201034749 六、發明說明： 【發明所屬之技術領域】 本發明係揭示一種吸附材之再生方法，特別是指用於 去除低濃度有機廢氣污染物所使用吸附材之淨化再生 法’且使用高活性物質如臭氧（〇3)或氫氧自兩基 (ΟΗ·/Η〇2·/02·)，可有效淨化再生吸附材。本發明係 < 用於 增加觸媒與吸附材效率、延長觸媒吸附材壽命且適商於淨 化處理高風量低濃度之晶圓製造、光電面板製造業等無慶 ❹ 室空氣淨化或其排放廢氣之淨化用途，同時適用於/躲廢 水廠、塗裝印刷業及相關化工業等空氣淨化之用。 【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，考量工業廢氟對攘 境及勞工以至於一般大眾身體產生之危害，對於工業廣氟 ❹ 排放標準日趨嚴格，國内外法規都已制定出相關的濃虞及 六味的排放標準；另一方面，近來高科技廠之高階製择對 於含硫化合物及低沸點有機化合物等難處理之分子汚染 物，在外氣引入潔淨室前的淨化程度要求愈為嚴苛。 在半導體晶圓製造廠及TFT-LCD面板光電製造業面扳 製輕中’去光阻程序(striPPing process)所使用之去光阻剝離 液(stripper)^要成分為高沸點且幾乎完全溶於水的有機化 合物’包括單乙醇胺(MEA)、二甲基亞石風(DMS〇)以及乙二 醇單丁醚(BDG)等。而在去光阻製程中，去光阻射的二甲 201034749 基亞礙雖然疋種回沸點水浴性而且揮發性低的液體，但 在處理過程中，極容易形成低沸點且惡臭的二甲基硫 (dimethyl sulfide, DMS)和二曱基二硫（dimethyl disulfide， DMDS)的氣態污染物。然而，以傳統吸附法、冷凝法及吸 收法並無法完全去除低沸點及低水溶性的二甲基硫與二甲 基二琉’而且其在低濃度下即會產生惡臭，極易影響礙房 周圍生活環境而引發民眾抗議，同時也影響到廠房周圍其 他高科技廠高階製程之產品良率。 空氣中低濃度有機化合物氣體之淨化技術可運用物理 方法、化學方法及其混合法。而物理方法係將空氣通過採 用吸收、吸附、分離等物理步驟之淨化設備以除去空氣中 低濃度有機化合物’常用的物理方法有機械分離法、過遽 法、吸附法、洗滌法和靜電法。 〜 其中吸附法係為現階段常見之有機氣體淨化方法，由 於人類在科技上不斷的突破與發展，致使吸附程序 (Adsorptionprocess)技術被廣範的應用於化工、生化、石化 及壞保專工業的純化及分離淨化應用上。吸附是一種義本 的固-氣（或固·液）兩相界面化學現象。當氣體分子 (Molecules)、原子(Atoms)或離子(Ions)靠近固_氣界面之吸 附劑表面時’由於彼此間分子之親和力（Affinity)作用而形 成的微弱分子間力（Weak inter-molecular forces)，使得氣體 (或液體）分子附著於固體吸附劑表面上，此種現象稱為 吸附（Adsorption，有日f 亦稱為 Adsorptive separation)。在一 般的固氣界面上，固體表面原子會有向内拉的頃向，於是 201034749 造成不平衡力，氣體（流體）中某些物質為了滿足表面平 衡’以降低固體表面張力及自由能(Free energy)，因此向固 體表面移動，並附著在固體上。在該系統中，具有表面作 用的固體稱為吸附劑（Adsorbent)，被吸附之氣體分子稱為 吸附質（Adsorbate)。吸附作用是揮發性機物在空污防治應 用中一個極為重要之反應作用，其中該吸附機制係包含三 個步驟：步驟一、揮發性有機物擴散至吸附材之表面；步 驟二、揮發性有機物於吸附材孔洞内擴散；步驟三、揮發 〇 性有機物被吸附材孔洞所吸附。如此即可藉由吸附材來吸 附揮發性有機物。 吸附性質依其鍵結作用方式可區分為： 1. 物理性吸附（Physical adsorption) 2. 化學性吸附（Chemisorption) 物理性吸附主要涉及的是交互作用力也就是所謂凡得 瓦爾力（Van der Waals force; dispersion-repulsion)以及吸 Q 附質分子與吸附材表面間產生之極化(Polarization)、偶極 (Dipole)或雙偶極作用力（Quadrupole)而形成之靜電吸引 力（Electrostatic interaction force)所形成，但對於非極性 吸附質而言，倫敦擴散力（London dispersion force)仍是最主 要之吸附力。在靜電吸引力，這種作用力比倫敦擴散力較 具專一性；尤其在偶極分子與離子固體物之間更為顯著。 靜電吸引力大小與固體表面電場強度及分子被極化程度有 關’靜電吸引力在極性及非極性分子與共價性的固體物之 間無明顯作用，因為缺少了電場的作用。例如：沸石，因 201034749 其為具有極性之吸附材’其吸附的主要引力來源則包含倫 敦擴散力及靜電吸引力。 化學性吸附則是吸附質與固體表面之間，因親和力而 產生分子執域重疊作用並產生化學鍵結，其性質與化學鍵 相似，此時彼此的化性及電性均會改變，同時比物理性吸 附來得複雜得多。當化學吸附形成共價建時，稱之為弱化 學性吸附（Weak chemosorption);而形成離子鍵(Ionic bond) 時，稱為強化學性吸附（Strong chemosorption)。化學性吸附 為不可逆反應，脫附時將改變吸附劑特性，因此以化學性 吸附為主之反應，通常吸附劑不予再生。化學性吸附鍵結 能隨著吸附質與吸附劑間距離增加而降低，故只形成單層 吸附。且吸附質分子因化學反應，可能會有解離的情況發 生，吸附一般又可分為活性（Activated)反應和非活性 (Non-activated)反應兩種，活性反應有相當大的活性能，而 且反應速率隨溫度而變。非活性反應的活化能則接近於 零，因此反應速率很快。通常氣、固相之間一開始為非活 性吸附，之後則發生吸附速率慢，且隨溫度變化的活性吸 附現象。 所有的吸附分離程序都是操作在吸脫附之循環狀態 中，再吸附階段吸附材交替地與吸附質及其載體接觸，分 子選擇性的吸附住所需攫取之被吸附質，接著再進入脫附 再生步驟，在此程序中主要是將被選擇性吸附住之吸附質 脫附驅離出來，此步驟就是所謂的脫附程序（Desorption process)，有時也稱為再生程序（Regeneration process)。有 201034749 些時候為了處理極低濃度下吸脫附分離程序之隔離冷卻作 用或者為了避免吸脫附循環程序時不必要之交差污染發生 (Cross contamination)，在脫吸附之循環程序間可加入一隔 離程序（Separation process;purge process)，有時也稱為冷 卻程序（Cooling process)。 吸附材之再生方式有以下幾種方式：丨.壓力變化式 (Pressure swing) ; 2.溫度變化式（Thermal swing ; temperature swing);或 3.濃度變更式（Purge/c〇ncentrati〇n201034749 VI. Description of the Invention: [Technical Field] The present invention discloses a method for regenerating an adsorbent material, in particular, a method for purifying and regenerating an adsorbent material used for removing low-concentration organic exhaust gas pollutants and using a highly active material For example, ozone (〇3) or hydrogen peroxide from the two bases (ΟΗ·/Η〇2·/02·) can effectively purify the regenerated adsorbent. The present invention is used for wafer manufacturing, photovoltaic panel manufacturing, etc., for improving the efficiency of the catalyst and the adsorbent, prolonging the life of the catalyst adsorbent, and purifying the high air volume and low concentration. For the purification of waste gas, it is also suitable for air purification in/to waste water plants, painting and printing industries and related industries. [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 fluorine on the environment and the workers and the general public, Fluoride emission standards are becoming more and more stringent, and domestic and foreign regulations have formulated relevant emission standards for concentrated and six flavors. On the other hand, high-order manufacturing of high-tech plants has recently made difficult to handle molecules such as sulfur compounds and low-boiling organic compounds. Contaminants, the degree of purification required before the introduction of external air into the clean room is more stringent. In the semiconductor wafer