TWI606994B - Ceramic catalytic membrane tube and method for preparing the same - Google Patents

Ceramic catalytic membrane tube and method for preparing the same Download PDF

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TWI606994B
TWI606994B TW102140441A TW102140441A TWI606994B TW I606994 B TWI606994 B TW I606994B TW 102140441 A TW102140441 A TW 102140441A TW 102140441 A TW102140441 A TW 102140441A TW I606994 B TWI606994 B TW I606994B
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ceramic catalyst
phenol
film tube
catalyst film
copper
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TW201518249A (en
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陳世雄
劉瑞美
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嘉藥學校財團法人嘉南藥理大學
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Description

陶瓷觸媒膜管製備方法 Ceramic catalyst film tube preparation method

本發明係有關於一種陶瓷觸媒膜管製備方法,尤指一種簡便成型且可有效去除廢水所含酚類及總有機碳之陶瓷觸媒膜管製備方法。 The invention relates to a method for preparing a ceramic catalyst film tube, in particular to a method for preparing a ceramic catalyst film tube which is simple and can effectively remove phenols and total organic carbon contained in waste water.

按,台灣現今工業型態主要為重化工業、鋼鐵業及晶圓與半導體等產業,該些產業皆為高耗能、高耗水之產業型態,且於產品生產過程中所排放出廢水常含有酚類化合物,而難以傳統廢水處理技術妥善處理,更無法將廢水回收再利用。該酚類化合物係為毒性物質,對人體健康影響甚鉅,少量的酚即能對水中生物造成嚴重的污染,當人們食用受污染的水中魚類,便容易於體內累積酚而中毒致癌。 According to the current industrial pattern in Taiwan, the industries are mainly heavy chemical industry, steel industry, wafer and semiconductor industries. These industries are high-energy, high-consumption industrial types, and wastewater is often discharged during production. Containing phenolic compounds, it is difficult to properly treat traditional wastewater treatment technologies, and it is even more difficult to recycle and reuse wastewater. The phenolic compound is a toxic substance, which has a great impact on human health. A small amount of phenol can cause serious pollution to aquatic organisms. When people eat contaminated water fish, they are prone to accumulate phenol in the body and become poisonous and carcinogenic.

由於酚類化合物為高毒性難分解之有機化合物,且對環境具有嚴重危害,因此國內外許多學者對於酚類化合物都視為公敵,也 紛紛對含酚廢水處理上進行研究,而含酚類污染物廢水由於具有生物毒性,因此無法以現有活性污泥法進行廢水處理,故目前對含酚類污染物廢水常以高階氧化程式(Advanced Oxidation Processes,AOPs)進行污染物之降解以降低毒性,該高階氧化程式作用機制主要以具強氧化能力的氫氧自由基在均相與非均相條件下與有機物反應,在反應程式中與有機物反應得到一個電子,在得到有機物之電子時會使有機物的結構受改變或是導致分解形成較小分子量之有機物,但由於具強氧化能力的氫氧自由基是極不穩定物質,因此,高階氧化程式存在許多無法克服缺點,而無法大量應用於含酚類污染物廢水之處理。 Since phenolic compounds are highly toxic and difficult to decompose organic compounds and have serious environmental hazards, many scholars at home and abroad regard phenolic compounds as public enemies. The research on the treatment of phenol-containing wastewater has been carried out, and the wastewater containing phenolic pollutants cannot be treated by the existing activated sludge method because of its biological toxicity. Therefore, the high-order oxidation program is often used for wastewater containing phenolic pollutants. Oxidation Processes (AOPs) are used to reduce the toxicity of pollutants. The mechanism of high-order oxidation is mainly to react with organic substances in homogeneous and heterogeneous conditions with hydroxyl radicals with strong oxidizing power. The reaction yields an electron. When the electron of the organic substance is obtained, the structure of the organic substance is changed or the organic substance is decomposed to form a smaller molecular weight. However, since the hydroxyl radical having a strong oxidizing ability is a highly unstable substance, high-order oxidation is performed. There are many shortcomings in the program that cannot be overcome, and it cannot be applied to the treatment of wastewater containing phenolic pollutants.

緣是,本發明人有鑑於現有高階氧化程式對含酚類污染物廢水進行處理時之不穩定性,及無法大量應用等缺失,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,針對現有含酚類污染物廢水處理方法進行研發改良,而研創出本發明。 The reason is that the present inventors have in view of the instability of the existing high-order oxidation program for treating wastewater containing phenolic pollutants, and the inability to apply in large quantities, etc., thanks to years of manufacturing and design experience and knowledge in related fields. And through various ingenuity, research and development of the existing wastewater treatment method containing phenolic pollutants, and research and development of the present invention.

本發明係有關於一種陶瓷觸媒膜管製備方法,尤指一種簡便成型且可有效去除廢水所含酚類及總有機碳之陶瓷觸媒膜管製備方法。 The invention relates to a method for preparing a ceramic catalyst film tube, in particular to a method for preparing a ceramic catalyst film tube which is simple and can effectively remove phenols and total organic carbon contained in waste water.

為了達到上述實施目的,本發明人乃研擬如下陶瓷觸媒膜管製備方法,係主要設有可燒結粉體,該可燒結粉體係至少包含二氧 化鈦、高嶺土及活性氧化鋁其中之一,且該二氧化鈦、高嶺土及活性氧化鋁其含量為30公克的二氧化鈦、15公克的高嶺土及5公克的活性氧化鋁,並於該可燒結粉體中添加有金屬鹽類,該金屬鹽類係為2~10%之氧化銅及2~10%之三氧化二鐵其中之一,再將該可燒結粉體及金屬鹽類均勻攪拌混合,繼添加入黏結劑及孔洞生成劑,該黏結劑係為聚乙烯醇,該孔洞生成劑為聚乙烯二醇,再將該可燒結粉體、金屬鹽類及黏結劑均勻攪拌混練形成坯料,又以擠壓裝置將該坯料擠壓成型為膜管狀,續將擠壓成型之膜管狀坯料陰乾除去表面水分,再將該膜管狀坯料進行高溫燒結,該高溫燒結係採階段升溫至欲成型之溫度1100℃,其一開始升溫速率為1.21℃/分鐘,升溫至400℃時停留30分鐘,再以升溫速率2.78℃/分鐘升溫至900℃時停留1小時,接著以升溫速率3.33℃/分鐘升溫至1100℃時停留1小時,待降至室溫後取出,以成型陶瓷觸媒膜管。 In order to achieve the above-mentioned object, the present inventors have developed a method for preparing a ceramic catalyst film tube, which is mainly provided with a sinterable powder, and the sinterable powder system contains at least dioxin. One of titanium oxide, kaolin and activated alumina, and the titanium dioxide, kaolin and activated alumina have a content of 30 g of titanium dioxide, 15 g of kaolin and 5 g of activated alumina, and are added to the sinterable powder. There is a metal salt, which is one of 2 to 10% copper oxide and 2 to 10% of ferric oxide. The sinterable powder and the metal salt are uniformly stirred and mixed, and then added. a binder and a pore generating agent, the binder is polyvinyl alcohol, the pore generating agent is polyethylene glycol, and the sinterable powder, the metal salt and the binder are uniformly stirred and kneaded to form a billet, and extruded. The device extrudes the blank into a tubular shape, and continues to extrude the formed tubular tubular blank to remove surface moisture, and then the tubular tubular blank is subjected to high-temperature sintering, and the high-temperature sintering is heated to a temperature of 1100 ° C to be formed. The initial heating rate is 1.21 ° C / min, the temperature is raised to 400 ° C for 30 minutes, and then the temperature is raised at 2.78 ° C / min to 900 ° C for 1 hour, followed by the temperature increase rate of 3.33 ° C / minute to 1100 1 hour residence time, to be taken down to room temperature, to mold a ceramic catalytic membrane tube.

