TW201625356A - Preparation of ceramic supported catalyst and the applications for catalytic ozonation to degrade organic wastewater - Google Patents
Preparation of ceramic supported catalyst and the applications for catalytic ozonation to degrade organic wastewater Download PDFInfo
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本發明係有關於一種陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法，尤指一種將承載有鐵、錳或銅其中之一活性金屬之陶瓷觸媒，運用於催化臭氧產生自由基氧化，以有效降解有機廢水之陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法。The invention relates to a method for preparing a ceramic catalyst and a method for a ceramic catalyst for catalyzing the degradation of organic wastewater by ozone, in particular to a ceramic catalyst carrying one of iron, manganese or copper active metals for use in catalysis. A method for preparing a ceramic catalyst for ozone to generate free radical oxidation, to effectively degrade organic wastewater, and a ceramic catalyst for catalyzing ozone degradation of organic wastewater.
按，石化工業、鋼鐵業及半導體晶圓產業等皆為高耗能、高耗水產業型態，且其所排放廢水中常含芳香環類具毒性之有機化合物，該未經處理的有毒廢水被直接排入環境中，不僅對環境造成嚴重污染，且經食物鏈等途徑進入人體後，更導致各種疾病的發生。According to the petrochemical industry, the steel industry and the semiconductor wafer industry, all of which are high-energy-consumption and high-consumption water-based industries, and the discharged wastewater often contains aromatic compounds with toxicity, and the untreated toxic waste water is Direct discharge into the environment not only causes serious pollution to the environment, but also causes various diseases after entering the human body through the food chain and other means.
目前對含芳香環類具毒性之有機化合物廢水處理技術包括生物處理程序(Biological treatment process)、化學法及高階氧化程序(Advanced Oxidation Processes AOPs)等，由現行操作經驗得知生物法無法有效解決其高毒性問題，化學法又具反應條件等限制，因此，高階氧化程序係成為現有解決有毒廢水的主要方法，近年來高階氧化程序係包含有芬頓氧化法(Fenton oxidation)及濕式氧化法(Wet air oxidation)等，高階氧化程序分解污染物關鍵在於氫氧自由基(OH．)生成量，其所生成的氫氧自由基具強氧化能力，可有效分解污染物，然利用芬頓法氧化有機物後，同時會產生大量的三價鐵離子，又須另藉由化學混凝法去除鐵離子，而造成處理成本增加，另濕式氧化程序則須在高溫及高壓下提高液相的溶氧量，以將生物不易分解的有機質或難分解物質直接礦化或快速分解成具小分子量的中間產物，然此處理程序係易受到供應氧氣純度、操作壓力及操作溫度等因素影響，反應條件複雜不易控制，而造成實施上困難性。At present, the treatment technology of organic compound wastewater containing aromatic rings includes biological treatment process, chemical method and Advanced Oxidation Processes (AOPs). It is learned from current operational experience that biological methods cannot effectively solve them. High toxicity problems, chemical methods and reaction conditions, etc., therefore, high-order oxidation procedures have become the main method to solve toxic waste water. In recent years, high-order oxidation procedures include Fenton oxidation and wet oxidation ( Wet air oxidation), etc., the high-order oxidation process to decompose pollutants is the key to the formation of hydroxyl radicals (OH.), the hydrogen-oxygen radicals generated by them have strong oxidizing ability, can effectively decompose pollutants, and then use Fenton oxidation After the organic matter, a large amount of ferric ions are generated at the same time, and the iron ions are removed by chemical coagulation, which causes an increase in the processing cost, and the wet oxidation process must increase the dissolved oxygen in the liquid phase at a high temperature and a high pressure. Amount that directly mineralizes or rapidly decomposes organic matter or hardly decomposable substances that are not easily decomposed by organisms into small molecules. The intermediate product, then the handler system is susceptible to supply oxygen purity, operating pressure and operating temperature, etc., the reaction conditions are complicated and difficult to control, resulting in difficulty on the embodiment.
緣是，本發明人有鑑於現有高階氧化程序法於處理含芳香環類具毒性之有機化合物廢水時，仍具有上述諸多缺失，乃藉其多年於相關領域的製造及設計經驗和知識的輔佐，並經多方巧思，針對現有進行研發改良，而研創出本發明。The reason is that the present inventors have the above-mentioned many shortcomings in view of the existing high-order oxidation procedure for treating waste water containing organic compounds containing aromatic rings, which is supported by many years of manufacturing and design experience and knowledge in related fields. And through various ingenuity, research and development of the existing research and development, and research and development of the present invention.
本發明係有關於一種陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法，其主要目的係為了提供一種將承載有鐵、錳或銅其中之一活性金屬之陶瓷觸媒，運用於催化臭氧產生自由基氧化，以有效降解有機廢水之陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法。The invention relates to a method for preparing a ceramic catalyst and a method for preparing a ceramic catalyst for catalyzing ozone degradation of organic wastewater, the main purpose of which is to provide a ceramic catalyst which will carry one of iron, manganese or copper as active metal. The invention relates to a method for preparing a ceramic catalyst for catalyzing the generation of free radical oxidation of ozone, for effectively degrading organic wastewater, and a ceramic catalyst for catalyzing the degradation of organic wastewater by ozone.
為了達到上述實施目的，本發明人乃研擬如下陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法，係主要以陶瓷為載體，並將該陶瓷載體以濕式含浸法浸泡入含有鐵、錳或銅其中之一金屬活化劑之溶液中，使其進行離子交換，且以不同升溫梯度將陶瓷觸媒上之金屬轉化成高臭氧催化活性之金屬氧化物，以製成承載有鐵、錳或銅其中之一活性金屬氧化物之陶瓷觸媒，藉此承載有鐵、錳或銅等活性金屬氧化物之陶瓷觸媒，以運用於催化臭氧產生自由基氧化降解有機廢水。In order to achieve the above-mentioned object, the present inventors have developed the following ceramic catalyst preparation method and a ceramic catalyst for catalyzing the degradation of organic wastewater by ozone, mainly using ceramic as a carrier, and the ceramic carrier is wet impregnated. Soaking into a solution containing one of iron, manganese or copper as a metal activator, ion-exchange, and transforming the metal on the ceramic catalyst into a high-ozone catalytically active metal oxide with different heating gradients. a ceramic catalyst carrying one of iron, manganese or copper as an active metal oxide, thereby carrying a ceramic catalyst of active metal oxide such as iron, manganese or copper for catalytic generation of free radical oxidation of organic wastewater by ozone .
如上所述之陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法，其中，該陶瓷觸媒製備過程中係提高其含浸活性金屬濃度，以增加陶瓷觸媒中活性金屬含量。The ceramic catalyst preparation method and the ceramic catalyst as described above are used for catalyzing the ozone degradation of organic wastewater, wherein the ceramic catalyst is prepared to increase the concentration of the impregnated active metal to increase the active metal content in the ceramic catalyst. .
如上所述之陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法，其中，該有機廢水其pH值為pH8時，對含鐵金屬之陶瓷觸媒有最佳降解效果。The ceramic catalyst preparation method and the ceramic catalyst as described above are used for catalyzing the ozone degradation of organic wastewater, wherein the organic wastewater has a pH of 8 and has the best degradation effect on the ceramic catalyst containing iron metal.
