藉由田口法規劃並以燃燒合成法合成銅基氧化物觸媒

Fabrication of Cu-based oxide catalyst by combustion and Modified via Taguchi method

邱振輝(Jen-HueiChiou)

指導教授 ： 余炳盛 ； 楊顯整

國立臺北科技大學/工程學院/資源工程研究所/碩士(2013年)

https://doi.org/10.6841/NTUT.2013.00689

摘要

隨著時代演進，染整工業扮演著重要的角色，其使用大量的染料、染色助劑、整理劑等，常會殘留於廢水中，除了污染河川外，也會妨礙觀感與陽光進入水中，造成水中植物無法行光合作用，降低水中溶氧量，進而破壞水體中的生態平衡。因此，如何處理高色度的染整廢水將其脫色之方法的研究就成為相當重要的課題。
使用轉換效率高的觸媒用於染整廢水脫色是常用的方法之一，但大部分普遍使用貴金屬觸媒進行脫色，因價格昂貴、不易量產等問題，故近年來許金屬觸媒的研究朝向低成本的過渡金屬，銅基材便是其中一項課題。銅基觸媒具有價格便宜、催化能力佳、穩定性高、可回收再利用等優點，是近年來工業界與學術界廣泛研究的觸媒材料之一。本研究採用田口方法L 36 (23 ×313 )直交表進行規劃，藉由控制G/N比、煆燒溫度、添加13種不同活性的金屬配比，並配合燃燒合成法合成銅基氧化物觸媒。分別探討過氧化氫經觸媒催化後的活性，並以Fenton-like法來增加RB-19染料的色度去除率，搭配理論計算，得到不同金屬摻雜與控制因子影響與最佳脫色配比。
結果顯示在催化過氧化氫部分，經田口方法得知對S/N比與品質特性有影響力的因子為G/N比、煆燒溫度、Al、Cr、Mn、Co、Ce，其中G/N比、Al、Mn、Co、Ce的添加或酌量添加有助於提升催化過氧化氫效果。僅對品質特性有影響力的因子有Zn、La、Sm等元素，其添加有助於增加氧催化能力。僅對S/N比有影響力的因子為Ca、Fe、Sr，其中Ca、Sr的添加可提高S/N比提升整體觸媒品質。對S/N比與品質特性都沒有影響的因子有Ni、Ag。本研究經兩階段最佳化之催化過氧化氫觸媒其反應速率常數達1670、2080、2100(x104)與前人文獻相比，具有相當高的催化過氧化氫能力。
在染料脫色部分，經田口方法得知對S/N比與品質特性有影響力的因子為煆燒溫度、過氧化氫的添加量、Al 、Ni 、Sm等，其中過氧化氫的添加量、Al、Sm的添加或酌量添加有助於提升染料脫色效果。僅對品質特性有影響力的因子有Ca、Cr、Mn、Fe 、Co、Zn、Sr、Ag 、La，其中Ca、Cr、Mn、Co、Sr、Ag 、La等元素酌量添加有助於提升增加脫色效果。僅對S/N比有影響力的因子為G/N比。對S/N比與品質特性都沒有影響的因子為Ce。本研究經兩階段最佳化之染料脫色能力達93%與前人文獻相比，具有優異的染料降解能力。

關鍵字

銅基觸媒 ； 類-芬頓反應 ； 過氧化氫 ； 田口法 ； 燃燒合成法

並列摘要

As time progresses, the dyeing and finishing industry continues to play a vital role. However, the large amounts of dyes, chemical auxiliaries and finishing agents used by the industry often remain in wastewater. Besides polluting rivers to which wastewater is discharged and diminishing the appearances thereof, such remnantscan destroy ecological balances in thesewaters by preventing sunlight from entering the water, thereby crippling photosynthesis in aquatic plants and reducing the amount of oxygen dissolved in water. It has therefore become a critical issue to find out how to decolor high chroma dyeing wastewater.
One common method is using catalysts with high conversion efficiency in dyeing wastewater decolorization. Since precious metal catalysts are the most commonly used although expensive and not easily mass-producible, many have turned to study low cost transition metals as alternatives, among which is copper. Having the merits of low prices, good catalytic ability, high stability and reusability, copper-based catalysts have become one type of catalysts intensively researched by industry and academia in recent years. This study used L 36 (23 ×313) orthogonal arrays in the Taguchi method to control G/N ratios, calcination temperatures, ratio of 13 metalswith different activities to synthesized copper-based oxide catalysts using combustion synthesis. Activities of these catalysts were individually examined following hydrogen peroxide catalysis. Decolorization of RB-19 dyes was enhanced using Fenton-like reactions. Together with theoretical calculations, the effects of different metal mixtures and control factors as well as the best decolorization ratios were established.
The results reveal that the most influential factors for S/N ratios and characteristics of quality during the hydrogen peroxide catalysis were G/N ratios, calcination temperatures, Al, Cr, Mn, Co and Ce according to the Taguchi method. Among these, the addition or discretionary addition of Al, Mn, Co and Ce helped enhance the effect of hydrogen peroxide. Factors affecting only characteristics of quality were Zn, La and Sm. The addition thereof helped increase the catalytic ability of oxygen. Factors affecting only S/N ratios were Ca, Fe and Sr. The addition of Ca and Sr improved S/N ratios and the overall quality of the catalysts. Factors affecting neither S/N ratios nor characteristics of quality were Ni and Ag. Rate constants of the reaction between the catalytic hydrogen peroxide and catalystsduring the two-stage optimization in this study were as high as1670, 2080 and 2100(x104), which show an extraordinary catalytic ability of hydrogen peroxide in comparison with the results in past papers.
Regarding dye decolorization, the most influential factors for S/N ratios and characteristics of quality were calcination temperatures, the added amounts of hydrogen peroxide, Al, Ni and Sm according to the Taguchi method. Among these, the addition of hydrogen peroxide and that or discretionary addition of Al and Sm helped enhance dye decolorization. Factors affecting only characteristics of quality were Ca, Cr, Mn, Fe, Co, Zn, Sr, Agand La. Among these, the discretionary addition of Ca, Cr, Mn, Co, Sr, Ag and La helped enhance decolorization. Factors affecting only S/N ratios were G/N ratios. Ce is the only factor affecting neither S/N ratios nor characteristics of quality. The dye decoloring ability after the two-stage optimization in this study was up to 93%, which denotes excellent dye degradation in comparison with the results in past papers.

並列關鍵字

Copper-based catalysts ； Fenton-like reactions ； hydrogen peroxide ； Taguchi method ； combustion synthesis

參考文獻

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