藉此,當將該陶瓷觸媒膜管應用於觸媒催化氧化系統,以氧化降解含酚廢水時,係可將含酚廢水內污染物有效轉化及將總有機碳有效去除,據此,藉由該簡易成型之陶瓷觸媒膜管及其製備方法,係可達到經濟、便利且高效能之廢水淨化效果。 Thereby, when the ceramic catalyst film tube is applied to the catalytic catalytic oxidation system to oxidize and degrade the phenol-containing wastewater, the pollutants in the phenol-containing wastewater can be effectively converted and the total organic carbon can be effectively removed, thereby The simple molded ceramic catalyst film tube and the preparation method thereof can achieve an economical, convenient and high-efficiency wastewater purification effect.

第一圖:本發明之陶瓷觸媒膜管製備流程圖 First: Flow chart of preparation of ceramic catalyst film tube of the present invention

第二圖:本發明之不同含量之氧化銅所製備之銅型陶瓷觸媒膜管其電子顯微鏡觀察圖(一) Second: Electron microscopic observation of a copper-type ceramic catalyst film tube prepared by different amounts of copper oxide of the present invention (1)

第三圖:本發明之不同含量之氧化銅所製備之銅型陶瓷觸媒膜管其電子顯微鏡觀察圖(二) The third figure: electron microscopic observation of copper-type ceramic catalyst film tube prepared by different content of copper oxide of the present invention (2)

第四圖:本發明之不同含量之氧化銅所製備之銅型陶瓷觸媒膜管其電子顯微鏡觀察圖(三) Figure 4: Electron microscopic observation of a copper-type ceramic catalyst film tube prepared by different amounts of copper oxide of the present invention (3)

第五圖:本發明之不同含量之三氧化二鐵所製備之鐵型陶瓷觸媒膜管其電子顯微鏡觀察圖(一) Figure 5: Electron microscopic observation of an iron-type ceramic catalyst film tube prepared by different amounts of ferric oxide according to the present invention (I)

第六圖:本發明之不同含量之三氧化二鐵所製備之鐵型陶瓷觸媒膜管其電子顯微鏡觀察圖(二) Figure 6: Electron microscopic observation of an iron-type ceramic catalyst film tube prepared by different amounts of ferric oxide according to the present invention (II)

第七圖:本發明之不同含量之三氧化二鐵所製備之鐵型陶瓷觸媒膜管其電子顯微鏡觀察圖(三) Figure 7: Electron microscopic observation of an iron-type ceramic catalyst film tube prepared by different amounts of ferric oxide according to the present invention (3)

第八圖:本發明之銅型陶瓷觸媒膜管催化過氧化氫產生氫氧自由基之時間變化圖 Figure 8: Time-dependent diagram of hydrogen peroxide radical generation by hydrogen peroxide catalyzed by copper-type ceramic catalyst film tube of the present invention

第九圖:本發明之銅型陶瓷觸媒膜管催化臭氧產生氫氧自由基之時間變化圖 Figure 9: Time-varying diagram of the generation of hydroxyl radicals by ozone in the copper-type ceramic catalyst membrane tube of the present invention

第十圖:本發明之鐵型陶瓷觸媒膜管催化過氧化氫產生氫氧自由基之時間變化圖 Figure 10: Time-dependent diagram of hydrogen peroxide radical generation catalyzed by hydrogen peroxide in the iron-type ceramic catalyst film tube of the present invention

第十一圖:本發明之鐵型陶瓷觸媒膜管催化臭氧產生氫氧自由基之時間變化圖 Figure 11: Time-varying diagram of the generation of hydroxyl radicals by ozone in the iron-type ceramic catalyst membrane tube of the present invention

第十二圖:本發明之銅型陶瓷觸媒膜管於不同pH值對含酚廢水氧化降解變化圖 Twelfth Figure: Oxidative degradation of phenol-containing wastewater at different pH values of the copper-type ceramic catalyst film tube of the present invention

第十三圖:本發明之銅型陶瓷觸媒膜管於不同pH值對含酚廢水之總有機碳去除率變化圖 Thirteenth Figure: Variation of total organic carbon removal rate of phenol-containing wastewater at different pH values of the copper-type ceramic catalyst film tube of the present invention

第十四圖:本發明之鐵型陶瓷觸媒膜管於不同pH值對含酚廢水氧化降解變化圖 Figure 14: Oxidative degradation of phenol-containing wastewater at different pH values of the iron-type ceramic catalyst film tube of the present invention

第十五圖:本發明之鐵型陶瓷觸媒膜管於不同pH值對含酚廢水之總有機碳去除率變化圖 Figure 15: Variation of total organic carbon removal rate of phenol-containing wastewater at different pH values of the iron-type ceramic catalyst film tube of the present invention

第十六圖:本發明之銅型陶瓷觸媒膜管於不同過氧化氫濃度對含酚廢水氧化降解變化圖 Figure XVI: Oxidative degradation of phenol-containing wastewater by different hydrogen peroxide concentrations in the copper ceramic catalyst tube of the present invention

第十七圖:本發明之銅型陶瓷觸媒膜管於不同過氧化氫濃度對含酚廢水之總有機碳去除率變化圖 Figure 17: Variation of total organic carbon removal rate of phenol-containing wastewater by different copper peroxide concentrations in the copper ceramic catalyst tube of the present invention

第十八圖:本發明之鐵型陶瓷觸媒膜管於不同過氧化氫濃度對含酚廢水氧化降解變化圖 Figure 18: Oxidative degradation of phenol-containing wastewater by different concentrations of hydrogen peroxide in the iron-type ceramic catalyst tube of the present invention

第十九圖:本發明之鐵型陶瓷觸媒膜管於不同過氧化氫濃度對含酚廢水之總有機碳去除率變化圖 Figure 19: Variation of total organic carbon removal rate of phenol-containing wastewater by different concentrations of hydrogen peroxide in the iron-type ceramic catalyst tube of the present invention

第二十圖:本發明之銅型陶瓷觸媒膜管於穩定性試驗對含酚廢水氧化降解變化圖 Fig. 20 is a graph showing the oxidative degradation of phenol-containing wastewater in the stability test of the copper-type ceramic catalyst film tube of the present invention

第二十一圖:本發明之銅型陶瓷觸媒膜管於穩定性試驗對含酚廢水之總有機碳去除率變化圖 Figure 21: Change of total organic carbon removal rate of phenol-containing wastewater in the stability test of copper-type ceramic catalyst film tube of the present invention

第二十二圖:本發明之鐵型陶瓷觸媒膜管於穩定性試驗對含酚廢水氧化降解變化圖 Figure 22: Oxidative degradation of phenol-containing wastewater in the stability test of the iron-type ceramic catalyst tube of the present invention

第二十三圖:本發明之鐵型陶瓷觸媒膜管於穩定性試驗對含酚廢水之總有機碳去除率變化圖 Twenty-third figure: variation of total organic carbon removal rate of phenol-containing wastewater in the stability test of the iron-type ceramic catalyst film tube of the present invention