如上所述之陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法，其中，該含鐵金屬之陶瓷觸媒於催化臭氧降解有機廢水時，係進一步以延長時間與控制pH值，提升降解效率。The ceramic catalyst preparation method and the ceramic catalyst as described above are used for catalyzing the ozone degradation of organic wastewater, wherein the ferrous metal-containing ceramic catalyst is further used to prolong the time and control the pH when catalyzing the ozone degradation of the organic wastewater. Value, improve degradation efficiency.
如上所述之陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法，其中，係主要以含銅金屬之陶瓷觸媒進行催化氧化效果，另次之以含錳金屬之陶瓷觸媒進行催化氧化效果。The ceramic catalyst preparation method and the ceramic catalyst as described above are used for catalyzing the ozone degradation of organic wastewater, wherein the catalytic oxidation effect is mainly carried out by a ceramic catalyst containing copper metal, and the ceramic containing manganese metal is further used. The catalyst performs a catalytic oxidation effect.
如上所述之陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法，其中，該含浸之鐵金屬濃度以0.15莫耳(M)為最佳。The ceramic catalyst preparation method and the ceramic catalyst as described above are used for the method for catalyzing the ozone degradation of organic wastewater, wherein the metal concentration of the impregnated iron is preferably 0.15 mol (M).
如上所述之陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法，其中，該含浸之錳金屬濃度以0.25莫耳(M)為最佳。The ceramic catalyst preparation method and the ceramic catalyst as described above are used for the method for catalyzing the ozone degradation of organic wastewater, wherein the impregnated manganese metal concentration is preferably 0.25 mol (M).
如上所述之陶瓷觸媒製備方法及陶瓷觸媒用於催化臭氧降解有機廢水之實施方法，其中，該陶瓷載體係以球型為最佳。The ceramic catalyst preparation method and the ceramic catalyst as described above are used for the method for catalyzing the ozone degradation of organic wastewater, wherein the ceramic carrier is preferably spherical.
而為令本發明之技術手段及其所能達成之效果，能夠有更完整且清楚的揭露，茲詳細說明如下，請一併參閱揭露之圖式及圖號：In order to make the technical means of the present invention and the effects thereof can be more completely and clearly disclosed, the following is a detailed description. Please refer to the disclosed drawings and drawings:
首先，請參閱第一圖所示，為本發明之用於催化臭氧降解有機廢水之陶瓷觸媒製備方法，其實施步驟係包含：First, referring to the first figure, the method for preparing a ceramic catalyst for catalyzing ozone degradation of organic wastewater according to the present invention comprises the following steps:
Ａ.製備載體：係製備一多孔性陶瓷為載體，該多孔性陶瓷載體以球型為最佳；A. preparing a carrier: preparing a porous ceramic as a carrier, the porous ceramic carrier is preferably spherical;
Ｂ.金屬活化劑選擇：選用鐵、錳或銅其中之一為金屬活化劑；B. Metal activator selection: one of iron, manganese or copper is selected as a metal activator;
Ｃ.濕式含浸：將乾燥之陶瓷載體浸泡入含有金屬活化劑之溶液中，使其進行離子交換，含浸時間約為24小時；C. Wet impregnation: soaking the dried ceramic carrier into a solution containing a metal activator for ion exchange, the impregnation time is about 24 hours;
Ｄ.清洗：將浸泡於金屬活化劑溶液中之陶瓷載體取出，再將其泡入去離子水中清洗，以將殘留其上之金屬活化劑溶液洗去；D. cleaning: the ceramic carrier soaked in the metal activator solution is taken out, and then washed in deionized water to wash away the metal activator solution remaining thereon;
Ｅ.乾燥：將洗淨之陶瓷載體瀝乾，再置入恆溫烘箱中去除水分；E. Drying: draining the washed ceramic carrier and placing it in a constant temperature oven to remove moisture;
Ｆ.鍛燒：再將去除水分乾燥後之陶瓷載體進行鍛燒程序，以不同升溫梯度將陶瓷載體上之金屬轉化成高臭氧催化活性之金屬氧化物；F. calcination: the ceramic carrier after removing the moisture is subjected to a calcination process, and the metal on the ceramic carrier is converted into a metal oxide having high ozone catalytic activity by different heating gradients;
Ｇ.成品：製成承載有鐵、錳或銅其中之一活性金屬氧化物之陶瓷觸媒成品。G. Finished product: a finished ceramic catalyst loaded with one of iron, manganese or copper active metal oxide.
據此，請一併參閱第二圖所示，當將該多孔性陶瓷觸媒應用於臭氧催化氧化系統時，係以填充床批式反應器進行臭氧催化降解含酚等溶液之有機廢水，以催化臭氧產生自由基氧化降解含酚等有機廢水，並以高壓液相層析儀(HPLC)與總有機碳分析儀(TOC)測定水中酚轉化率及水中總有機碳去除率，且利用感應耦合電漿原子發射光譜儀(ICP)分析實驗過程中金屬溶出情形，另以螢光分析儀探討臭氧催化氧化反應器催化產生自由基之活性，以比表面積分析儀(BET)分析陶瓷觸媒球之孔隙特性，並以掃描式電子顯微鏡(SEM)觀察陶瓷觸媒球表面結構及金屬分佈狀態，另以X射線能量分散光譜儀(EDS)分析觸媒球體表面金屬元素組成。藉上述設備輔助，本發明主要進行二部分試驗，第一部分試驗係探討將鐵型陶瓷觸媒應用於臭氧催化氧化系統對含酚溶液之降解，以不同變數探討去除效率，另第二部分則係探討以其他金屬陶瓷觸媒與鐵型陶瓷觸媒比較其催化活性與氧化效果。Accordingly, please refer to the second figure, when the porous ceramic catalyst is applied to the ozone catalytic oxidation system, the ozone-catalyzed degradation of the organic wastewater containing the phenol and the like is carried out by using a packed bed batch reactor. Catalytic Ozone Produces Free Radical Oxidative Degradation of Organic Wastewater Containing Phenol, and Determination of Phenol Conversion Rate and Total Organic Carbon Removal Rate in Water by High Pressure Liquid Chromatography (HPLC) and Total Organic Carbon Analyzer (TOC), and Inductive Coupling Plasma atomic emission spectrometer (ICP) was used to analyze the metal dissolution during the experiment. The fluorescence analyzer was used to investigate the activity of the catalytic activity of the ozone catalytic oxidation reactor. The specific surface area analyzer (BET) was used to analyze the pores of the ceramic catalyst sphere. Characteristics, and the surface structure and metal distribution of the ceramic catalyst sphere were observed by scanning electron microscopy (SEM). The composition of the metal elements on the surface of the catalyst sphere was analyzed by X-ray energy dispersive spectroscopy (EDS). With the aid of the above equipment, the present invention mainly conducts two-part test. The first part of the experiment discusses the application of the iron-type ceramic catalyst to the degradation of the phenol-containing solution by the ozone catalytic oxidation system, and discusses the removal efficiency with different variables, and the second part is The catalytic activity and oxidation effect of other cermet catalysts compared with iron-type ceramic catalysts were investigated.