fabrication plant and TFT-LCD panel optoelectronic manufacturing, the photoresist is used in the striPPing process. The composition is high boiling point and almost completely soluble. Organic compounds of water include monoethanolamine (MEA), dimethyl sapphire (DMS®), and ethylene glycol monobutyl ether (BDG). In the photoresist-removing process, the light-blocking dimethyl 201034749 keith is a kind of liquid with low boiling point and low volatility, but it is easy to form a low-boiling and malodorous dimethyl group during the treatment. Gaseous pollutants of dimethyl sulfide (DMS) and dimethyl disulfide (DMDS). However, conventional adsorption, condensation and absorption methods cannot completely remove low-boiling and low-water-soluble dimethyl sulfide and dimethyl dioxime, and they will produce malodor at low concentrations, which can easily affect the house. The surrounding living environment has triggered public protests, and it has also affected the product yield of high-end processes in other high-tech factories around the plant. The purification technique of low concentration organic compound gas in air can use physical methods, chemical methods and mixing methods. The physical method is to remove air from low-concentration organic compounds by using a physical purification step such as absorption, adsorption, separation, etc. The physical methods commonly used are mechanical separation, percolation, adsorption, washing and electrostatic methods. ~ The adsorption method is a common organic gas purification method at this stage. Due to the continuous breakthrough and development of human science and technology, the adsorption process (Adsorptionprocess) technology is widely used in chemical, biochemical, petrochemical and bad insurance industries. Purification and separation purification applications. Adsorption is a solid-gas (or solid-liquid) two-phase interface chemistry phenomenon. When the gas molecules (Molecules), atoms (Atoms) or ions (Ions) are close to the surface of the adsorbent at the solid-gas interface, the weak inter-molecular forces formed by the affinity of the molecules (Affinity) between them (Weak inter-molecular forces) ), causing gas (or liquid) molecules to adhere to the surface of the solid adsorbent. This phenomenon is called adsorption (adsorption, also known as Adsorptive separation). At the general solid-gas interface, the solid surface atoms will have an inward pulling direction, so 201034749 causes an imbalance force, and some substances in the gas (fluid) satisfy the surface balance to reduce the solid surface tension and free energy (Free Energy), thus moving toward the solid surface and attaching to the solid. In this system, a solid having a surface action is called an adsorbent, and the adsorbed gas molecule is called an adsorbent. Adsorption is an extremely important reaction of volatile organic compounds in air pollution control applications. The adsorption mechanism consists of three steps: step one, diffusion of volatile organic compounds to the surface of the adsorbent; step two, volatile organic compounds The diffusion of the adsorbent material is carried out in the hole; in step 3, the volatile organic matter is adsorbed by the pores of the adsorbent material. In this way, volatile organic compounds can be adsorbed by the adsorbent material. The adsorption properties can be distinguished according to the way of bonding: 1. Physical adsorption 2. Chemical adsorption (Chemisorption) Physical adsorption mainly involves interaction force, also known as Van der Waals force. Dispersion-repulsion) and electrostatic static interaction force formed by polarization (polarization), dipole or quadrupole generated between the Q-linked molecule and the surface of the adsorbent. Formed, but for non-polar adsorbates, London dispersion force is still the most important adsorption force. At electrostatic attraction, this force is more specific than London's diffusivity; especially between dipole molecules and ionic solids. The magnitude of the electrostatic attraction is related to the electric field strength of the solid surface and the degree to which the molecule is polarized. The electrostatic attraction has no significant effect between the polar and non-polar molecules and the covalent solids because of the lack of an electric field. For example: zeolite, because 201034749 is a polar adsorbent material's main source of gravity