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:首先,請參閱第一圖所示,為本發明之陶瓷觸媒膜管製備方法,係將固定配比之可燒結粉體,該可燒結粉體係至少包含二氧化鈦(TiO2)、高嶺土(Kaolin)及活性氧化鋁(γ-Al2O3)其中之一,該二氧化鈦、高嶺土及活性氧化鋁最佳含量為30公克的二氧化鈦、15公克的高嶺土及5公克的活性氧化鋁,又於該可燒結粉體中添加不同克數之氧化銅(CuO)或三氧化二鐵(Fe2O3)等其中之一金屬鹽類後,置於500毫升的燒杯中,再使用高速攪拌裝置乾混,攪拌8小時使其均勻,繼緩緩添加配製好的聚乙烯醇(PVA)黏結劑與聚乙 烯二醇(PEG200、PEG400、PEG600)孔洞生成劑,並攪拌約30分鐘至1小時,以混練成型坯料,再以研缽將成型坯料中的空氣敲打擠出,並使用手推式擠壓裝置將坯料擠壓成型為膜管狀坯料,續將擠壓成型之膜管狀坯料放至氧化鋁板上,並置入盒子密閉陰乾一天先除去表面水分,再把膜管狀坯料與氧化鋁板一起置入可程式高溫爐內進行高溫燒結,以六個階段的升溫方式,逐漸升溫至欲成型之溫度1100℃,一開始先開高溫爐電源,升溫速率為1.21℃/分鐘,升溫至400℃時停留30分鐘,再以升溫速率2.78℃/分鐘升溫至900℃時停留1小時,接著以升溫速率3.33℃/分鐘升溫至1100℃時停留1小時,待降至室溫後取出,即可獲得本發明之陶瓷觸媒膜管。 In order to make the technical means of the present invention and the effects thereof can be more completely and clearly disclosed, the details are as follows. Please refer to the disclosed drawings and drawings: First, please refer to the first figure. The method for preparing a ceramic catalyst film tube according to the present invention is to fix a ratio of the sinterable powder, the sinterable powder system comprising at least titanium dioxide (TiO2), kaolin (Kaolin) and activated alumina (γ-Al2O3). One of the titanium dioxide, kaolin and activated alumina has an optimum content of 30 g of titanium dioxide, 15 g of kaolin and 5 g of activated alumina, and different amounts of copper oxide (CuO) are added to the sinterable powder. ) or one of the metal salts such as ferric oxide (Fe2O3), placed in a 500 ml beaker, dry mixed using a high-speed stirring device, stirred for 8 hours to make it uniform, and then slowly added the prepared polyethylene. Alcohol (PVA) Adhesive and Polyethylene B The olefinic diol (PEG200, PEG400, PEG600) pore-forming agent is stirred for about 30 minutes to 1 hour to knead the formed blank, and then the air in the shaped blank is tapped and extruded by a mortar, and a hand-pushing extrusion device is used. The blank is extruded into a tubular tubular blank, and the extruded tubular blank is continuously placed on an alumina plate, and placed in a box to be sealed and dried for one day to remove surface moisture, and then the tubular tubular blank is placed together with the alumina plate. The high-temperature furnace is subjected to high-temperature sintering, and the temperature is gradually increased to a temperature of 1100 ° C in a six-stage heating mode. The high-temperature furnace power supply is first turned on, the heating rate is 1.21 ° C / min, and the temperature is raised to 400 ° C for 30 minutes. Then, the temperature is raised to 900 ° C at a heating rate of 2.78 ° C / min for 1 hour, then the temperature is raised to 1.100 ° C at a heating rate of 3.33 ° C / min for 1 hour, and after being taken down to room temperature, the ceramic contact of the present invention can be obtained. Media tube.

據此,當使用實施時,係將本發明之陶瓷觸媒膜管設置於氧化系統之反應器中,再以臭氧(O3)及過氧化氫(H2O2)為氧化劑,每隔20分鐘採樣一次,採樣時間分別為0、20、40、60、80、100及120分鐘,反應時間為2小時,於氧化系統中係以連續循環式來氧化降解水中污染物,當有機物擴散到本發明之陶瓷觸媒膜管表面後,係先與陶瓷觸媒膜管表面之鐵、銅等金屬活化物產生化學性吸附,由於反應的活化能降低,因此,在特定的溫度與氧氣供應下,有機物會發生斷鍵反應,並釋放出熱能,及生成二氧化碳和水,而由陶瓷觸媒膜管表面脫附,另擴散到陶瓷觸媒膜管內孔隙之有機物,則會由陶瓷觸媒膜管內孔隙擴散至外面。 Accordingly, when used, the ceramic catalyst film tube of the present invention is placed in a reactor of an oxidation system, and ozone (O3) and hydrogen peroxide (H2O2) are used as oxidants, and samples are taken every 20 minutes. The sampling time is 0, 20, 40, 60, 80, 100 and 120 minutes, and the reaction time is 2 hours. In the oxidation system, the continuous oxidation system is used to oxidize and degrade the pollutants in the water, and when the organic matter diffuses to the ceramic touch of the present invention. After the surface of the film tube, the metal activator such as iron or copper on the surface of the ceramic catalyst tube is chemically adsorbed, and the activation energy of the reaction is lowered. Therefore, the organic substance is broken at a specific temperature and oxygen supply. The bond reacts and releases heat energy, and generates carbon dioxide and water. The organic matter which is desorbed from the surface of the ceramic catalyst film tube and diffused into the pores of the ceramic catalyst film tube is diffused from the pores in the ceramic catalyst film tube to outside.

繼之,本發明係進一步對陶瓷觸媒膜管添加不同濃度氧化銅, 於燒結溫度1100℃下,探討添加不同濃度之氧化銅所成型之銅型陶瓷觸媒膜管(TKA)其比表面積(BET)及孔隙(Å)大小之影響,請參閱表1係於陶瓷觸媒膜管(TKA)製程中未添加氧化銅,及依序添加有2%(TKA-C2)、4%(TKA-C4)、6%(TKA-C6)、8%(TKA-C8)及10%(TKA-C10)之氧化銅的測試結果。由表1之結果顯示,於未添加氧化銅時,陶瓷觸媒膜管(TKA)之比表面積(BET)為2.7平方公尺/克(m 2/g),平均孔隙為1231.7(Å),隨著氧化銅含量增加至10%時,其比表面積(BET)為0.6平方公尺/克,平均孔隙大小749.4(Å),故由該結果得知,隨著氧化銅含量增加,可明顯降低比表面積(BET)及孔隙大小。 In addition, the present invention further adds different concentrations of copper oxide to the ceramic catalyst film tube. At the sintering temperature of 1100 ° C, the effect of the specific surface area (BET) and pore size (Å) of the copper-type ceramic catalyst film tube (TKA) formed by adding different concentrations of copper oxide is discussed. No copper oxide was added to the process of the TKA process, and 2% (TKA-C2), 4% (TKA-C4), 6% (TKA-C6), 8% (TKA-C8) and Test results for 10% (TKA-C10) copper oxide. The results of Table 1 show that the ceramic catalyst tube (TKA) has a specific surface area (BET) of 2.7 m ^ 2 /g (m 2 / g) and an average pore size of 1231.7 (Å) when copper oxide is not added. As the copper oxide content increases to 10%, the specific surface area (BET) is 0.6 m ^ 2 / g, and the average pore size is 749.4 (Å). Therefore, it is known from the results that as the copper oxide content increases, it can be significantly reduced. Specific surface area (BET) and pore size.