於此，本發明第一部分試驗係將鐵型陶瓷觸媒（含浸氯化鐵濃度0.05莫耳(M)、0.1莫耳(M)、0.15莫耳(M)、0.2莫耳(M)、0.25莫耳(M)）各取相同質量加入氧化處理系統中，探討不同含浸金屬濃度的變化對氧化效果的影響，依其含鐵離子濃度，下述以F5、F10、F15、F20、F25為其名稱。實驗觸媒分別為（F5、F10、F15、F20、F25）分別取0.5公斤(Kg)，加入含對苯二甲酸之螢光試劑中，並以4升/分鐘(L/min)臭氧曝氣，每分鐘採樣並稀釋10倍進行螢光分析，探討不同鐵離子濃度對氫氧自由基的生成量及螢光值關係。請參閱第三圖所示，為不同鐵離子濃度製備成之鐵型陶瓷觸媒於反應系統中，於螢光試驗中F10～F25陶瓷觸媒，含鐵離子濃度隨含浸量增加而增加，但於反應初期時(1分鐘)F20螢光值約350高於F25莫耳(M)與其他濃度之觸媒，其可能因為陶瓷載體金屬交換最大量發生於F20，此觀點亦可由表1電子顯微鏡之X射線能量分散光譜儀(SEM EDS)元素分析可得到佐證。Here, the first part of the test of the present invention is an iron-type ceramic catalyst (concentration of ferric chloride impregnated with 0.05 mol (M), 0.1 mol (M), 0.15 mol (M), 0.2 mol (M), 0.25. Moer (M)) is added to the oxidation treatment system by the same mass, and the influence of the variation of different impregnated metal concentrations on the oxidation effect is discussed. According to its iron ion concentration, F5, F10, F15, F20 and F25 are as follows. name. The experimental catalysts were respectively 0.5 kg (Kg) of F5, F10, F15, F20, and F25, added to the fluorescent reagent containing terephthalic acid, and aerated with ozone at 4 liters/min (L/min). Fluorescence analysis was performed by sampling and diluting 10 times per minute to investigate the relationship between the formation of hydrogen radicals and the fluorescence value of different iron ion concentrations. Referring to the third figure, the iron-type ceramic catalyst prepared for different iron ion concentrations is used in the reaction system. In the F10-F25 ceramic catalyst in the fluorescence test, the concentration of iron ions increases with the increase of the impregnation amount, but At the initial stage of the reaction (1 minute), the F20 fluorescence value is about 350 higher than that of the F25 molar (M) and other concentrations of the catalyst, which may occur due to the maximum amount of ceramic carrier metal exchange occurring in F20. The elemental analysis of the X-ray energy dispersive spectrometer (SEM EDS) can be confirmed.
表1鐵型陶瓷觸媒之表面元素特性分析
由表1得知含浸不同濃度之最大交換量發生在F20，由於提高含浸液濃度製備出的陶瓷觸媒之鐵含量因含浸劑形成膠羽緣故，因此，過高含浸濃度並不會再提升觸媒中之含鐵量，另於第三圖所示，在2分鐘時可發現F5之螢光值高於其他觸媒，其原因可能是因為其他濃度觸媒催化之氫氧自由基數量比F5觸媒多，因試驗中氧化劑(臭氧)採持續供給，持續供給氧化劑會造成觸媒將臭氧(O3)催化成氫氧自由基，當自由基產量高於螢光劑中的對苯二甲酸反應量，造成氫氧自由基自我分解或臭氧直接反應將螢光物質分解使螢光值大量衰減，所以F5在2分鐘與3分鐘螢光質明顯高於其他觸媒，由此試驗中可知F20濃度之觸媒氫氧自由基產量最多。It is known from Table 1 that the maximum exchange amount of different concentrations of impregnation occurs in F20. The iron content of the ceramic catalyst prepared by increasing the concentration of the impregnation liquid is due to the formation of rubber feathers by the impregnation agent. Therefore, the excessively high impregnation concentration does not rise again. The iron content in the medium, as shown in the third figure, can be found that the fluorescence value of F5 is higher than other catalysts at 2 minutes, which may be due to the fact that the number of hydroxyl radicals catalyzed by other concentrations of catalyst is higher than that of F5. There are many catalysts. Due to the continuous supply of oxidant (ozone) in the test, the continuous supply of oxidant will cause the catalyst to catalyze the oxidation of ozone (O3) into hydroxyl radicals, when the free radical yield is higher than the terephthalic acid reaction in the phosphor. The amount of hydrogen peroxide radical self-decomposition or direct ozone reaction decomposes the fluorescent material to a large extent of the fluorescence value, so the fluorescence of F5 in 2 minutes and 3 minutes is significantly higher than other catalysts, so the F20 concentration can be known from the test. The catalyst has the largest production of hydroxyl radicals.
另再探討不同濃度變化所製備鐵型陶瓷觸媒在不同pH條件之氧化效果，由於臭氧自由產生路徑可分自行分解與催化反應機制，因此，自由基進行氧化反應中pH及觸媒活性位置影響其氧化降解能力，故試驗主要以不同濃度變化所製備鐵型陶瓷觸媒於不同pH值條件下探討臭氧催化氧化程序之活性，同時探討不同濃度之陶瓷觸媒對於酚之轉化與總有機碳(TOC)降解效率之影響。反應條件是1升(L)溶液體積、酚溶液濃度500毫克/升(mg/L)、pH值為8、9、10，鐵型陶瓷金屬觸媒濃度各別為F5、F10、F15、F20、F25，臭氧流量為4升/分鐘(L/min)，每20分鐘採樣反應時間2小時，探討不同濃度鐵型陶瓷觸媒於不同pH值下對於含酚溶液之酚轉化率及總有機碳(TOC)氧化降解率變化結果，如第四、五圖所示。由第四圖之不同濃度鐵型陶瓷觸媒於pH範圍內對含酚溶液氧化降解之情形，其廢水中酚轉化率於反應時間內幾乎完全轉化，雖然酚轉化率極高，但其氧化程度需進一步以化學需氧量(COD)或總有機碳(TOC)移除率來界定其氧化效率，因此，可以得知自由基可於很短時間內將酚轉化成中間產物，為進一步探討有機物之礦化程度，因此本試驗探討不同濃度鐵型陶瓷觸媒於不同pH值下對於氧化過程有機物之總有機碳(TOC)轉化率降解之情況。請再參閱第五圖其圖(A)所示，可發現20分鐘時F5陶瓷觸媒pH8之總有機碳去除效率高於pH10，雖然高pH值會使臭氧加速分解成氫氧自由基，但是當pH提升時也會造成觸媒表面之電荷改變，導致觸媒表面吸附效果改變，含酚溶液pH8時，觸媒表面之電位變化不明顯，因此影響吸附現象非常有限，pH8對於吸附酚效果高於pH9、pH10，因於觸媒表面進行催化氧化情況遠較於高pH情況明顯，因此於40分鐘可明顯的看見pH10去除率約57%高於pH9、pH8，其原因可能是較高的pH加強了鹼催化臭氧產生自由基，使總有機碳去除率提高。請一併參閱第五圖其圖(B)所示，可在20分鐘發現F10觸媒pH8之總有機碳(TOC)去除效略高於pH9，雖然高pH值會使臭氧加速分解成氫氧自由基，但是當含酚溶液pH提升時，也會造成觸媒表面之電荷改變影響吸附能力，使pH8之觸媒催化氧化酚效果在20分鐘前高於pH9、pH10，則從20分鐘至120分鐘顯示pH9與 pH10之總有機碳去除率相差不多但優於pH8，此結果與F5濃度試驗相比較，可觀察到因較高的金屬濃度加強了陶瓷觸媒催化臭氧產生自由基量，因此F10在pH10試驗則因為高pH使觸媒催化氧化效果下降，故在反應條件範圍內自由基之產生機制於pH8時，主要以催化臭氧分解產生自由基為主，但pH9、pH10因鹼催化機制為主，但自由基之產量以觸媒催化分解產生自由基佔優勢。請一併參閱第五圖其圖(C)所示，可在20分鐘發現F15陶瓷觸媒pH8試驗之總有機碳去除率高於其他pH質試驗，原因是自由基之產量以觸媒催化分解產生自由基佔優勢，F15較高的金屬濃度加強了陶瓷觸媒催化臭氧產生氫氧自由基量，雖然在溶液中提高pH值會使臭氧加速分解成氫氧自由基，但是含酚溶液pH提升時也會造成觸媒表面之電荷使吸附與觸媒催化效果改變，反應時鹼催化臭氧產生氫氧自由基濃度會低於觸媒催化，使pH8試驗之觸媒催化臭氧氧化酚效果遠高於pH9、pH10，則從20分鐘至120分鐘顯示pH10去總有機碳(TOC)除率高於pH9，原因可能是因為其pH值低於pH10，使鹼催化效果低於pH10，pH9試驗觸媒催化產生之氫氧自由基少於pH8試驗，使其總有機碳(TOC)去除效果不佳。另在第五圖其圖(D)及圖(E)中可在20分鐘發現F20及F25陶瓷觸媒pH8試驗之總有機碳去除率高於其他pH質試驗，原因是F20較高的金屬濃度加強了陶瓷觸媒催化臭氧產生氫氧自由基量，雖然在溶液中提高pH值會使臭氧加速分解成氫氧自由基，但是當含酚溶液pH提升時也會造成觸媒表面之電荷使吸附與觸媒催化效果改變，當臭氧上未完全溶入水中反應時鹼催化臭氧產生氫氧自由基濃度會低於觸媒催化，使pH8試驗之觸媒催化臭氧產生氫氧自由基氧化酚效果高於pH9、pH10，則從20分鐘至120分鐘顯示pH10去總有機碳(TOC)除率高於pH9，原因可能是因為其pH值低於pH10，使鹼催化效果低於pH10，而觸媒催化產生之氫氧自由基少於pH8試驗，使其總有機碳(TOC)去除效果不佳，由第四、五圖結果顯示陶瓷觸媒催化臭氧氧化系統對於酚之轉化率在各濃度均有99%之轉化效果，總有機碳(TOC) 移除率最高皆達80%以上，故由試驗結果發現，以微鹼性條件下不論酚轉化率及廢水總有機碳去除率以pH8為最佳反應條件。