for adsorption includes London diffusivity and electrostatic attraction. Chemical adsorption is the interaction between the adsorbate and the solid surface due to the affinity of the molecules, and the chemical bond is generated. The properties are similar to the chemical bonds. At this time, the chemical and electrical properties of each other change, and the physical properties are changed. Adsorption is much more complicated. When chemical adsorption forms a covalent build, it is called Weak chemosorption; when an Ionic bond is formed, it is called Strong chemosorption. Chemical adsorption is an irreversible reaction, and the characteristics of the adsorbent are changed during desorption. Therefore, the chemical adsorption is the main reaction, and usually the adsorbent is not regenerated. The chemical adsorption bond energy decreases as the distance between the adsorbate and the adsorbent increases, so that only a single layer of adsorption is formed. And the adsorbed molecules may be dissociated due to chemical reactions. The adsorption is generally divided into two types: activated reaction and non-activated reaction. The active reaction has considerable activity and reaction. The rate varies with temperature. The activation energy of the inactive reaction is close to zero, so the reaction rate is fast. Usually, the gas and solid phases are initially inactively adsorbed, and then the adsorption rate is slow and the activity is adsorbed as a function of temperature. All of the adsorption separation procedures are operated in a cycle state of adsorption and desorption. In the adsorption phase, the adsorbent material is alternately contacted with the adsorbate and its carrier, and the molecularly selective adsorption of the adsorbed material to be adsorbed is followed by desorption. The regeneration step, in which the main adsorbent is desorbed by the selectively adsorbed adsorbent, this step is called the desorption process, sometimes called the regeneration process. In 201034749, in order to deal with the isolation cooling of the very low concentration adsorption and desorption separation procedure or to avoid unnecessary cross contamination during the desorption and desorption cycle, a separation can be added between the desorption cycles. The procedure (Separation process; purge process) is sometimes referred to as the cooling process. There are several ways to regenerate the adsorbent: 丨. Pressure swing; 2. Temperature swing; temperature swing; or 3. Concentration change (Purge/c〇ncentrati〇n
swing)，又可區分為沖提式（Inen purge)及取代式 (Displacement purge)。 而吸附材之再生係攸關去除空氣中有機氣體之淨化效 率，然傳統上之吸附材再生主要以壓力變化式及溫度變化 式為主，二者在吸附材之再生淨化程度僅可達七至八成左 右，也就是說’再生後之吸附材仍殘存許多吸附質（冷染 物）’吸附材之出口終極濃度受限’於吸附材之重覆使用上 有其缺陷，同時也耗費許多能源。再者，若採Μ汽取代 式來再生吸附材’則又有廢水問題。 、 因此，如财料錢麵本，並_料分再生吸 附材之功效，有效淨化再线吸_以錢使用來淨化空 氣中有機氣體，係為處理有機廢氣之—重要課題。 【發明内容】 心研究克服 全，二:其，生… 201034749 憑其從事該項產業多年之累積經驗，進而研發出一種吸附 材之淨化再生方法及系統，其係利用高活性物質如臭氧(〇 3 ) 或氫氧自由基(〇Η/Η〇2·/〇2·)等，可有效淨化再生吸附材， 使經淨化再生之吸附材得以重覆進行有機氣體之吸附作 用，降低有機氣體淨化之成本，同時有效達成資源重覆利 用功效，並完成節能減碳之目的。 本發明係利用高活性物質來進行吸附材之脫附作用， 其係為一種吸附材於吸附有機物質後之化學再生方法，所 使用的高活性物質係為臭氧(03)、氧氧自由基(ΟΗ·/Η〇27〇·) 等，該等高活性物質之氧化電位及反應如下表一所示： 表一、高活性物質之氧化電位及反應 種類 化學式 氧化電位（volt) 氧化反應 氫氧基 0H. 2.80 OH +H++e'—>HT〇 氧原子 0. 2.42 〇·+2Η++2β·-^Η,〇 臭氧 〇3 2.07 〇3+2H++2e.~^r^+fj 〇 過氧化氫 ηο2· 1.70 ---— w ηοΛ+3ΗΤ+3£-=>2Η2〇 而臭氧與有機物的反應機制可分為（一）直接 化反應（directozonztion，D-type)及（二）自由基式連鎖反應 (free radical chain reaction，R-type)，兩大類氧化機制之比孝六 如表二所不. 201034749 表二、臭氧氧化機制之比較 項目 直接反應 間接反應 氧化劑 臭氧分子(〇3) 氫氧自由基(ΟΗ·、Η〇2·) 氧化能力 強 更強 反應pH值 酸性(pH < 7) 中性(pH=7) 鹼性(pH >7) _反應速率 慢 快 作用機制 電偶極加成反應、親電子反應、親核 反應 親電子反應、脫氫反應、電子轉移 作用 作用物 選擇性 1. 未飽和芳香族、烯類簡單胺類 2. 含OH、NH2、0CH3等官能基之 化合物 微極性分手 無 -基化產物 一次氧化 j物生成 、羧酸生合早 易 "-- 醛類、酮類、羧類、醇類 不易 由上述臭氧氧化機制可知，直接反應適用於相對濕度 為85%RH以下’尤其是3〇〜6〇%RH為最佳；而該間接反 應則適用於含濕氣之場合，適用於相對濕度為7〇%RH a 〇 上，且為有加濕之反應場合。 為達成上述之目的，本發明係提供一種吸附材之淨化 再生方法，其係包含下列步驟： (1) 提供一種有機氣體淨化裝置，其中該有機氣體淨化 裝置係包含一吸附材，且該吸附材用於吸附所欲淨 化之有機氣體； (2) 提供一種高活性物質產生單元，其係用於淨化再生 被吸附於該吸附材之有機物質； (3) 將已吸附有機氣體之吸附材導入該高活性物質產 201034749 生單元所產生之高活性物質，以進行該吸附材之淨 化再生。 如上述之淨化再生方法，其中於該步驟（2)之後，進一 步包含(2-1)步驟，其係提供一加濕器，以於步驟(3)中提高 該吸附材淨化再生時之水汽含量（濕度），增加淨化再生之 效能。 如上述之淨化再生方法，其中該步驟(2)中之高活性物 質產生單元所產生之高活性物質係為：臭氧(〇3)或氫氧自由 基(0Η7Η02702·)等。 如上述之淨化再生方法，其中該吸附材係為蜂巢狀吸 附單體，且該蜂巢狀吸附單體係可為蜂巢狀沸石吸附單 體、蜂巢狀活性碳纖維紙吸附單體或蜂巢狀瓦楞紙吸附單 體。 如上述之淨化再生方法，其中該有機氣體淨化裝置係 可為：轉輪濃縮器、轉環式濃縮器、直立式淨化塔或卧式 淨化塔。 如上述之淨化再生方法，其中該有機氣體之濃度係為 0.001〜100 ppmv。 如上述之淨化再生方法，其係可作為吸附材之最終淨 化再生方法。 本發明之再一目的係提供一種吸附材之淨化再生系 統，其係包含： 一有機氣體淨化裝置，其中該有機氣體淨化裝置係包 含一吸附材，且該吸附材用於吸附所欲淨化之有機氣體； 10 201034749 一高活性物質產生單元，其係用於淨化再生被吸附於 該吸附材之有機物質； 其特徵在於：將該高活性物質產生單元所產生之高活 性物質導入已吸附有機氣體之吸附材，以進行該吸附材之 淨化再生。 