之混合物;其觸媒吸附材成形形狀可 為圓柱狀或顆粒狀或真球狀或蜂巢狀或多層次堆疊狀或 發泡狀。 4. 如申請專利範圍第2項之含硫化合物之氣體淨化滤材裝 置’其中該觸媒之活性部分為N-orbit金屬,其係選自 Mn、Fe、Co、Ni、Cu 或 Zn。 5. 如申請專利範圍第1項之含硫化合物之氣體淨化滤材裝 置’其中該裝置觸媒吸脫附單元型式可為固定床式或轉 輪式或轉塔式或或浮動床式或流體化床式。 6. 如申請專利範圍第1項之含硫化合物之氣體淨化濾材裝 置’其中該裝置進一步包含一水氣或蒸氣產生單元,其 可提供水氣或蒸氣於該觸媒吸脫附單元,與臭氧產生單 元所提供之臭氧一併作為觸媒吸附活化再生還原反應之 17 1361719 修正版修正曰期:2011/11/4 K年〃月4曰修(fo正替換良 用。 ___ 7. 如申請專利範圍第1項之含硫化合物之氣體淨化濾材裝 置,其中於該裝置之下游端可進一步設置空氣淨化處理 設備。 8. 如申請專利範圍第7項之含硫化合物之氣體淨化濾材裝 置,其中該空氣淨化處理設備為臭氧分解觸媒或濕式洗 滌塔或吸附床。 9. 如申請專利範圍第1項之含硫化合物之氣體淨化濾材裝 置,其中該觸媒吸脫附單元可同時進行吸附反應及觸媒 氧化分解反應。 10. 如申請專利範圍第1項之含硫化合物之氣體淨化濾材 裝置,其中該吸附觸媒單元可部分進行吸附反應,同時 部分進行觸媒氧化分解反應。 11. 一種含硫化合物之氣體淨化方法,該含硫化合物不包含 二氧化硫,其包含下列步驟: (1) 提供一種如申請專利範圍第1至10項中任一項 之含硫化合物之氣體淨化濾材裝置,其中該觸媒 吸脫附單元令充塡有觸媒吸附材; (2) 經由風機將欲處理之含有含硫化合物之空氣導 入該裝置,開啟及/或關閉相關閥組,同時導入 臭氧產生單元所產生之臭氧,使充填觸媒吸附材 之觸媒吸脫附單元進一步進行化學性吸附反應 及低溫氧化分解反應,同時排出經吸附後之氣 流, 18 1361719 ___ 广年/月〆日修(愛)正替換頁修正版修正日期,l/11,4 (3)開啟及/或關閉相關閥組,將已吸附飽和之觸媒 吸脫附單元導入臭氧產生單元所產生之臭氧及/ 或進一步導入一水氣或蒸氣產生單元產生之水 軋或蒸氣,以進行觸媒吸附材之再生還原反應。 . u·如申請專利範圍第11項之含硫化合物之氣體淨化方 法’其中該裝置包含-水氣或蒸氣產生單元,可為喷霧 加濕器或超音波加濕器或蒸氣加濕器。 鲁 如申咕專利範圍第11項之含硫化合物之氣體淨化方 法,其進一步包含步驟(4),係設置一空氣淨化處理設 備以終處理步驟(3)所生成之新污染物。 14.如ΐ請專利範圍第13項之含硫化合物之氣體淨化方 法’其中該空氣淨化處理設備為臭氧分解觸媒或濕式洗 滌塔或吸附床。 15. 如申請專利範圍第11項之含硫化合物之氣體淨化方 法,其中該至少二個觸媒吸脫附單元可同時進行步驟 (2)及步驟(3)。 16. 如申凊專利範圍第u項之含硫化合物之氣體淨化方 法’其中該觸媒吸脫附單元可部分進行步驟(2),同時 部分進行步驟(3)。 1入如申請專利範圍第U項之含硫化合物之氣體淨化方 法’其中該觸媒吸脫附單元可於線上進行步驟⑴或 步驟(1)及(2)’可;^線外進行步驟⑵及步驟⑴。 .如申明專利u狀含硫化合物之氣體淨化方 法’、中該觸媒吸附材係由觸媒載體與觸媒組成。 1361719 修正版修正日期:2011/11/4 19丨如申請專利範圍第18項之含硫化合物之氣體淨化方 _法,其中該觸媒載體係選自活性碳、沸石、氧化鋁、其 他多孔性物質或其之混合物;其觸媒吸附材成形形狀可 為圓柱狀或顆粒狀或真球狀或蜂巢狀或多層次堆疊狀 或發泡狀。 : 20.如申請專利範圍第18項之含硫化合物之氣體淨化方 法,其中該觸媒之活性部分為N-orbit金屬,其係選自 Mn、Fe、Co、Ni、Cu 或 Zn。 201361719 __ Revised revision date: 2011/Ί1/4 f Month/day 晗 (avoidance) is being replaced on page 10, the scope of patent application is ~1. - A gas-containing net U-containing material containing Wei compound, the sulfur-containing compound is not Containing sulfur dioxide, comprising: at least one catalytic absorption and desorption unit disposed in parallel and/or in series, wherein the catalyst adsorption unit is filled with a catalyst adsorption material; and an ozone generating unit that provides ozone The catalyst adsorption and desorption unit serves as a catalyst adsorption adsorption function and a low temperature oxidative decomposition reaction. 2. The gas purifying coffin device of the sulfur-containing compound as claimed in claim 1 wherein the catalyst adsorbing material is composed of a catalyst carrier and a catalyst. 3. A gas purifying coffin device containing a sulfur compound according to item 2 of the patent scope, wherein the catalyst carrier is selected from the group consisting of activated carbon, zeolite, oxidized mineral, other porous materials or a mixture thereof; The shape of the material may be cylindrical or granular or true spherical or honeycomb or multi-layered stacked or foamed. 4. The gas purifying filter device of the sulfur-containing compound of claim 2, wherein the active portion of the catalyst is an N-orbit metal selected from the group consisting of Mn, Fe, Co, Ni, Cu or Zn. 5. The gas purification filter device of the sulfur-containing compound of claim 1 wherein the device catalytic release unit type may be a fixed bed or a rotary or turret or a floating bed or a fluid Bed type. 6. The gas purification filter device of the sulfur-containing compound of claim 1, wherein the device further comprises a water vapor or vapor generating unit, which can provide moisture or vapor to the catalyst adsorption and desorption unit, and ozone. The ozone provided by the generating unit is used as a catalyst to activate and regenerate the reduction reaction. 13 1361719 Revised edition Revision period: 2011/11/4 K year 〃 month 4 曰 repair (fo is replacing good use. ___ 7. If applying for a patent The gas purification filter device of the sulfur-containing compound of the first aspect, wherein the air purification treatment device is further disposed at the downstream end of the device. 