In addition, the oxidation effect of the iron-type ceramic catalyst prepared by different concentration changes at different pH conditions is discussed. Since the ozone free generation path can be separated into self-decomposition and catalytic reaction mechanism, the influence of free radicals on the pH and the catalytic activity position in the oxidation reaction Its oxidative degradation ability, so the experiment mainly investigated the activity of the ozone-catalyzed oxidation process of iron-type ceramic catalyst prepared by different concentration changes under different pH conditions, and discussed the conversion of phenol and total organic carbon by ceramic catalysts with different concentrations ( TOC) The effect of degradation efficiency. The reaction conditions are 1 liter (L) of solution volume, phenol solution concentration of 500 mg / liter (mg / L), pH of 8, 9, 10, the concentration of iron-type ceramic metal catalyst is F5, F10, F15, F20 , F25, ozone flow rate is 4 liters / minute (L / min), sampling reaction time every 20 minutes for 2 hours, to explore the phenol conversion rate and total organic carbon of phenol-containing solutions at different pH values of different concentrations of iron-type ceramic catalysts (TOC) results of changes in oxidative degradation rate, as shown in Figures 4 and 5. The phenolic conversion rate in the wastewater is almost completely converted in the reaction time by the oxidative degradation of the phenol-containing solution in the pH range by the different concentrations of the iron-type ceramic catalyst in the fourth figure, although the phenol conversion rate is extremely high, but the degree of oxidation It is necessary to further define the oxidation efficiency by chemical oxygen demand (COD) or total organic carbon (TOC) removal rate. Therefore, it can be known that free radicals can convert phenol into intermediate products in a short time, in order to further explore organic matter. The degree of mineralization, therefore, this test explores the degradation of total organic carbon (TOC) conversion of organic matter in the oxidation process at different pH values of different concentrations of iron-type ceramic catalyst. Referring to Figure 5 (A), it can be found that the total organic carbon removal efficiency of F5 ceramic catalyst pH 8 is higher than pH 10 at 20 minutes, although high pH will accelerate the decomposition of ozone into hydroxyl radicals, but When the pH is raised, the charge on the surface of the catalyst will change, resulting in a change in the adsorption effect on the surface of the catalyst. When the pH of the phenol solution is pH 8, the potential change on the surface of the catalyst is not obvious, so the adsorption phenomenon is very limited, and the pH 8 has a high effect on the adsorption of phenol. At pH9 and pH10, the catalytic oxidation on the catalyst surface is much more obvious than the high pH. Therefore, the pH10 removal rate is obviously seen at 40 minutes over 40 minutes, which is higher than pH9 and pH8. The reason may be higher pH. The base is catalyzed by ozone to generate free radicals, and the total organic carbon removal rate is increased. Please refer to the fifth figure (B). It can be found that the total organic carbon (TOC) removal efficiency of F10 catalyst pH8 is higher than pH9 in 20 minutes, although the high pH will accelerate the decomposition of ozone into hydrogen and oxygen. Free radicals, but when the pH of the phenol-containing solution is increased, the charge change on the surface of the catalyst will also affect the adsorption capacity, so that the catalyst for the oxidation of phenol at pH 8 is higher than pH 9 and pH 10 before 20 minutes, from 20 minutes to 120 minutes. Minutes show that the total organic carbon removal rate of pH9 and pH10 is similar but better than pH8. Compared with the F5 concentration test, it can be observed that the higher the metal concentration enhances the amount of free radical generated by the ceramic catalyst to catalyze ozone, so F10 In the pH10 test, the catalytic oxidation effect of the catalyst is lowered because of the high pH. Therefore, the mechanism of free radical generation in the range of reaction conditions is mainly based on catalytic ozonolysis to generate free radicals, but pH9 and pH10 are based on the base catalytic mechanism. Lord, but the production of free radicals is dominated by catalytically catalyzed decomposition of free radicals. Please refer to the fifth figure (C). It can be found in 20 minutes that the total organic carbon removal rate of the F15 ceramic catalyst pH8 test is higher than other pH tests because the free radical production is catalytically decomposed by the catalyst. The generation of free radicals predominates, and the higher metal concentration of F15 enhances the amount of hydroxyl radicals generated by the ceramic catalyst to catalyze the generation of ozone. Although increasing the pH in the solution accelerates the decomposition of ozone into hydroxyl radicals, the pH of the phenol-containing solution increases. At the same time, the charge on the surface of the catalyst will change the adsorption and catalytic effect. The concentration of hydroxide-generated ozone in the reaction will be lower than that of the catalyst, so that the catalyst of pH8 test is much higher than that of ozone. pH9, pH10, from 20 minutes to 120 minutes, the pH 10 is lower than the total organic carbon (TOC) rate higher than pH9, probably because the pH value is lower than pH10, the base catalytic effect is lower than pH10, pH9 test catalyst catalysis The resulting hydroxyl radicals were less than the pH 8 test, making their total organic carbon (TOC) removal poor. In Figure 5 (D) and (E), the total organic carbon removal rate of the F20 and F25 ceramic catalysts in the pH8 test was found to be higher than the other pH tests in 20 minutes because of the higher metal concentration of F20. The ceramic catalyst is used to catalyze the amount of hydroxyl radical generated by ozone, although increasing the pH in the solution accelerates the decomposition of ozone into hydroxyl radicals, but when the pH of the phenol-containing solution increases, it also causes the adsorption of the catalyst surface. The catalytic effect of the catalyst is changed. When the ozone is not completely dissolved in water, the alkali-catalyzed ozone-generated hydrogen-oxygen radical concentration will be lower than the catalyst catalysis, so that the catalyst of pH8 test catalyzes the generation of hydrogen-oxygen radicals to oxidize phenol. At pH9 and pH10, the pH-10 is shown to be higher than pH9 from 20 minutes to 120 minutes, probably because the pH is lower than pH10, and the base catalysis is lower than pH10, and the catalyst is catalyzed. The produced hydroxyl radicals are less than the pH 8 test, and the total organic carbon (TOC) removal effect is not good. The results of the fourth and fifth graphs show that the ceramic catalyst-catalyzed ozone oxidation system has a conversion rate of phenol at each concentration of 99. % conversion effect, total organic carbon (TOC) shift The highest rates are more than 80%, it was found from the test results, the following conditions regardless slightly alkaline phenol conversion and removal of total organic carbon in the wastewater pH8 under the best conditions.