如上所述之淨化再生系統，其係進一步包含一加濕 器，以提高該吸附材淨化再生時之水汽含量（濕度），增加 淨化再生之效能。 〇 如上所述之淨化再生系統，其中該高活性物質產生單 元所產生之高活性物質係為：臭氧（〇3)或氫氧自由基 (οη·/ηο2·/ο2·)等。 如上所述之淨化再生系統，其中該吸附材係為蜂巢狀 吸附單體，且該蜂巢狀吸附單體係可為蜂巢狀沸石吸附單 體、蜂巢狀活性碳纖維紙吸附單體或蜂巢狀瓦楞紙吸附單 體。 0 如上所述之淨化再生系統，其中該有機氣體淨化裝置 係可為：轉輪濃縮器、轉環式濃縮器、直立式淨化塔或卧 式淨化塔。 如上所述之淨化再生系統，其中該有機氣體之濃度係 為 0.001 〜100 ppmv。 如上所述之淨化再生系統，其係可作為觸媒與吸附材 之最終淨化再生系統。 藉由上述之再生方法及系統，係利用一高活性物質產 生單元以提供高活性物質：臭氧（03)或氫氧自由基 11 201034749 (OH7H027〇〇等，針對已經吸附有機物質之吸附材進行化 學氧化再生反應，以有效淨化再生該吸附材，以使該經再 生之吸附材得以重覆進行有機氣體之吸附及除污，可有效 增加該吸附材之效能、降低該吸附材之出口終極濃度、延 長該觸媒與吸附材之壽命。 【實施方式】 為使充分瞭解本發明之目的、特徵及功效，茲藉由下 述具體之實施例，並配合所附之圖式，對本發明做一詳細 說明，說明如後： 實施例一 本發明第一具體實施例之一種觸媒吸附材之淨化再生 系統1係如第一圖所示，其中該系統係包含：一有機氣體 淨化裝置10，其内包含一觸媒吸附單元Π，並該觸媒吸附 單元11填充有觸媒吸附材13，一高活性物質產生單元20 及一蒸氣加濕器30。 當該有機氣體淨化裝置10進行有機氣體淨化時，低濃 度VOCs氣體自一氣體入口 A經由一風車15吹入該有機氣 體淨化裝置10之内，而隨著第一圖中該有機氣體淨化裝置 10内之箭頭進行氣體之流動，而該低濃度VOCs氣體中之 有機物質則被該觸媒吸附單元11中之觸媒吸附材13所吸 附，而該觸媒吸附材13係為蜂巢狀吸附單體，且該蜂巢狀 吸附單體係可為蜂巢狀沸石吸附單體、蜂巢狀活性碳纖維 紙吸附單體或蜂巢狀瓦楞紙吸附單體；經吸附後之淨化氣 12 201034749 體則自氣體出口 B流出。 而於淨化該低濃度有VOCs氣體後，該觸媒吸附材13 中吸附著有機物質，會減低後續有機氣體之淨化效能，故 需針對該觸媒吸附材13進行淨化再生之反應。 . 本發明係利用一活性物質產生單元20來提供高活性物 質：臭氧(〇3)或氫氧自由基(〇H7H027CV)等，經由該風車 15之抽送，流入該有機氣體淨化裝置10之内，並流經該觸 媒吸附單元11中之觸媒吸附材13，針對該觸媒吸附材13 〇 中含吸附之有機物質進行淨化再生反應，利用該等高活性 物質來脫附該觸媒吸附材13内之有機物質，以完成該觸媒 吸附材之淨化再生。 本發明同時提供一加濕器30，其可提供水蒸氣於該有 機氣體淨化裝置10之中，以利該等高活性物質於高相對濕 度環境下進行該觸媒吸附材之淨化再生反應。 於本實施例中，所使用之低濃度之VOCs係為：丙酮 八 lOOOppbv、丙烯lOOppbv及MIBK(曱基異丁基曱酮） 5 Oppbv ;而實施例一係無提供蒸氣加濕，其入口之相對濕 度為40〜75%RH;另，實施例二則提供該蒸氣加濕，其入 口之相對濕度為75〜85%RH，該等觸媒吸附材13經淨化再 生後之淨化效率如表三所示。 比較實施例 第二圖係為習知濕式臭氧氧化洗滌法之裝置，係用為 本發明之比較實施例說明，其係為一直立式濕式洗滌塔2， 其内具有一灑水器40、一停滯層50，其係用以填充馬鞍型 13 201034749 陶瓷材，以使有機氣體於其内停滯進行氧化反應、一臭氧 供給器60，其係用以提供臭氧以使有機氣體與該臭氧於該 停滯層50進行氧化反應。使相同低濃度之VOCs :丙酮 lOOOppbv、丙烯 lOOppbv 及 MIBK(曱基異丁基曱酮）50ppbv 流經該直立式濕式洗滌塔2，並將其淨化效率記錄於表三。 表三、淨化效率結果比較表 填充材 接觸時間 RT (秒） 淨化效率 臭氧濃度 比較實施例 馬鞍型 陶瓷材 10秒 70%~85% 2000 ppb 實施例1 (無加濕） 蜂巢狀 疏水性 沸石單體 0.5秒 95% 〜98% 2000 ppb 實施例2 (有加濕） 蜂巢狀 疏水性 沸石單體 0.5秒 >99% 2000 ppb 由上表中可知，經本發明提供之高活性物質淨化再生 後之觸媒吸附材，由於其内淨化再生較為完全，故其淨化 效率可達95%以上，尤其是，當提供蒸氣加濕後，該淨化 效率更可達99%以上，可見本發明所提供之高活性物質可 有效淨化該觸媒吸附材。 實施例二 本發明第二具體實施例係如第三圖所示，其係將本發 明所提供之一高活性物質產生單元2 0連接於習知之濃縮轉 輪70，該濃縮轉輪70具一吸附區I及一脫附區II，且該濃 縮轉輪70之運轉方式係為連續性轉動或步進式轉動，其中 該濃縮轉輪70係為一蜂巢狀沸石轉輪（吸附材為蜂巢狀沸 石），而所欲淨化之低濃度VOCs氣體係自一氣體入口 A流 14 201034749Swing), can be divided into Inen purge and Displacement purge. The regeneration of the adsorbent material is used to remove the purification efficiency of the organic gas in the air. However, the regeneration of the adsorbent material is mainly based on the pressure change type and the temperature change type, and the regeneration degree of the adsorbent material is only up to seven. About 80%, that is to say, 'there is still a lot of adsorbent (cold dye) remaining in the adsorbent after regeneration. 'The ultimate concentration of the adsorbent material is limited.' It has its defects in the repeated use of the adsorbent material, and it also consumes a lot of energy. Furthermore, there is a problem of wastewater if the sulphur gas is replaced by a regenerative adsorbent. Therefore, such as the money and money, and the effect of reclaiming the adsorbent material, effectively purifying and re-absorbing _ using money to purify the organic gas in the air is an important issue for the treatment of organic waste gas. [Summary of the Invention] Heart research overcomes all, two: it, raw... 201034749 Based on its accumulated experience in the industry for many years, it has developed a purification method and system for adsorbing materials, which utilizes highly active substances such as ozone (〇 3) or hydroxyl radicals (〇Η/Η〇2·/〇2·), etc., can effectively purify the regenerated adsorbent material, so that the purified and regenerated adsorbent material can be repeatedly adsorbed by organic gases, reducing organic gas purification. The cost, while effectively achieving the repeated use of resources, and the goal of energy saving and carbon reduction. The invention utilizes a highly active substance to perform the desorption of the adsorbent material, which is a chemical regeneration method of the adsorbent material after adsorbing the organic substance, and the high active substance used is ozone (03), oxygen oxygen free radical ( ΟΗ·/Η〇27〇·), etc., the oxidation potentials and reactions of these highly active substances are shown in Table 1 below: Table 1. Oxidation potential and reaction type of highly active substances Chemical oxidation potential (volt) Oxidation reaction hydroxyl group 0H. 2.80 OH +H++e'—>HT〇Oxygen atom 0. 