又請參閱第二~四圖所示,為不同含量之氧化銅所製備成型之銅型陶瓷觸媒膜管其電子顯微鏡(SEM)觀察圖,於第二圖中係可明顯看出未添加氧化銅之陶瓷觸媒膜管其晶體尺寸大小為不均勻之分佈,大晶體上係附著有許多小晶體,另表面孔隙係明顯呈現,而添加2%~6%氧化銅類之陶瓷觸媒膜管,其膜管表面顆粒均為大顆粒,且顆粒形狀為圓形、橢圓形,另膜管表面結構呈現半融熔狀, 而孔隙慢慢變小,隨著氧化銅含量增加至8%以上時,膜管表面之圓形、橢圓形顆粒隨之消失,晶體尺寸呈現長柱狀,膜管表面結構呈現完全融熔、緻密狀態,而明顯可見再結晶現象並呈現不規則排列。 Please also refer to the second to fourth figures, the electron microscope (SEM) observation of the copper-type ceramic catalyst film tube prepared for different content of copper oxide. In the second figure, it is obvious that no oxidation is added. The crystal size of the copper ceramic catalyst tube is uneven. The large crystals are attached with many small crystals, and the surface pores are obviously present. The ceramic catalyst tube with 2%~6% copper oxide is added. The surface of the membrane tube is large particles, and the shape of the particles is round and elliptical, and the surface structure of the membrane tube is semi-melted. The pores gradually become smaller. As the copper oxide content increases to more than 8%, the circular and elliptical particles on the surface of the membrane tube disappear, and the crystal size is long columnar. The surface structure of the membrane tube is completely melted and dense. State, and recrystallization is clearly visible and presents an irregular arrangement.

續之,本發明係再進一步針對陶瓷觸媒膜管於添加不同濃度之三氧化二鐵,於燒結溫度1100℃下,探討添加不同濃度之三氧化二鐵所成型之鐵型陶瓷觸媒膜管(TKA)其比表面積(BET)及孔隙(Å)大小之影響,請參閱表2係於陶瓷觸媒膜管(TKA)製程中未添加三氧化二鐵,及依序添加有2%(TKA-F2)、4%(TKA-F4)、6%(TKA-F6)、8%(TKA-F8)及10%(TKA-F10)之三氧化二鐵的測試結果。由表2之結果顯示,當未添加三氧化二鐵時,陶瓷觸媒膜管(TKA)之比表面積(BET)為2.7平方公尺/克(m 2/g),隨著三氧化鐵含量增加至10%時,其比表面積(BET)為1.9平方公尺/克(m 2/g),孔隙大小為498.2(Å),故由研究結果可知,隨著三氧化鐵含量增加,陶瓷觸媒膜管之比表面積(BET)及孔隙大小亦明顯降低。 Continuing, the present invention further relates to adding a different concentration of ferric oxide to the ceramic catalyst film tube, and discussing the iron-type ceramic catalyst film tube formed by adding different concentrations of ferric oxide at a sintering temperature of 1100 ° C. (TKA) The effect of specific surface area (BET) and pore size (Å), please refer to Table 2 for the addition of ferric oxide in the ceramic catalyst tube (TKA) process, and 2% (TKA) Test results of -F2), 4% (TKA-F4), 6% (TKA-F6), 8% (TKA-F8) and 10% (TKA-F10) ferric oxide. From the results of Table 2, when the ferric oxide is not added, the specific surface area (BET) of the ceramic catalyst film tube (TKA) is 2.7 m ^ 2 / gram (m 2 / g), along with the content of iron trioxide When increased to 10%, the specific surface area (BET) is 1.9 m ^ 2 / g (m 2 / g), and the pore size is 498.2 (Å). Therefore, it is known from the research results that as the content of ferric oxide increases, the ceramic touch The specific surface area (BET) and pore size of the membrane tube are also significantly reduced.

另請參閱第五~七圖所示,為不同含量之三氧化二鐵所製備成型之鐵型陶瓷觸媒膜管其電子顯微鏡(SEM)觀察圖,由圖中係可明顯看出未添加三氧化二鐵之陶瓷觸媒膜管其晶體尺寸大小不均勻分佈,大晶體上附著許多細小顆粒,表面孔隙呈現顯著,當添加2%~6%三氧化二鐵於陶瓷觸媒膜管中時,膜管表面顆粒尺寸大小係呈不均勻分佈,顆粒形狀為不規則長片狀,於大晶體上有細小顆粒融於表面,膜管表面與添加氧化銅相較之下尚未呈現熔融狀態,孔隙係明顯呈現,而當三氧化二鐵含量增加至8%以上時,膜管表面結構相較於氧化銅,係明顯未呈現熔融、緻密狀態,另晶體型態、孔隙度相當顯著,故由此可推斷,氧化銅與三氧化二鐵於燒結溫度1100℃時,氧化銅燒結於膜管表面結構明顯呈現完全緻密、熔融狀態,晶體可呈再結晶現象,而三氧化二鐵燒結於膜管表面結構係明顯呈晶體型態且孔隙度明顯,表示燒結溫度尚未達到三氧化二鐵之熔點。 Please also refer to the electron microscope (SEM) observation chart of the iron-type ceramic catalyst film tube prepared by different content of ferric oxide as shown in the fifth to seventh figures. It can be clearly seen from the figure that no three are added. The ceramic catalyst tube of ferric oxide has a non-uniform crystal size distribution, and many fine particles are attached to the large crystal, and the surface pores are prominent. When 2% to 6% of ferric oxide is added to the ceramic catalyst tube, The particle size on the surface of the membrane tube is unevenly distributed, and the shape of the particles is irregularly long. The small particles are melted on the surface of the large crystal. The surface of the membrane tube is not in a molten state compared with the addition of copper oxide. Obviously, when the content of ferric oxide increases to 8% or more, the surface structure of the membrane tube is obviously not molten or dense compared with that of copper oxide, and the other crystal type and porosity are quite remarkable, so It is concluded that when the copper oxide and ferric oxide are sintered at a temperature of 1100 °C, the surface structure of the copper oxide sintered on the film tube is completely dense and molten, and the crystal can be recrystallized, and the ferric oxide is sintered in the membrane tube. In crystalline structure based surface patterns and significant apparent porosity, the sintering temperature is not yet reached represents the melting point of iron oxide.

再者,本發明係再針對不同氧化劑對氫氧自由基生成量之影響進行螢光試劑之測試,乃以臭氧(O3)、過氧化氫(H2O2)為氧化劑,以0.05莫耳一次添加,反應溫度約25℃,請參閱第八圖所示,為含量10%氧化銅之銅型陶瓷觸媒膜管於氧化劑環境中,比較氫氧自由基生最佳生成量,結果顯示,於過氧化氫(H2O2)為氧化劑條件下,氫氧自由基有最佳生成量,將其以稀釋100倍進行分析,其螢光強度約為400,而當以臭氧(O3)做為氧化劑時,將其以稀釋10倍進行分析,則螢光強度約在150~200以內〔如第九圖所示〕。另請 參閱第十、十一圖所示,為含量10%三氧化二鐵之鐵型陶瓷觸媒膜管於氧化劑環境中,比較氫氧自由基生最佳生成量,將其以稀釋100倍及10倍分別進行分析,係顯示於過氧化氫(H2O2)及臭氧(O3)為氧化劑之條件下,其氫氧自由基均有良好的生成量,其螢光強度都約在400左右。 Furthermore, the present invention further tests the effect of different oxidizing agents on the amount of hydroxyl radical generation, and uses ozone (O3) and hydrogen peroxide (H2O2) as oxidizing agents to add 0.05 mol at a time. The temperature is about 25 ° C, please refer to the eighth figure, the copper-type ceramic catalyst film tube with 10% copper oxide in the oxidant environment, compare the optimal production of hydroxyl radicals, the results show that in hydrogen peroxide (H2O2) is an oxidant, the optimal production of hydroxyl radicals, which is analyzed by diluting 100 times, the fluorescence intensity is about 400, and when ozone (O3) is used as the oxidant, When the analysis is diluted 10 times, the fluorescence intensity is about 150 to 200 (as shown in the ninth figure). Please also Referring to the tenth and eleventh figures, the iron-type ceramic catalyst film tube containing 10% ferric oxide is compared in the oxidant environment, and the optimal production amount of hydroxyl radicals is compared, and the dilution is 100 times and 10 times. The analysis was carried out separately. Under the conditions of hydrogen peroxide (H2O2) and ozone (O3) as oxidants, the hydroxyl radicals have a good amount of formation, and the fluorescence intensity is about 400.