又再以微鹼性條件下不論酚轉化率及廢水總有機碳去除率以pH8為最佳反應條件做為實驗依據，由不同含浸劑濃度下所製備陶瓷觸媒催化氧化活性試驗結如第六、七圖所示，如第六圖之結果顯示，無論觸媒或非觸媒催化反應酚之轉化率於2小時皆可達完全轉換，由第七圖之試驗結果可以得知非觸媒催化反應其總有機碳(TOC)僅有少部分降解，其原因為弱鹼條件下，臭氧自行分解自由基產生部分氧化效果有限，且因其自由基產生效率不佳。因此僅能產生部分氧化效果，但當反應系統加入鐵型陶瓷觸媒時，明顯觀察到總有機碳去除率提高，其反應F25觸媒120分鐘時總有機碳去除率可達到82%，則F20與F15陶瓷觸媒在80分鐘時總有機碳去除率已達到80%，其中在120分鐘時F15陶瓷觸媒其總有機碳去除率高達85%明顯優於其它觸媒，由實驗結果得知，F15陶瓷觸媒具有是適當活性金屬分布，於pH8進行氧化時具有最佳之氧化效果，但其承載鐵離子濃度如果增加F20觸媒、F25觸媒，由發明結果得知其總有機碳(TOC)降解效果並無法有效進一步提升，其原因為觸媒載體於高濃度含浸下並無法有更多披覆鐵離子於陶瓷載體。Under the condition of slightly alkaline, no matter the phenol conversion rate and the total organic carbon removal rate of wastewater, pH 8 is the optimal reaction condition. The experimental activity of the catalytic activity of ceramic catalyst prepared by different impregnation agent concentrations is as follows. As shown in the seventh figure, as shown in the sixth graph, the conversion rate of the catalyst or the non-catalytic phenol can be fully converted in 2 hours. The non-catalytic catalysis can be seen from the test results in the seventh graph. The reaction of total organic carbon (TOC) is only partially degraded. The reason is that under the condition of weak base, the partial oxidation effect of ozone self-decomposing free radicals is limited, and the efficiency of free radical generation is not good. Therefore, only partial oxidation effect can be produced, but when the reaction system is added with the iron-type ceramic catalyst, the total organic carbon removal rate is obviously observed to be increased, and the total organic carbon removal rate of the F25 catalyst can reach 82% in 120 minutes, then F20 The total organic carbon removal rate of the F15 ceramic catalyst reached 80% at 80 minutes, and the total organic carbon removal rate of the F15 ceramic catalyst was as high as 85% at 120 minutes, which was significantly better than other catalysts. The F15 ceramic catalyst has a proper active metal distribution and has the best oxidation effect when oxidized at pH 8. However, if the iron ion concentration is increased, the F20 catalyst and the F25 catalyst are added, and the total organic carbon (TOC) is known from the invention. The degradation effect cannot be effectively further improved because the catalyst carrier does not have more coating of iron ions on the ceramic carrier under high concentration impregnation.
另為更進一步瞭解陶瓷觸媒氧化系統之耐久性，係以陶瓷觸媒與含酚溶液進行臭氧催化氧化反應進行長時間測以了解觸媒重覆使用特性。本實驗以同一批陶瓷觸媒進行反應，每次反應後之經水洗、過濾、烘乾後，再將陶瓷觸媒以相同條件重覆進行氧化反應，用以評估氧化效能穩定性。請參閱第八、九圖所示，為陶瓷觸媒在穩定性反覆試驗對酚降解效率及總有機碳去除率之關係圖，如第八圖所示在試驗中觸媒對酚轉化率皆在20分鐘時達到99%以上，如第九圖顯示總有機碳去除率顯示隨反應次數增加，其試驗總有機碳去除率隨之降低，其重複試驗1次、2次、3次、4次試驗中總有機碳去除率分別降低為76%、73%、69%、56%，由上述結果顯示反覆性試驗對觸媒於酚之轉化效率無明顯之影響，但在總有機碳去除率則因金屬溶出及觸媒曝氣滾動反覆清洗摩擦使觸媒破裂造成活性減低之現象，由實驗結果可獲知如欲維持本觸媒氧化系統之氧化活性，反應系統應於氧化降解過程中進行pH控制，pH控制用以避免活性金屬溶出之問題，另外反應系統應以固定式反應槽進行氧化用以避免觸媒滾動產生破裂之情形。In order to further understand the durability of the ceramic catalyst oxidation system, the ceramic catalyst and the phenol-containing solution are subjected to ozone catalytic oxidation reaction for long-term measurement to understand the repeated use characteristics of the catalyst. In this experiment, the same batch of ceramic catalyst was used for the reaction. After each reaction, after washing, filtering and drying, the ceramic catalyst was repeatedly subjected to oxidation reaction under the same conditions to evaluate the oxidation performance stability. Please refer to the eighth and ninth figures for the relationship between the phenol degradation efficiency and the total organic carbon removal rate of the ceramic catalyst in the stability test. As shown in the eighth figure, the catalyst-to-phenol conversion rate is in the test. At 20 minutes, it reached 99% or more. As shown in the ninth figure, the total organic carbon removal rate showed that the total organic carbon removal rate decreased with the increase of the number of reactions, and the test was repeated once, twice, three times, and four times. The total organic carbon removal rate was reduced to 76%, 73%, 69%, and 56%, respectively. The above results show that the reversal test has no significant effect on the conversion efficiency of the catalyst to phenol, but the total organic carbon removal rate is due to The metal dissolution and the catalytic aeration rolling repeatedly wash the friction to reduce the activity caused by the catalyst rupture. It is known from the experimental results that if the oxidation activity of the catalyst oxidation system is to be maintained, the reaction system should be pH controlled during the oxidative degradation process. The pH control is used to avoid the problem of dissolution of the active metal. In addition, the reaction system should be oxidized in a fixed reaction tank to avoid cracking of the catalyst.