2.42 〇·+2Η++2β·-^Η, 〇Ozone 〇3 2.07 〇3+2H++2e.~^r^+ Fj 〇 hydrogen peroxide ηο2· 1.70 ---- w ηοΛ+3ΗΤ+3£-=>2Η2〇 and the reaction mechanism between ozone and organic matter can be divided into (1) direct zoning (D-type) and ( b) Free radical chain reaction (R-type), the two major oxidation mechanisms of the filial piety are as shown in Table 2. 201034749 Table II, comparison of ozone oxidation mechanism Direct reaction indirect reaction oxidant ozone molecule ( 〇3) Hydroxyl radicals (ΟΗ·,Η〇2·) Strong oxidizing ability and stronger reaction pH Acidity (pH < 7) Neutral (pH=7) Alkaline (pH > 7) _ Slow reaction rate mechanism Electric dipole addition reaction, electrophilic reaction, nucleophilic reaction, electrophilic reaction, dehydrogenation reaction, Electron transfer interaction selectivity 1. Unsaturated aromatic, olefinic simple amines 2. Compounds containing functional groups such as OH, NH2, 0CH3, etc. Micropolar separation of non-based products, primary oxidation, formation of carboxylic acid, carboxylic acid synthesis Early easy "-- aldehydes, ketones, carboxyls, alcohols are not easily known by the above ozone oxidation mechanism, direct reaction is suitable for relative humidity of 85% RH or less 'especially 3〇~6〇% RH is the best; The indirect reaction is suitable for applications containing moisture, suitable for relative humidity of 7〇% RH a ,, and for humidification reactions. In order to achieve the above object, the present invention provides a method for purifying and regenerating an adsorbent material, which comprises the following steps: (1) Providing an organic gas purifying device, wherein the organic gas purifying device comprises an adsorbent material, and the adsorbent material For adsorbing the organic gas to be purified; (2) providing a high active material generating unit for purifying and regenerating the organic substance adsorbed to the adsorbing material; (3) introducing the adsorbing material of the adsorbed organic gas into the The highly active substance produces a highly active substance produced by the unit of 201034749 to purify and regenerate the adsorbed material. The purification and regeneration method as described above, wherein after the step (2), further comprising a step (2-1), which provides a humidifier to increase the water vapor content of the adsorbent material during the purification and regeneration in the step (3). (Humidity), increasing the efficiency of purification and regeneration. The purification and regeneration method as described above, wherein the highly active substance produced by the high active substance generating unit in the step (2) is ozone (〇3) or hydrogen-oxygen free radical (0Η7Η02702·). The purification and regeneration method as described above, wherein the adsorbent material is a honeycomb adsorbent monomer, and the honeycomb adsorption single system may be a honeycomb zeolite adsorption monomer, a honeycomb activated carbon fiber paper adsorption monomer or a honeycomb corrugated paper adsorption sheet. body. The purification and regeneration method as described above, wherein the organic gas purification device is a rotary concentrator, a rotary concentrator, a vertical purification tower or a horizontal purification tower. The purification regeneration method as described above, wherein the concentration of the organic gas is 0.001 to 100 ppmv. The purification and regeneration method as described above can be used as a final purification method for the adsorption material. A further object of the present invention is to provide a purification and regeneration system for an adsorbent material, comprising: an organic gas purification device, wherein the organic gas purification device comprises an adsorbent material, and the adsorbent material is used for adsorbing organic substances to be purified. Gas; 10 201034749 A high-activity substance generating unit for purifying and regenerating an organic substance adsorbed to the adsorbing material; characterized in that the high-active substance produced by the high-active substance generating unit is introduced into the adsorbed organic gas The adsorbent material is used to purify and regenerate the adsorbent material. The purification and regeneration system as described above further comprises a humidifier to increase the water vapor content (humidity) of the adsorbent material during