又本發明係再針對不同酸鹼值(pH)變化對含酚廢水氧化效果影響進行測試,於氧化系統中,最適pH值範圍產生較大的自由基生成量,在氧化反應中,pH值較低時,係可使氫氧自由基有效被啟動,而在pH值過高時,氧化劑所釋出的氫氧自由基量則會減少,故pH值高低會影響到氫氧自由基之生成量,於測試結果pH值介於3~4間係最有助於對污染物氧化降解。然,由於金屬氧化物於低pH值環境下有溶解性增加情況,因此,對銅型及鐵型陶瓷觸媒膜管是否亦有溶出問題,本發明係以感應耦合電漿原子發射光譜儀(Inductively Coupled Plasma,ICP)來分析陶瓷觸媒膜管之金屬溶出量,本發明係將反應槽溶液pH控制於pH4~7,以探討於不同pH值之氧化環境下,對其氧化降解含酚廢水與廢水之總有機碳(TOC)去除效果影響。請參閱第十二、十三圖所示,為含量10%氧化銅之銅型陶瓷觸媒膜管於不同pH環境中,對氧化反應系統廢水中酚轉化率及總有機碳(TOC)去除率之影響,反應期間pH值分別控制在4~7,其含酚廢水氧化降解效率分別為100%、99.9%、93.5%、75.6%,而總有機碳(TOC)去除率分別為48.2%、38.6%、31.5%、20.4%。另含量10%氧化銅之銅型陶瓷觸媒膜管於氧化反 應系統之銅金屬鹽溶出量分別為pH4為3.0毫克/升(mg/L)、pH5為1.1毫克/升、pH6為0.2毫克/升、pH7為0.2毫克/升,故由第十二圖之含酚廢水氧化降解效果與pH值變化之關係中得知,當pH值7時,降低降解速率,隨pH值降低則其pH值降解速率則有明顯加快之現象,而pH7之水溶液其起初水中含H+濃度太低不易促進H2O2分解生成氫氧自由基(OH‧),因此氫氧自由基數量太少而導致含酚廢水降解無明顯之降解,當中性溶液反應進行一段時間時,因中間產物所生成有機酸,有利於pH值降低,因此氫氧自由基生成係產生加速現象,此一結果生成更多有機酸創造更低之pH值環境,因此更有利於含酚廢水降解反應,於低pH環境初始條件時,則因氫氧自由基生成則有利於含酚廢水降解率皆達95%以上,此一現象印證氧化反應中氧化速率與pH值之相互關聯性。 The invention further tests the effect of different pH values on the oxidation effect of the phenol-containing wastewater, and in the oxidation system, the optimum pH value range produces a large amount of free radical formation, and in the oxidation reaction, the pH value is compared. When low, the hydroxyl radicals can be effectively activated, and when the pH is too high, the amount of hydroxyl radicals released by the oxidant will decrease, so the pH value will affect the amount of hydroxyl radical generation. In the test results, the pH value is between 3 and 4, which is most helpful for the oxidative degradation of pollutants. However, since the metal oxide has a solubility increase in a low pH environment, whether or not there is a problem of dissolution of the copper type and the iron type ceramic catalyst tube, the present invention is an inductively coupled plasma atomic emission spectrometer (Inductively Coupled Plasma (ICP) to analyze the metal elution amount of the ceramic catalyst film tube. The present invention controls the pH of the reaction tank solution to pH 4-7 to investigate the oxidative degradation of phenol-containing wastewater under different pH values in an oxidizing environment. The effect of total organic carbon (TOC) removal from wastewater. Please refer to the twelfth and thirteenth figures, the phenol conversion rate and the total organic carbon (TOC) removal rate in the oxidation reaction system wastewater in a different pH environment for a copper-type ceramic catalyst film tube containing 10% copper oxide. The effect of pH value during the reaction was controlled at 4~7, and the oxidative degradation efficiencies of phenol-containing wastewater were 100%, 99.9%, 93.5%, and 75.6%, respectively, while the total organic carbon (TOC) removal rates were 48.2% and 38.6, respectively. %, 31.5%, 20.4%. Another 10% copper oxide copper type ceramic catalyst film tube is oxidized The amount of copper metal salt dissolved in the system is pH 4 of 3.0 mg / liter (mg / L), pH 5 of 1.1 mg / liter, pH of 0.6 mg / liter, pH of 0.2 mg / liter, so by the twelfth figure The relationship between the oxidative degradation effect of phenol-containing wastewater and the change of pH value shows that when the pH value is 7, the degradation rate is decreased, and the pH degradation rate is obviously accelerated as the pH value is lowered, and the pH 7 aqueous solution is in the initial water. The H+ concentration is too low to promote the decomposition of H2O2 to form hydroxyl radicals (OH‧). Therefore, the amount of hydroxyl radicals is too small, resulting in no degradation of phenol-containing wastewater degradation. The neutral solution reacts for a period of time due to intermediates. The organic acid produced is beneficial to the pH value reduction, so the hydroxyl radical generation system accelerates, which results in more organic acid to create a lower pH environment, and thus is more favorable for the degradation reaction of the phenol-containing wastewater. In the initial conditions of pH environment, the formation of phenolic wastewater is more than 95% due to the formation of hydroxyl radicals. This phenomenon confirms the correlation between the oxidation rate and pH value in the oxidation reaction.

另請參閱第十四、十五圖所示,係為含量10%三氧化二鐵之鐵型陶瓷觸媒膜管於不同pH環境中,對氧化反應系統廢水中酚轉化率及總有機碳(TOC)去除率影響,反應期間pH值分別控制在4~7,其含酚廢水氧化降解效率分別為100%、96.6%、92.1%、72.6%,對總有機碳(TOC)之去除率分別為43.8%、35.6%、27.2%、18.8%,另含量10%三氧化二鐵之鐵型陶瓷觸媒膜管於氧化反應系統之金屬鹽溶出量分別為pH4為無檢出(ND)、pH5為無檢出(ND)、pH6為無檢出(ND)、pH7為0.6mg/L,相較於銅型陶瓷觸媒膜管,其金屬溶出量鐵離子溶出量更低於銅離子,由以上結果得知,不同pH環境中,於銅、鐵型陶瓷觸媒膜管含酚廢水轉化率、總有機碳(TOC) 之去除率與金屬鹽溶出量顯然不同,改變反應槽內之pH值對氧化反應效果有顯著影響,氧化降解效果隨著pH值越低其效果越佳,總有機碳之去除率也隨著pH值降低而提高。又由圖示中可看出在pH值4之氧化環境下,其氧化去除效果顯然較佳,但會導致陶瓷觸媒膜管之金屬鹽有溶出現象,於pH值為5時,含酚廢水轉化率皆有96%、總有機碳去除率有45%以上,pH值為6、7時,會因不易產生氫氧自由基以致於氧化效果變低,但陶瓷觸媒膜管之金屬鹽溶出現象較低。 Please also refer to the fourteenth and fifteenth figures, which are the phenol conversion rate and total organic carbon in the oxidation reaction system wastewater in different pH environments for iron-type ceramic catalyst tubes with 10% ferric oxide. TOC) removal rate, the pH value during the reaction was controlled at 4~7, and the oxidative degradation efficiency of phenol-containing wastewater was 100%, 96.6%, 92.1%, 72.6%, respectively. The removal rate of total organic carbon (TOC) was 43.8%, 35.6%, 27.2%, 18.8%, the content of the metal salt in the oxidation reaction system of the iron-type ceramic catalyst tube of another 10% ferric oxide is pH 4 is no detection (ND), and pH 5 is No detection (ND), pH 6 is no detection (ND), pH 7 is 0.6 mg / L, compared with the copper ceramic catalyst film tube, the metal elution amount of iron ion elution amount is lower than copper ion, from above The results show that the conversion rate of phenol-containing wastewater and total organic carbon (TOC) in copper and iron-type ceramic catalyst membrane tubes in different pH environments The removal rate is obviously different from the metal salt elution amount. Changing the pH value in the reaction tank has a significant effect on the oxidation reaction effect. The oxidative degradation effect is better with the lower pH value, and the total organic carbon removal rate also follows the pH. The value is lowered and increased. It can be seen from the figure that in the oxidizing environment of pH 4, the oxidative removal effect is obviously better, but the metal salt of the ceramic catalyst film tube is dissolved, and the phenol wastewater is used at a pH of 5. The conversion rate is 96%, the total organic carbon removal rate is more than 45%, and when the pH is 6, 7, the hydrogen peroxide radical is not easily generated, so that the oxidation effect is low, but the metal salt of the ceramic catalyst film tube is dissolved. The phenomenon is lower.