又為探討酚降解的主要機制為臭氧直接反應或由觸媒催化臭氧產生氫氧自由基對酚氧化反應，故添加0.05莫耳(M)丁醇於添加觸媒與無添加觸媒氧化系統中，由第十、十一圖所示分別自由基捕捉劑對為添加對觸媒催化氧化試驗酚轉化率及總有機碳去除率之關係圖，添加捕捉劑會稍許影響觸媒催化氧化酚之轉化率，但卻對整體總有機碳去除率產生很大之影響，又總有機碳去除率遠低於無添自由基捕捉劑之氧化試驗，其原因為當自由基捕捉劑添加於觸媒氧化系統中，自由基產生很快被捕捉，因此中斷酚氧化降解之途徑，許多降解後之中間產物並無法完全氧化，由試驗結果可以得到印證，氧化反應自由基捕捉對於臭氧觸媒催化或臭氧氧化產生自由基有明顯抑制作用，並可歸納出，臭氧觸媒催化系統受自由基捕捉劑之影響，將來如欲將本發明系統應用於其他有機污染物之氧化降解時，應盡量避免自由基捕捉劑對於本氧化反應之干擾。In order to explore the main mechanism of phenol degradation is ozone direct reaction or catalyst-catalyzed ozone to generate hydroxyl radicals to phenol oxidation reaction, so add 0.05 mol (M) butanol in the addition of catalyst and no added catalyst oxidation system According to the relationship between the phenol conversion rate and the total organic carbon removal rate of the catalyst-catalyzed oxidation test, the addition of the capture agent will slightly affect the conversion of the catalyst-catalyzed oxidation of phenol. Rate, but it has a great impact on the overall total organic carbon removal rate, and the total organic carbon removal rate is much lower than the oxidation test without the addition of free radical trapping agent, because the free radical scavenger is added to the catalytic oxidation system. In the middle, free radicals are quickly captured, thus interrupting the phenol oxidative degradation pathway, many intermediates after degradation can not be completely oxidized, which can be confirmed by the test results. Oxidation reaction free radical capture for ozone catalyst catalysis or ozone oxidation Free radicals have obvious inhibitory effects, and it can be concluded that the ozone catalyst catalytic system is affected by the free radical scavenger, and the system of the present invention is to be applied in the future. He oxidation degradation of the organic pollutants, should avoid interference with a radical scavenger of the present oxidation reaction.
再者，本發明第二部分試驗，係探討以錳金屬作為陶瓷觸媒活化金屬，以離子交換至陶瓷載體，製備成錳陶瓷觸媒，並對其進行氮氣吸脫附試驗分析其孔隙特性。錳鹽含浸濃度0.05莫耳(M)、0.1莫耳(M)、0.15莫耳(M)、0.2莫耳(M)、0.25莫耳(M)活化劑製備之陶瓷觸媒(依其含錳離子濃度，下述以M5、M10、M15、M20、M25為其名稱)，其比表面積介於520~612平方公尺/克(m2/g)，由於空白陶瓷載體具有相當大之比表面積(569公尺/克(m2/g))，因錳離子交換後除無明顯金屬氧化物沉澱產生，即對載體表面積及孔隙特性影響不大。利用環境掃描式電子顯微鏡（E-SEM）來觀察觸媒之表面結構且使用X射線能量分散分析儀(EDS)探討陶瓷觸媒之元素種類與其含量其結果如表2所示，由表2中發現當錳離子交換量增加時，錳型陶瓷觸媒孔隙無明顯降低，由於高濃度之錳鹽相較鐵鹽不易形成鐵膠羽與阻塞載體表面孔隙，在微孔分析中也無產生明顯損失，故由實驗結果證實，錳金屬在0.25莫耳(M)尚未達其交換飽和濃度。Furthermore, in the second part of the present invention, the manganese metal is used as a ceramic catalyst to activate the metal, and the manganese ceramic catalyst is prepared by ion exchange to a ceramic carrier, and the pore characteristics are analyzed by nitrogen adsorption and desorption. Manganese salt impregnated with a concentration of 0.05 mol (M), 0.1 mol (M), 0.15 mol (M), 0.2 mol (M), 0.25 mol (M) activator ceramic catalyst (including manganese The ion concentration, which is named after M5, M10, M15, M20, and M25, has a specific surface area of 520 to 612 m 2 /g (m 2 /g) because the blank ceramic carrier has a relatively large specific surface area ( 569 m / g (m2 / g)), due to manganese ion exchange, no significant metal oxide precipitation, that is, has little effect on the surface area and pore characteristics of the support. The surface structure of the catalyst was observed by an environmental scanning electron microscope (E-SEM) and the element type and content of the ceramic catalyst were investigated using an X-ray energy dispersive analyzer (EDS). The results are shown in Table 2, as shown in Table 2. It is found that when the manganese ion exchange amount increases, the pores of the manganese-type ceramic catalyst are not significantly reduced. Since the high-concentration manganese salt is less likely to form iron gelatin and block the surface pores of the carrier than the iron salt, no significant loss occurs in the micropore analysis. Therefore, it was confirmed by experimental results that the manganese metal had not reached its exchange saturation concentration at 0.25 m (M).
表2錳型陶瓷觸媒之孔隙特性分析
另由表3中陶瓷觸媒錳元素之含量隨製備時含浸錳鹽濃度增加而提高，由於本發明製備之陶瓷觸媒是利用金屬離子與陶瓷載體進行離子交換而形成金屬氧化物，因此其金屬分佈較為均勻，結果顯示當製備錳金屬含浸液濃度由0.05莫耳(M)提高到0.25莫耳(M)時，EDS元素分析中錳元素仍有增加之趨勢，當離子交換飽和時多餘的金屬離子則不會再被交換至載體，結果顯示在0.25莫耳(M)時載體表面元素質增加趨勢減緩，因此由EDS元素分析表可看出錳金屬含進濃度與離子交換飽和濃度相差不多。In addition, the content of the manganese element in the ceramic catalyst in Table 3 increases as the concentration of the impregnated manganese salt increases during preparation. Since the ceramic catalyst prepared by the present invention uses metal ions to exchange ions with a ceramic carrier to form a metal oxide, the metal thereof The distribution is relatively uniform. The results show that when the concentration of manganese metal impregnation solution is increased from 0.05 m (M) to 0.25 m (M), the manganese content in the EDS elemental analysis still has an increasing tendency. When the ion exchange is saturated, the excess metal The ions are no longer exchanged to the carrier, and the results show that the increase in the surface elementality of the carrier is slowed down at 0.25 m (M). Therefore, it can be seen from the EDS elemental analysis table that the manganese metal concentration is similar to the ion exchange saturation concentration.