purification and regeneration, and to improve the efficiency of purification and regeneration. The purification and regeneration system as described above, wherein the highly active substance produced by the high-activity substance generating unit is ozone (〇3) or hydroxide radical (οη·/ηο2·/ο2·). The purification and regeneration system as described above, wherein the adsorbent material is a honeycomb adsorbent monomer, and the honeycomb adsorption single system can be a honeycomb adsorbent monomer, a honeycomb activated carbon fiber paper adsorbent monomer or a honeycomb corrugated paper adsorption. monomer. The purification regeneration system as described above, wherein the organic gas purification device can be: a rotary concentrator, a rotary concentrator, a vertical purification tower or a horizontal purification tower. The purification regeneration system as described above, wherein the concentration of the organic gas is 0.001 to 100 ppmv. The purification and regeneration system as described above can be used as a final purification and regeneration system for the catalyst and the adsorbent. By the above-mentioned regeneration method and system, a high active substance generating unit is used to provide a highly active substance: ozone (03) or hydroxyl radical 11 201034749 (OH7H027〇〇, etc., for the adsorption material of the organic substance adsorbed Oxidizing the regeneration reaction to effectively purify and regenerate the adsorbent material, so that the regenerated adsorbent material can be repeatedly adsorbed and decontaminated by the organic gas, thereby effectively increasing the efficiency of the adsorbent material and reducing the ultimate concentration of the adsorbent material. Extending the life of the catalyst and the adsorbent material. [Embodiment] In order to fully understand the object, features and effects of the present invention, the present invention will be described in detail by the following specific embodiments and the accompanying drawings. DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 A purification and regeneration system 1 for a catalyst adsorbing material according to a first embodiment of the present invention is as shown in the first figure, wherein the system comprises: an organic gas purifying device 10, wherein A catalyst adsorption unit 包含 is included, and the catalyst adsorption unit 11 is filled with a catalyst adsorbing material 13, a high active material generating unit 20 and a steam humidifier 3 When the organic gas purification device 10 performs organic gas purification, the low concentration VOCs gas is blown into the organic gas purification device 10 from a gas inlet A via a windmill 15, and the organic gas purification is performed in the first figure. The arrow in the device 10 carries out the flow of the gas, and the organic matter in the low-concentration VOCs gas is adsorbed by the catalyst adsorbing material 13 in the catalyst adsorbing unit 11, and the catalytic adsorbing material 13 is honeycomb-like adsorbed. Monomer, and the honeycomb adsorption single system may be a honeycomb zeolite adsorption monomer, a honeycomb activated carbon fiber paper adsorption monomer or a honeycomb corrugated paper adsorption monomer; the adsorbed purified gas 12 201034749 is from the gas outlet B After purifying the VOCs gas at a low concentration, the organic matter is adsorbed in the catalyst adsorbing material 13, which reduces the purification efficiency of the subsequent organic gas, so that the catalyst adsorbing material 13 needs to be purified and regenerated. The present invention utilizes an active material generating unit 20 to provide a highly active substance: ozone (〇3) or hydroxide radical (〇H7H027CV), etc., and is pumped through the windmill 15 to flow into the The organic gas purification device 10 flows through the catalyst adsorption material 13 in the catalyst adsorption unit 11, and purifies and regenerates the organic substance adsorbed in the catalyst adsorption material 13 to utilize the highly active substances. The organic substance in the catalyst adsorbing material 13 is desorbed to complete the purification and regeneration of the catalyst adsorbing material. The present invention also provides a humidifier 30 for supplying water vapor to the organic gas purifying device 10, In order to facilitate the purification and regeneration reaction of the catalyst adsorbent in the high