故由上述不同酸鹼值(pH)變化對含酚廢水氧化效果影響進行測試結果顯示,銅型陶瓷觸媒膜管之總有機碳(TOC)去除率雖優於鐵型陶瓷觸媒膜管,但銅型陶瓷觸媒膜管金屬溶出現象卻高於鐵型陶瓷觸媒膜管。另於pH值降低時,係使過氧化氫快速消耗,說明反應中低pH值有利於氫氧自由基(OH‧)產生,故可使得過氧化氫殘存量迅速減少,也因為偏酸溶液中高量氫氧自由基與有機物反應之總有機碳(TOC)去除率亦隨即提高,反之於高pH值環境下,則不利於對氧化系統中氫氧自由基產生,對於總有機碳也無明顯去除,因此,由本發明之測試結果得知,當反應於pH5環境下對於污染物有高轉化率及具低金屬溶出量之效果。 Therefore, the results of the above-mentioned different acid-base value (pH) changes on the oxidation effect of phenol-containing wastewater show that the total organic carbon (TOC) removal rate of the copper-type ceramic catalyst film tube is better than that of the iron-type ceramic catalyst film tube. However, the appearance of metal dissolution of the copper-type ceramic catalyst film tube is higher than that of the iron-type ceramic catalyst film tube. In addition, when the pH is lowered, the hydrogen peroxide is rapidly consumed, indicating that the low pH value in the reaction is favorable for the generation of hydroxyl radicals (OH‧), so that the residual amount of hydrogen peroxide can be rapidly reduced, and also because the acid solution is high. The removal rate of total organic carbon (TOC) in the reaction of hydroxyl radicals with organic matter is also increased. Conversely, in the high pH environment, it is not conducive to the production of hydroxyl radicals in the oxidation system, and there is no obvious removal of total organic carbon. Therefore, it is known from the test results of the present invention that the reaction has a high conversion rate for contaminants and a low metal elution amount when reacted in a pH 5 environment.

再者,本發明係又進一步進行不同過氧化氫濃度對含酚廢水氧化效果之影響測試,本發明係以反應溫度60℃,pH5之氧化環境下,添加不同過氧化氫濃度,分別為0.05莫耳、0.10莫耳、0.15 莫耳、0.20莫耳,以探討銅、鐵型陶瓷觸媒膜管氧化降解酚轉化率、總有機碳(TOC)去除率與陶瓷觸媒膜管之金屬鹽溶出率等影響,請參閱第十六、十七圖所示,為含量10%氧化銅之銅型陶瓷觸媒膜管於溫度60℃、pH5氧化條件,分別添加濃度為0.05莫耳、0.10莫耳、0.15莫耳、0.20莫耳之過氧化氫對其氧化反應系統之含酚廢水之酚轉化率及總有機碳(TOC)之去除率之影響,反應期間添加0.05莫耳之過氧化氫時,反應於120分鐘後,含酚廢水氧化降解效率可達96.6%,總有機碳去除率為38.6%,又當添加0.10莫耳之過氧化氫,反應於60分鐘時,含酚廢水氧化降解效率為99.3%,80分鐘時,含酚廢水氧化降解效率為100%,總有機碳去除率為57.6%,另當添加0.15莫耳之過氧化氫,反應於40分鐘時,含酚廢水氧化降解效率為85%,60分鐘時,含酚廢水氧化降解效率為100%,總有機碳去除率為63.7%,而當添加0.20莫耳過氧化氫時,反應於40分鐘時,含酚廢水氧化降解效率為90%,60分鐘時,含酚廢水氧化降解效率為100%,總有機碳去除率為69.9%。由過氧化氫濃度提升對氧化效果有明顯之影響,過氧化氫濃度提高可有效提高酚轉化率及總有機碳去除率。 Furthermore, the present invention further tests the effect of different hydrogen peroxide concentrations on the oxidation effect of the phenol-containing wastewater. The present invention adds different hydrogen peroxide concentrations under the oxidation temperature of 60 ° C and pH 5, respectively. Ear, 0.10 m, 0.15 Moer, 0.20 Mo, to investigate the effect of oxidative degradation of phenol conversion, total organic carbon (TOC) removal rate and metal salt dissolution rate of ceramic catalyst tube in copper and iron ceramic catalyst tubes, please refer to the tenth As shown in Fig. 6 and Fig. 17, the copper-type ceramic catalyst film tube containing 10% copper oxide is added at a concentration of 0.05 m, 0.10 m, 0.15 m, and 0.20 m at a temperature of 60 ° C and pH 5, respectively. The effect of hydrogen peroxide on the phenol conversion rate and total organic carbon (TOC) removal rate of the phenol-containing wastewater in the oxidation reaction system. When 0.05 mol of hydrogen peroxide is added during the reaction, the reaction is carried out for 120 minutes, and the phenol is contained. The oxidative degradation efficiency of wastewater is up to 96.6%, the total organic carbon removal rate is 38.6%, and when 0.10 moles of hydrogen peroxide is added, the oxidative degradation efficiency of phenol-containing wastewater is 99.3% at 60 minutes. At 80 minutes, The oxidative degradation efficiency of phenol wastewater is 100%, the total organic carbon removal rate is 57.6%, and 0.15 moles of hydrogen peroxide is added. When the reaction is 40 minutes, the oxidative degradation efficiency of phenol-containing wastewater is 85%. At 60 minutes, The oxidative degradation efficiency of phenol wastewater is 100%, and the total organic carbon removal rate is 63.7%. When 0.20 mol of hydrogen peroxide was added, the oxidative degradation efficiency of the phenol-containing wastewater was 90% at 40 minutes, and the oxidative degradation efficiency of the phenol-containing wastewater was 100% at 60 minutes, and the total organic carbon removal rate was 69.9%. The increase of hydrogen peroxide concentration has a significant effect on the oxidation effect, and the increase of hydrogen peroxide concentration can effectively increase the phenol conversion rate and the total organic carbon removal rate.