表3陶瓷觸媒之表面元素特性分析
又由於臭氧自由產生路徑可分自分解機制與催化反應，因此自由基進行氧化反應中pH及觸媒活性位置影響其氧化降解能力，本發明主要使用M15觸媒於不同pH值條件下探討臭氧催化氧化程序之活性，及對於酚之轉化與總有機碳(TOC)降解效率之影響，反應條件:1L溶液體積、酚溶液濃度500毫克/升(mg/L)、pH值為8、9、10，M15觸媒1公斤(KG)，臭氧流量為4升/分鐘(L/min)，反應時間2小時每20分鐘採樣，請參閱第十二圖顯示M15觸媒在20分鐘時酚轉化率及達100%，另第十三圖顯示M15觸媒於pH8、pH9、pH10對分之總有機碳去除率分別為94.%、91%、95%，由此試驗可知M15觸媒擁有良好的觸媒催化活性，因此，在不同pH條件下皆能在含酚溶液中有良好的降解效果。Since the free generation path of ozone can be separated from the decomposition mechanism and the catalytic reaction, the pH and the catalytic activity position of the free radicals affect the oxidative degradation ability of the oxidation reaction. The present invention mainly uses the M15 catalyst to investigate the ozone catalysis under different pH conditions. The activity of the oxidation procedure, and the effect on the conversion of phenol and the total organic carbon (TOC) degradation efficiency, reaction conditions: 1L solution volume, phenol solution concentration 500 mg / liter (mg / L), pH of 8, 9, 10 , M15 catalyst 1 kg (KG), ozone flow rate of 4 l / min (L / min), reaction time 2 hours every 20 minutes sampling, please refer to the twelfth figure shows M15 catalyst phenol conversion rate at 20 minutes and Up to 100%, and the thirteenth figure shows that the total organic carbon removal rate of M15 catalyst at pH8, pH9, and pH10 is 94.%, 91%, and 95%, respectively. From this test, it is known that M15 catalyst has good contact. The catalyst has a good catalytic activity and therefore has a good degradation effect in the phenol-containing solution under different pH conditions.
復本發明再以銅金屬作為陶瓷觸媒活化金屬，以離子交換至陶瓷載體，製備成銅陶瓷觸媒，其銅鹽含浸濃度由0.05莫耳(M)、0.1莫耳(M)、0.15莫耳(M)、0.2莫耳(M)、0.25莫耳(M)活化劑製備之陶瓷觸媒(依其含銅離子濃度，下述以C5、C10、C15、C20、C25為其名稱)，所製備之陶瓷觸媒其比表面積介於550~608公尺/克(m2/g)。又配製1升(L)螢光試劑與0.5公斤(Kg)銅型觸媒陶瓷觸媒進行反應，臭氧則4升/分鐘(L/min)加入臭氧催化氧化處理系統中，採集樣本稀釋10倍進行螢光分析，探討其氫氧自由基的生成量與螢光值相關性，氫氧自由基的生成量決定廢水高級氧化之效率，隨著臭氧曝氣時間的增加，自由基的生成量隨之增加，因此氧化降解效果也跟著提高，如第十四圖所示，氫氧自由基的生成量與螢光強度成正比同時，證明了C15觸媒對於催化臭氧產生自由基的效率優於F15陶瓷觸媒與無添加觸媒。另本發明使用C15觸媒於不同pH值條件下進行臭氧催化氧化程序之活性，同時探討C15觸媒對於酚之轉化與總有機碳(TOC)降解效率之影響，反應條件為1L溶液體積、酚溶液濃度500毫克/升(mg/L)、pH值為8、9、10，C15觸媒1公斤(KG)，臭氧流量為每分鐘4公升，反應時間2小時如第十五圖顯示C15觸媒於pH8、pH9、pH10對分之總有機碳去除率分別為92%、96%、84%，如第十六圖顯示C15觸媒在20分鐘時酚轉化率及達100%，由此試驗可之C15觸媒擁有良好的催化活性，因此在不同pH條件下皆能有良好的降解效果。The invention further uses copper metal as a ceramic catalyst to activate the metal, and ion exchange to a ceramic carrier to prepare a copper ceramic catalyst having a copper salt impregnation concentration of 0.05 mol (M), 0.1 mol (M), 0.15 Mo. Ceramic catalyst prepared from ear (M), 0.2 mol (M), 0.25 mol (M) activator (according to its copper ion concentration, the following names are C5, C10, C15, C20, C25), The prepared ceramic catalyst has a specific surface area of 550 to 608 meters/gram (m2/g). 1 liter (L) of the fluorescent reagent is reacted with 0.5 kg (Kg) of copper-type catalyst ceramic catalyst, and ozone is added to the ozone catalytic oxidation treatment system at 4 liters/min (L/min), and the sample is diluted 10 times. Fluorescence analysis was carried out to investigate the correlation between the amount of hydroxyl radical generation and the fluorescence value. The amount of hydroxyl radical generation determines the efficiency of advanced oxidation of wastewater. With the increase of ozone aeration time, the amount of free radicals produced The increase, so the oxidative degradation effect is also improved, as shown in Figure 14, the formation of hydroxyl radicals is proportional to the fluorescence intensity, and it is proved that the C15 catalyst is better than F15 in catalyzing the generation of free radicals by ozone. Ceramic catalyst and no added catalyst. In addition, the present invention uses the C15 catalyst to carry out the activity of the ozone catalytic oxidation process under different pH conditions, and simultaneously discusses the effect of the C15 catalyst on the conversion of phenol and the total organic carbon (TOC) degradation efficiency, the reaction condition is 1 L solution volume, phenol The concentration of the solution is 500 mg/L (mg/L), the pH is 8, 9, 10, the C15 catalyst is 1 kg (KG), the ozone flow rate is 4 liters per minute, and the reaction time is 2 hours. The fifteenth figure shows the C15 touch. The total organic carbon removal rates of the media at pH 8, pH 9, and pH 10 were 92%, 96%, and 84%, respectively. As shown in Figure 16, the C15 catalyst showed a phenol conversion rate of 100% at 20 minutes. The C15 catalyst has good catalytic activity, so it can have good degradation effect under different pH conditions.
是以，本發明採用陶瓷做為觸媒載體，以承載活性金屬氧化物，並以濕式含浸法製成鐵、銅、錳型陶瓷觸媒，且以不同升溫梯度將陶瓷觸媒上之金屬轉化成高臭氧催化活性之金屬氧化物，並將其有效成功運用於催化臭氧產生自由基氧化降解含酚等有機廢水。另於各項實驗中係發現不同金屬含浸液濃度所製備鐵型觸媒對於酚氧化效果之有顯著影響，含浸液活性金屬濃度的提高有助提高觸媒中活性金屬含量，利於氧化降解含酚溶液，其中最佳之鐵離子濃度為0.15M，過多含浸液濃度並無法更進一步提升陶瓷觸媒中之活性金屬含量；又由實驗結果得知提高不同金屬濃度對於觸媒比表面積與微孔特性影響並不一致，以錳金屬為例，濃度升至0.25莫耳(M)時觸媒比表面積與微孔特性並不會因金屬濃度提高而下降；另自由基螢光分析結果證明活性金屬觸媒對於催化臭氧產生氫氧自由基量明顯；活性金屬陶瓷觸媒於催化氧化系統中容易受pH影響，以鐵觸媒為例pH8對含酚溶液之降解效果為最佳；鐵觸媒處理高濃度之酚溶液時可以利用延長時間與控制pH，提升降解效率；在pH變化試驗得知pH質變化對銅與錳觸媒於對於臭氧催化氧化系統影響不大；添加自由機捕捉劑試驗中得知本研究氧化機至皆為觸媒催化臭氧產生自由基氧化降解含酚溶液；研究結果得知銅觸媒其催化氧化效果為最佳，錳觸媒次之，故本發明主要以含銅金屬之陶瓷觸媒進行催化氧化效果，另次之以含錳金屬之陶瓷觸媒進行催化氧化效果。Therefore, the present invention uses ceramic as a catalyst carrier to carry an active metal oxide, and is made into an iron, copper, manganese type ceramic catalyst by a wet impregnation method, and the metal on the ceramic catalyst is heated at different temperature gradients. It is converted into a metal oxide with high ozone catalytic activity, and it is effectively applied to catalyze the generation of free radical oxidation of ozone to decompose organic wastewater containing phenol. In addition, in various experiments, the iron-type catalyst prepared by different metal impregnation liquid concentrations has a significant effect on the phenol oxidation effect. The increase of the active metal concentration in the impregnation liquid helps to increase the active metal content in the catalyst, which is beneficial to the oxidative degradation of phenol. The optimum iron ion concentration is 0.15M. The excessive concentration of the impregnation solution can not further increase the active metal content in the ceramic catalyst. It is also found from the experimental results that the specific metal surface area and microporous properties of the catalyst are improved. The effects are not consistent. In the case of manganese metal, the specific surface area and microporous properties of the catalyst do not decrease due to the increase of metal concentration when the concentration is raised to 0.25 m (M). The free radical fluorescence analysis proves that the active metal catalyst The amount of hydroxyl radical generated by catalytic ozone is obvious; the active cermet catalyst is easily affected by pH in the catalytic oxidation system, and the degradation effect of the phenol-containing solution is best with the iron catalyst as an example; the high concentration of the iron catalyst treatment The phenol solution can be extended to adjust the pH and improve the degradation efficiency; in the pH change test, the pH change is known to the copper and manganese catalyst to catalyze the ozone. The influence of the chemical system is not great; the free-capacitor trapping agent test shows that the oxidizer is the catalyst-catalyzed ozone-generated radical oxidative degradation of the phenol-containing solution; the results show that the copper catalyst has the best catalytic oxidation effect. The manganese catalyst is the second, so the present invention mainly uses a ceramic catalyst containing a copper metal for catalytic oxidation, and secondly a ceramic catalyst containing manganese metal for catalytic oxidation.