relative humidity environment, in the present embodiment, the low concentration VOCs used are: acetone 810 ppbv, propylene 100 ppbv and MIBK (曱) Isobutyl ketone ketone) 5 Oppbv; while Example 1 does not provide steam humidification, the relative humidity of the inlet is 40~75% RH; in addition, the second embodiment provides the steam humidification, the relative humidity of the inlet The purification efficiency of the catalyst adsorbing materials 13 after purification and regeneration is as shown in Table 3, which is 75 to 85% RH. The second embodiment of the comparative example is a conventional wet ozone oxidation washing apparatus, which is described as a comparative embodiment of the present invention, which is an upright wet scrubber 2 having a sprinkler 40 therein. a stagnant layer 50 for filling the saddle type 13 201034749 ceramic material to cause the organic gas to stagnate therein for oxidation reaction, and an ozone feeder 60 for supplying ozone to the organic gas and the ozone The stagnant layer 50 is subjected to an oxidation reaction. The same low concentration of VOCs: acetone lOOOOppbv, propylene lOOppbv and MIBK (nonylisobutyl fluorenone) 50 ppbv were passed through the vertical wet scrubber 2, and the purification efficiency thereof was recorded in Table 3. Table 3, purification efficiency results comparison table filler contact time RT (seconds) purification efficiency ozone concentration comparison example saddle ceramic material 10 seconds 70% ~ 85% 2000 ppb Example 1 (no humidification) Honeycomb hydrophobic zeolite single Body 0.5 sec 95% ～98% 2000 ppb Example 2 (with humidification) Honeycomb hydrophobic zeolite monomer 0.5 sec > 99% 2000 ppb As can be seen from the above table, the high active substance provided by the present invention is purified and regenerated. The catalyst adsorption material has a purification efficiency of more than 95% due to its complete purification and regeneration. In particular, when the steam is humidified, the purification efficiency is more than 99%, which can be seen by the present invention. The active material can effectively purify the catalyst adsorbing material. The second embodiment of the present invention is as shown in the third figure. The high active material generating unit 20 provided by the present invention is connected to a conventional concentrated rotating wheel 70, and the concentrated rotating wheel 70 has a The adsorption zone I and a desorption zone II, and the operation mode of the concentration reel 70 is continuous rotation or stepwise rotation, wherein the concentration reel 70 is a honeycomb zeolite runner (the adsorption material is honeycomb) Zeolite), and the low concentration VOCs gas system to be purified from a gas inlet A stream 14 201034749
經該濃縮轉輪70之吸附區I，而該等有機廢氣即被吸附於 該濃縮轉轉70之蜂巢狀沸石上，而淨化後之氣體即由一氣 體出口 B排出；而本發明利用一高活性物質產生單元20(本 實施例中係為一非熱電漿）提供產生高活性物質：臭氧(03) 或氫氧自由基(0Η7Η02702·)等，流經該濃縮轉輪70之脫附 區II，與已吸附有機物質之蜂巢狀沸石進行淨化再生，而 取代習知之熱氣流之脫附作用，而本實施例中所使用之低 濃度 VOCs 氣體為：IPA lOOppbv、PGMEA 20ppbv，其結 果’經本發明所提供之高活性物質：臭氧(〇3)或氫氧自由基 (OH/H〇2_/CV)等淨化再生後，該濃縮轉輪70之淨化效率可 持續達90%以上。 本實施例中之濃縮轉輪70若改為經貴金屬改質之蜂巢 狀濟石觸媒所構成，除彻本發明-高活性物質產生單元 20提供產生南活性物質來再生外，並搭配一加熱器卯加熱 ^ 150〜25GC ’促進彿石觸媒進—步氧化有機物，則該濃 縮轉輪7G觸媒吸附材之淨化效率可進—步持續達娜以 實施例三 本發明第三具體實施例係如第四圖所示，其係將^ 剛，生單元2。連接於習知樣 由複數個1 辰縮轉％ 8G料—蜂巢狀活性碳轉環，^ 由後數個吸附箱塊82所椹 、 '、仙·、，、乂該浪縮轉環80之一吸附區I，汗 15 201034749 等有機廢氣即被吸附於該濃縮轉環80中吸附箱塊82内之 蜂巢狀活性竣吸附材之上上，而淨化後之氣體即由一氣體 出口 B排出，而本發明利用一高活性物質產生單元20 (本 實施例中係為一臭氧產生器）提供高活性物質：臭氧(〇3)， 流經該濃縮轉環80之一脫附區Π，與已吸附有機物質之蜂 巢狀活性碳吸附材進行淨化再生，而取代習知之加熱器90 之脫附作用，而本實施例中所使用之低濃度VOCs氣體為： PGMEA 1 Oppmv、入口相對濕度為4〇〜6〇%RH且入口溫度 為25°C，其結果，經本發明所提供之高活性物質：臭氧(〇3) f ? 等淨化再生後，該濃縮轉環80之淨化效率可達95%以上； 且習知濃縮轉環係使用圓柱狀活性碳，其係容易因為吸附 熱及VOCs氧化熱累積碎裂，而無法再生重覆使用。 由上述之具體實施例可知，本發明所提供一種吸附材 之淨化再生方法m其係利用高活性物質如臭氧㈣ 或氫氧自由基(QH./HCV/CV)等，可有效淨化再生吸附材， 亦可結合-加濕器，使經淨化再生之吸附材得以重覆進行 有機氣體之吸附作用’降低有機氣體淨化之成本，同時有U 效達成資源重覆利用功效’並完成節能減叙目的。 【圖式簡單說明】 第-圖係為本發明第一具體實施例之一觸媒吸附材之淨 化再生系統。 第二圖係為本發明-比較實施例之一直立式濕式洗滌 塔。 16 201034749 第三圖係為本發明第二具體實施例之結合一濃縮轉輪之 淨化再生系統。 第四圖係為本發明第三具體實施例之結合一漠縮轉環之 淨化再生系統。 