又請參閱第十八、十九圖所示,為含量10%三氧化二鐵之鐵型陶瓷觸媒膜管鐵型陶瓷觸媒膜管於溫度60℃、pH5氧化環境中,分別添加濃度為0.05莫耳、0.10莫耳、0.15莫耳、0.20莫耳之過氧化氫對其氧化反應系統之含酚廢水轉化率及總有機碳(TOC)之去除率之影響,反應期間添加0.05莫耳之過氧化氫,反應於120 分鐘,含酚廢水氧化降解效率為96.6%,總有機碳去除率為35.6%,而當添加0.10莫耳之過氧化氫,反應於80分鐘時,含酚廢水氧化降解效率為92%,100分鐘時,含酚廢水氧化降解效率為100%,總有機碳去除率為43.5%,又當添加0.15莫耳之過氧化氫,反應於60分鐘時,含酚廢水氧化降解效率為96.85%,80分鐘時,含酚廢水氧化降解效率為100%,總有機碳去除率為52.2%,另當添加0.20莫耳過氧化氫時,反應於60分鐘時,含酚廢水氧化降解效率為95.3%,80分鐘時,含酚廢水氧化降解效率為100%,總有機碳去除率為63%。又於過氧化氫濃度為0.05莫耳時為0.3毫克/升(mg/L)、0.10莫耳時為無檢出(ND)、0.15莫耳時為無檢出、0.20莫耳時為無檢出。故在不同過氧化氫濃度下,銅型陶瓷觸媒膜管之酚轉化率雖優於鐵型陶瓷觸媒膜管,但鐵型陶瓷觸媒膜管金屬溶出現象明顯低於銅型陶瓷觸媒膜管。 Please also refer to the eighteenth and nineteenth figures, for the content of 10% ferric oxide iron-based ceramic catalyst film tube iron-type ceramic catalyst film tube in the temperature of 60 ° C, pH5 oxidation environment, respectively, the concentration is 0.05 mol, 0.10 mol, 0.15 mol, 0.20 mol of hydrogen peroxide on the oxidation reaction system containing phenol wastewater conversion rate and total organic carbon (TOC) removal rate, adding 0.05 m during the reaction Hydrogen peroxide, reacted at 120 Minutes, the oxidative degradation efficiency of phenol-containing wastewater was 96.6%, and the total organic carbon removal rate was 35.6%. When 0.10 moles of hydrogen peroxide was added, the oxidative degradation efficiency of phenol-containing wastewater was 92%, 100 minutes. The oxidative degradation efficiency of the phenol-containing wastewater is 100%, the total organic carbon removal rate is 43.5%, and when 0.15 moles of hydrogen peroxide is added, the oxidative degradation efficiency of the phenol-containing wastewater is 96.85%, 80 minutes after the reaction for 60 minutes. When the phenol-containing wastewater has an oxidative degradation efficiency of 100% and a total organic carbon removal rate of 52.2%, when 0.20 moles of hydrogen peroxide is added, the oxidative degradation efficiency of the phenol-containing wastewater is 95.3%, 80 minutes after the reaction for 60 minutes. At the same time, the oxidative degradation efficiency of the phenol-containing wastewater was 100%, and the total organic carbon removal rate was 63%. Also, when the concentration of hydrogen peroxide is 0.05 mol, it is 0.3 mg/L (mg/L), 0.10 mol is no detection (ND), 0.15 mol is no detection, and 0.20 mol is no inspection. Out. Therefore, under different hydrogen peroxide concentrations, the phenol conversion rate of the copper-type ceramic catalyst film tube is better than that of the iron-type ceramic catalyst film tube, but the metal dissolution of the iron-type ceramic catalyst film tube is significantly lower than that of the copper-type ceramic catalyst. Membrane tube.

故由上述不同過氧化氫濃度對含酚廢水氧化效果影響測試結果可知,於反應槽pH5之氧化環境下,添加不同過氧化氫濃度,銅、鐵型陶瓷觸媒膜管含酚廢水轉化率、總有機碳(TOC)之去除率與金屬鹽溶出量顯然不同,隨著氧化反應中過氧化氫之濃度提高對氧化反應效果有一定提升之影響,含酚廢水氧化降解效果、總有機碳(TOC)之去除率隨著過氧化氫之濃度提高其效果越佳,而當銅型陶瓷觸媒膜管於添加0.10莫耳以上過氧化氫,反應60分鐘後,含酚廢水氧化降解效果即可達100%,總有機碳(TOC)之去除率也隨著過氧化氫濃度之提高可達69.9%之去除率,另當鐵型陶瓷觸媒膜 管其過氧化氫需添加0.15莫耳以上,反應80分鐘後,含酚廢水氧化降解效果才可達100%,總有機碳之去除率也隨著過氧化氫濃度之提高可達63%。 Therefore, from the test results of the effects of different hydrogen peroxide concentrations on the oxidation of phenol-containing wastewater, it is known that in the oxidation environment of pH 5 of the reaction tank, different hydrogen peroxide concentrations are added, and the conversion rate of phenol wastewater in copper and iron-type ceramic catalyst membrane tubes is The removal rate of total organic carbon (TOC) is obviously different from that of metal salt. With the increase of the concentration of hydrogen peroxide in the oxidation reaction, the effect of oxidation reaction is enhanced, the oxidative degradation effect of phenol-containing wastewater, total organic carbon (TOC) The removal rate is better with the concentration of hydrogen peroxide, and when the copper-type ceramic catalyst tube is added with 0.10 mol or more of hydrogen peroxide, the oxidative degradation effect of the phenol-containing wastewater can be achieved after 60 minutes of reaction. 100%, the removal rate of total organic carbon (TOC) also increases with the concentration of hydrogen peroxide up to 69.9%, and the other is the iron-type ceramic catalyst film. The hydrogen peroxide needs to be added above 0.15 mol. After 80 minutes of reaction, the oxidative degradation effect of the phenol-containing wastewater can reach 100%, and the total organic carbon removal rate can also increase by 63% with the hydrogen peroxide concentration.

復本發明係陶瓷觸媒膜管進行穩定性測試,本發明係在溫度60℃,pH5之氧化環境下,一次添加過氧化氫濃度為0.05莫耳,探討銅、鐵型陶瓷觸媒膜管氧化降解含酚廢水之酚轉化率、總有機碳(TOC)去除率與陶瓷觸媒膜管金屬溶出率之穩定性試驗。請參閱第二十、二十一圖所示,為含量10%氧化銅之銅型陶瓷觸媒膜管於穩定性試驗對含酚廢水降解效率之影響,穩定性試驗分為第1次、第2次、第3次、第4次、第5次、第6次、第7次,其含酚廢水降解效率分別為99.9%、100%、100%、100%、100%、100%、100%,而總有機碳去除效率則分別為38.6%、38.2%、42.9%、46.3%、50.1%、50.2%、51.1%,另含量10%氧化銅之銅型陶瓷觸媒膜管於氧化反應系統之金屬溶出量分別為1.197毫克/升、1.36毫克/升、1.49毫克/升、1.3毫克/升、1.4毫克/升、1.2毫克/升、0.8毫克/升。 The invention is a ceramic catalyst tube for stability test. The invention is characterized in that the concentration of hydrogen peroxide is 0.05 mol at a temperature of 60 ° C and pH 5, and the oxidation of copper and iron ceramic catalyst tubes is discussed. Degradation of phenol conversion rate of phenol-containing wastewater, total organic carbon (TOC) removal rate and stability of ceramic catalyst film tube metal dissolution rate. Please refer to the twentieth and twenty-first figures for the effect of the stability test on the degradation efficiency of phenol-containing wastewater for the copper-type ceramic catalyst film tube containing 10% copper oxide. The stability test is divided into the first and the first. 2, 3rd, 4th, 5th, 6th, 7th, the degradation efficiency of phenol-containing wastewater was 99.9%, 100%, 100%, 100%, 100%, 100%, 100, respectively. %, and the total organic carbon removal efficiency is 38.6%, 38.2%, 42.9%, 46.3%, 50.1%, 50.2%, 51.1%, and another 10% copper oxide copper-type ceramic catalyst film tube in the oxidation reaction system The metal dissolution amounts were 1.197 mg/L, 1.36 mg/L, 1.49 mg/L, 1.3 mg/L, 1.4 mg/L, 1.2 mg/L, and 0.8 mg/L, respectively.