綜上所述，本發明之實施例確能達到所預期功效，又其所揭露之具體構造，不僅未曾見諸於同類產品中，亦未曾公開於申請前，誠已完全符合專利法之規定與要求，爰依法提出發明專利之申請，懇請惠予審查，並賜准專利，則實感德便。In summary, the embodiments of the present invention can achieve the expected functions, and the specific structures disclosed therein have not been seen in the same products, nor have they been disclosed before the application, and have fully complied with the provisions of the Patent Law. It is required that if an application for a patent for invention is filed in accordance with the law, and if the application is granted, the patent will be granted.
無no
第一圖：本發明之陶瓷觸媒製備流程圖First: Flow chart of preparation of ceramic catalyst of the present invention
第二圖：本發明之實驗流程圖Second Figure: Experimental flow chart of the present invention
第三圖：本發明之不同濃度變化所製備鐵型觸媒之氫氧自由基螢光試驗曲線圖The third figure: the hydrogen-oxygen radical fluorescence test curve of the iron-type catalyst prepared by different concentration changes of the present invention
第四圖：本發明之鐵型觸媒各濃度不同pH值對於含酚溶液之氧化降解率變化曲線圖Figure 4: Curve of oxidative degradation rate of phenol-containing solution with different pH values of the iron-type catalyst of the present invention
第五圖：本發明之鐵型觸媒不同pH值對含酚溶液之總有機碳(TOC)去除效果曲線圖Fig. 5 is a graph showing the effect of different pH values of the iron-type catalyst of the present invention on total organic carbon (TOC) removal of a phenol-containing solution
第六圖：本發明之不同含浸金屬濃度陶瓷觸媒催化活性之影響含酚溶液轉化率曲線圖Fig. 6 is a graph showing the influence of the catalytic activity of the ceramic catalyst of different impregnated metal concentrations on the conversion rate of the phenol-containing solution of the present invention
第七圖：本發明之不同含浸金屬濃度陶瓷觸媒催化活性之影響總有機碳(TOC)去除效果曲線圖Fig. 7 is a graph showing the effect of the catalytic activity of the ceramic catalyst on the total organic carbon (TOC) removal effect of different impregnated metal concentrations of the present invention
第八圖：本發明之F15觸媒於反覆試驗中對於酚轉化率影響曲線圖Figure 8: Effect of the F15 catalyst of the present invention on the conversion of phenol in the repeated test
第九圖：本發明之F15觸媒於反覆試驗中對於含酚溶液之總有機碳(TOC)去除率影響曲線圖Figure 9: Effect of the F15 catalyst of the present invention on the removal rate of total organic carbon (TOC) in a phenol-containing solution in a repeated test
第十圖：本發明之F15鐵型觸媒於添加自由基捕捉劑入含酚溶液之氧化降解之變化曲線圖Fig. 10 is a graph showing the change of oxidative degradation of the F15 iron-type catalyst of the present invention with the addition of a radical scavenger into a phenol-containing solution
第十一圖：本發明之F15鐵型觸媒於添加自由基捕捉劑入含酚溶液之總有機碳(TOC)去除率變化曲線圖Eleventh figure: The curve of the total organic carbon (TOC) removal rate of the F15 iron-type catalyst of the present invention added with a radical scavenger into a phenol-containing solution
第十二圖：本發明之M15觸媒於不同pH值對含酚溶液之總有機碳(TOC)去除效果曲線圖Twelfth Figure: The effect of the M15 catalyst of the present invention on the removal of total organic carbon (TOC) of a phenol-containing solution at different pH values
第十三圖：本發明之M15觸媒於不同pH值對含酚溶液之總有機碳(TOC)去除效果曲線圖Thirteenth Graph: The effect of the M15 catalyst of the present invention on the removal of total organic carbon (TOC) of a phenol-containing solution at different pH values
第十四圖：本發明之C15觸媒於臭氧催化氧化系統中之氫氧自由基生成量曲線圖Figure 14: Graph of the generation of hydroxyl radicals in the catalytic catalytic oxidation system of C15 catalyst of the present invention
第十五圖：本發明之C15觸媒於不同pH值下對於含酚溶液之總有機碳(TOC)去除率圖Figure 15: Total organic carbon (TOC) removal rate of phenol-containing solution at different pH values of the C15 catalyst of the present invention
第十六圖：本發明之C15觸媒於不同pH值下對於含酚溶液之酚轉化率曲線圖Figure 16: Graph of phenol conversion rate of phenol-containing solution at different pH values of C15 catalyst of the present invention
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107758913A (en) * | 2016-08-19 | 2018-03-06 | 宝山钢铁股份有限公司 | A kind of method and apparatus for removing total organic carbon in cold rolling acid waste water |
| CN114471579A (en) * | 2022-01-25 | 2022-05-13 | 长沙瑞庭科技有限公司 | Ozone catalyst and preparation method thereof |
| CN115650175A (en) * | 2022-09-23 | 2023-01-31 | 北京理工大学 | Method for improving oxygen atom conversion efficiency of plate-type ozone generator |
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2015
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107758913A (en) * | 2016-08-19 | 2018-03-06 | 宝山钢铁股份有限公司 | A kind of method and apparatus for removing total organic carbon in cold rolling acid waste water |
| CN114471579A (en) * | 2022-01-25 | 2022-05-13 | 长沙瑞庭科技有限公司 | Ozone catalyst and preparation method thereof |
| CN115650175A (en) * | 2022-09-23 | 2023-01-31 | 北京理工大学 | Method for improving oxygen atom conversion efficiency of plate-type ozone generator |
| CN115650175B (en) * | 2022-09-23 | 2023-12-01 | 北京理工大学 | Method for improving oxygen atom conversion efficiency of plate-type ozone generator |
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