【主要元件符號說明】 1 吸附材之淨化再生系統 2 直立式濕式洗滌塔 10 有機氣體淨化裝置 11 一吸附單元 13 吸附材 15 風車 20 高活性物質產生單元 30 加濕器 40 灑水器 50 停滯層 60 臭氧供給器 70 濃縮轉輪 80 濃縮轉環 82 吸附箱塊 90 加熱器 A 氣體入口 B 氣體出口 I 吸附區 17 201034749 II 脫附區Through the adsorption zone I of the concentration runner 70, the organic waste gas is adsorbed on the honeycomb zeolite of the concentrated transfer 70, and the purified gas is discharged from a gas outlet B; and the present invention utilizes a high The active material generating unit 20 (which is a non-thermal plasma in the present embodiment) provides a highly active substance: ozone (03) or hydroxyl radical (0Η7Η02702·), etc., and the desorption zone II flowing through the concentrated reel 70 Purifying and regenerating the honeycomb zeolite with adsorbed organic matter instead of the desorption of the conventional hot gas stream, and the low concentration VOCs gas used in the present embodiment is: IPA 100 ppbv, PGMEA 20 ppbv, and the result 'by the present invention After purification and regeneration of the highly active substance provided by ozone (〇3) or hydroxyl radical (OH/H〇2_/CV), the purification efficiency of the concentrated runner 70 can be maintained at more than 90%. In the present embodiment, the concentrated reel 70 is composed of a honeycomb-shaped jewel catalyst modified by a noble metal, and the present invention-high active material generating unit 20 provides a south active material for regeneration, and is combined with a heating.卯 heating 150 150~25GC 'promotes the sulphur catalyst to step-oxidize the organic matter, the purification efficiency of the concentrating runner 7G catalyst adsorbing material can be further advanced to Dana to the third embodiment of the present invention As shown in the fourth figure, it will be ^, just unit 2. Connected to the conventional sample by a plurality of 1 缩 转 % 8 8 8 8 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂 蜂An organic waste gas such as an adsorption zone I, Khan 15 201034749 is adsorbed on the honeycomb-shaped active ruthenium adsorption material in the adsorption block 82 of the concentrated rotary ring 80, and the purified gas is discharged from a gas outlet B. The present invention utilizes a highly active material generating unit 20 (which is an ozone generator in this embodiment) to provide a highly active substance: ozone (〇3), flowing through one of the desorption zones of the concentrated rotating ring 80, and The honeycomb activated carbon adsorbing material adsorbing the organic substance is purified and regenerated to replace the desorption of the conventional heater 90, and the low concentration VOCs gas used in the present embodiment is: PGMEA 1 Oppmv, and the inlet relative humidity is 4〇. ～6〇% RH and the inlet temperature is 25° C. As a result, after purification and regeneration by the high active material provided by the present invention: ozone (〇3) f 等 , the purification efficiency of the concentrated rotary ring 80 can reach 95% or more. And the conventional concentrated rotating ring system uses cylindrical activated carbon, which is easy Because the heat of adsorption and the oxidation heat of VOCs accumulate and fragment, they cannot be regenerated and reused. It can be seen from the above specific embodiments that the present invention provides a method for purifying and regenerating an adsorbent material, which is capable of effectively purifying a regenerated adsorbent material by using a highly active material such as ozone (4) or a hydroxyl radical (QH./HCV/CV). It can also be combined with a humidifier to regenerate the adsorbed material that has been purified and regenerated to reduce the adsorption of organic gases, reduce the cost of organic gas purification, and at the same time achieve U-effects to achieve repeated use of resources' and complete energy saving and reduction purposes. . BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a purification system for a catalyst adsorbent according to a first embodiment of the present invention. The second figure is an upright vertical wet scrubber of the present invention - a comparative example. 16 201034749 The third figure is a purification and regeneration system incorporating a concentrated reel according to a second embodiment of the present invention. The fourth figure is a purification and regeneration system combined with a deserted swivel according to a third embodiment of the present invention. [Description of main component symbols] 1 Purification and regeneration system of adsorption material 2 Vertical wet scrubber 10 Organic gas purification device 11 One adsorption unit 13 Adsorbent material 15 Windmill 20 High active material generating unit 30 Humidifier 40 Sprinkler 50 Stagnant Layer 60 Ozone feeder 70 Concentrated runner 80 Concentrated swivel 82 Adsorption tank block 90 Heater A Gas inlet B Gas outlet I Adsorption zone 17 201034749 II Desorption zone