又請參閱第二十二、二十三圖所示,為含量10%三氧化二鐵之鐵型陶瓷觸媒膜管鐵型陶瓷觸媒膜管於穩定性試驗對含酚廢水降解效率之影響,穩定性試驗分為第1次、第2次、第3次、第4次、第5次、第6次、第7次,其含酚廢水降解效率分別為96.6%、98.8%、100%、99.8%、100%、100%、100%,總有機碳(TOC)去除效率分別為35.6%、35.1%、40.4%、40.5%、42.8%、42.1%、47.3%。 而含量10%三氧化二鐵之鐵型陶瓷觸媒膜管於氧化反應系統之金屬溶出量皆為在0.3毫克/升~0.4毫克/升。 Please also refer to the twenty-second and twenty-third figures, which is the effect of stability test on the degradation efficiency of phenol-containing wastewater in the iron-type ceramic catalyst tube of iron-type ceramic catalyst tube with 10% ferric oxide. The stability test is divided into the first, the second, the third, the fourth, the fifth, the sixth, and the seventh, and the degradation efficiency of the phenol-containing wastewater is 96.6%, 98.8%, and 100%, respectively. 99.8%, 100%, 100%, 100%, total organic carbon (TOC) removal efficiency was 35.6%, 35.1%, 40.4%, 40.5%, 42.8%, 42.1%, 47.3%, respectively. The amount of metal eluted in the oxidation reaction system of the iron-type ceramic catalyst tube containing 10% of ferric oxide is 0.3 mg/liter to 0.4 mg/liter.

故由該陶瓷觸媒膜管之穩定性測試結果可知,重覆進行反應對於破壞觸媒活性並不明顯,而於氧化降解效能上並未完全受到觸媒活性降低而影響,系統最終反應時間,不論銅型、鐵型陶瓷觸媒膜管於含酚廢水轉化率、總有機碳(TOC)去除率皆有不錯之去除效果,因此,在穩定性試驗能測試中,可知本發明之陶瓷觸媒膜管於重覆使用下,仍能持續保持良好氧化活性。 Therefore, from the stability test results of the ceramic catalyst film tube, it is known that the repeated reaction is not obvious for destroying the catalytic activity, and the oxidative degradation efficiency is not completely affected by the decrease of the catalytic activity, and the final reaction time of the system, Regardless of the copper-type and iron-type ceramic catalyst film tubes, the conversion rate of phenol-containing wastewater and the total organic carbon (TOC) removal rate have good removal effects. Therefore, in the stability test, the ceramic catalyst of the present invention can be known. The membrane tube can continue to maintain good oxidation activity under repeated use.

藉此,本發明將可燒結粉體、金屬鹽類及黏結劑相混合燒結成型陶瓷觸媒膜管之製備方法,於製作上不僅極具便利、經濟性,且當對材料組成及燒結溫度,做適當變化後更可簡便達到調控陶瓷觸媒膜管之結構及孔隙特性效果,另對本發明之陶瓷觸媒膜管進行螢光分析、高效能液相層析及總有機碳分析等分析測試,皆可驗證本發明之陶瓷觸媒膜管係具有良好污染物轉化率及總有機碳去除率,幾乎可以完全轉換廢水中之酚類,故於性能上亦確具優良的可靠性,可有效應用於重化工業、鋼鐵業及晶圓與半導體等產業,於產品生產過程中所排放出之含酚類廢水,進行氧化降解其毒性處理,並可將氧化處理完之廢水資源回收再利用,而更進一步提升其環保上之效益性者。 Therefore, the method for preparing the sintered ceramic powder catalyst tube by mixing the sinterable powder, the metal salt and the binder is not only convenient and economical, but also has a material composition and a sintering temperature. After appropriate changes, the structure and pore characteristics of the ceramic catalyst film tube can be easily controlled, and the ceramic catalyst tube of the present invention can be analyzed and tested by fluorescence analysis, high performance liquid chromatography and total organic carbon analysis. It can be verified that the ceramic catalyst film tube of the invention has good pollutant conversion rate and total organic carbon removal rate, and can completely convert the phenols in the wastewater, so the performance is also excellent in reliability and can be effectively applied. In the industries of heavy chemical industry, steel industry, wafer and semiconductor industry, the phenol-containing wastewater discharged from the production process is oxidatively degraded and toxic, and the oxidized wastewater resources can be recycled and reused. Further improve their environmental benefits.

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. Cheng has fully complied with the requirements and requirements of the Patent Law. He has filed an application for an invention patent in accordance with the law, and he is pleased to review it and grant a patent.

Claims (1)

一種陶瓷觸媒膜管製備方法,係設有可燒結粉體,該可燒結粉體係至少包含二氧化鈦、高嶺土及活性氧化鋁其中之一,且該二氧化鈦、高嶺土及活性氧化鋁其含量為30公克的二氧化鈦、15公克的高嶺土及5公克的活性氧化鋁,並於該可燒結粉體中添加有金屬鹽類,該金屬鹽類係為2~10%之氧化銅及2~10%之三氧化二鐵其中之一,再將該可燒結粉體及金屬鹽類均勻攪拌混合,繼添加入黏結劑及孔洞生成劑,該黏結劑係為聚乙烯醇,該孔洞生成劑為聚乙烯二醇,再將該可燒結粉體、金屬鹽類、黏結劑及孔洞生成劑均勻攪拌混練形成坯料,又以擠壓裝置將該坯料擠壓成型為膜管狀,續將擠壓成型之膜管狀坯料陰乾除去表面水分,再將該膜管狀坯料進行高溫燒結,該高溫燒結係採階段升溫至欲成型之溫度1100℃,其一開始升溫速率為1.21℃/分鐘,升溫至400℃時停留30分鐘,再以升溫速率2.78℃/分鐘升溫至900℃時停留1小時,接著以升溫速率3.33℃/分鐘升溫至1100℃時停留1小時,待降至室溫後取出,以成型陶瓷觸媒膜管。 The invention relates to a method for preparing a ceramic catalyst film tube, which is provided with a sinterable powder system, wherein the sinterable powder system comprises at least one of titanium dioxide, kaolin and activated alumina, and the content of the titanium dioxide, kaolin and activated alumina is 30 g. Titanium dioxide, 15 g of kaolin and 5 g of activated alumina, and a metal salt is added to the sinterable powder, the metal salt being 2 to 10% of copper oxide and 2 to 10% of trioxide One of the irons, the sinterable powder and the metal salt are uniformly stirred and mixed, and then added to the binder and the pore generating agent, the binder is polyvinyl alcohol, and the pore generating agent is polyethylene glycol, and then The sinterable powder, the metal salt, the binder and the pore generating agent are uniformly stirred and kneaded to form a blank, and the blank is extruded into a tubular shape by an extrusion device, and the extruded tubular tubular blank is continuously removed to remove the surface. Moisture, the film tubular material is subjected to high-temperature sintering, and the high-temperature sintering system is heated to a temperature of 1100 ° C to be formed, and the initial heating rate is 1.21 ° C / min, and the temperature is raised to 400 ° C to stay 30 The clock is further heated to 900 ° C at a heating rate of 2.78 ° C / min for 1 hour, then heated at a heating rate of 3.33 ° C / min to 1100 ° C for 1 hour, to be taken down to room temperature and then taken out to form a ceramic catalyst film tube.
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CN102666432A (en) * 2009-12-28 2012-09-12 住友化学株式会社 Method for producing aluminum titanate ceramic

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馬軍等人,臭氧多相催化氧化除污染技術研究動態,黑龍江大學自然科學學報,第26卷,第1期,2009年2月 *

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