8. The gas purification filter device of the sulfur-containing compound according to claim 7 of the patent scope, wherein The air purification treatment device is an ozone decomposition catalyst or a wet scrubber or an adsorption bed. 9. The gas purification filter device of the sulfur compound according to claim 1, wherein the catalyst adsorption and desorption unit can simultaneously perform the adsorption reaction And the oxidative decomposition reaction of the catalyst. 10. The gas purification filter device of the sulfur-containing compound according to claim 1 of the patent scope, wherein the adsorption catalyst unit can be partially The adsorption reaction is carried out while partially performing the catalytic decomposition reaction of the catalyst. 11. A gas purification method for a sulfur-containing compound, the sulfur-containing compound not comprising sulfur dioxide, comprising the following steps: (1) providing a range of patents 1 to 10 A gas purification filter device for a sulfur-containing compound according to any one of the preceding claims, wherein the catalyst adsorption and desorption unit is filled with a catalyst adsorption material; (2) introducing a sulfur-containing compound-containing air to be processed into the device via a fan Opening and/or closing the relevant valve group, and simultaneously introducing ozone generated by the ozone generating unit, so that the catalyst adsorption and desorption unit filled with the catalyst adsorbing material further performs chemical adsorption reaction and low temperature oxidative decomposition reaction, and simultaneously discharges the adsorbed Airflow, 18 1361719 ___ 广年/月〆日修 (Love) is replacing the page revision revision date, l/11, 4 (3) opening and/or closing the relevant valve group, aspirating the saturated saturated catalyst The unit is introduced into the ozone generated by the ozone generating unit and/or further introduced into the water rolling or steam generated by the water vapor or steam generating unit to carry out the catalyst adsorbing material. a reduction reaction. u. A method for purifying a sulfur-containing compound according to claim 11 wherein the device comprises a water vapor or vapor generating unit, which may be a spray humidifier or an ultrasonic humidifier or a vapor. A gas purification method for a sulfur-containing compound according to Item 11 of the patent application, further comprising the step (4) of providing an air purification treatment device to finally process the new pollutant generated in the step (3). 14. A method for purifying a sulfur-containing compound according to claim 13 of the patent scope, wherein the air purification treatment device is an ozone decomposition catalyst or a wet scrubber or an adsorption bed. A gas purification method of a sulfur-containing compound, wherein the at least two catalyst adsorption and desorption units can simultaneously perform the steps (2) and (3). 16. The gas purifying method of a sulfur-containing compound according to item u of the patent scope of the invention, wherein the catalyst-absorbing and desorbing unit can partially carry out the step (2) while partially performing the step (3). 1Into the gas purification method of the sulfur-containing compound according to the Uth article of the patent application, wherein the catalyst adsorption and desorption unit can perform the step (1) or the steps (1) and (2)' on the line; the step (2) is performed outside the line And step (1). For example, a gas purifying method for a patented U-shaped sulfur-containing compound is used, and the catalyst adsorbing material is composed of a catalyst carrier and a catalyst. 1361719 Revised revision date: 2011/11/4 19 For example, the gas purification method for sulfur compounds in claim 18, wherein the catalyst carrier is selected from the group consisting of activated carbon, zeolite, alumina, and other porous materials. The substance or a mixture thereof; the shape of the catalyst adsorbing material may be cylindrical or granular or true spherical or honeycomb or multi-layered stacked or foamed. 20. The gas purifying method of a sulfur-containing compound according to claim 18, wherein the active portion of the catalyst is an N-orbit metal selected from the group consisting of Mn, Fe, Co, Ni, Cu or Zn. 20
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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