臺灣博碩士論文加值系統

壬基苯酚聚乙氧基醇 (NP9EO) 為工業使用最廣泛之非離子型界面活性劑，其存在於環境中經微生物降解成較不易分解之壬基苯酚，壬基酚為持久性污染物且具有環境荷爾蒙之特性。本研究分為觸媒製備及光催化應用兩部分，觸媒製備部分利用不同甘胺酸與硝酸鹽之比例，並調整溶液在pH = 2 、6 及10 合成膠體前驅物，接著利用燃燒法合成觸媒，並使用燃燒合成法進行鐵、錳摻雜氧化銅觸媒之改質。最後將合成的觸媒進行有機污染物 NP9EO 的降解實驗。
G/N = 0.3 且pH = 2 所製備出的材料晶相以CuO為主，G/N和pH的上升會導致晶相變成 Cu2O 及 Cu，G/N = 0.5 及 0.7 會產生較多的金屬Cu，因為甘胺酸與氨水在整個燃燒反應過程中做為還原劑。合成顆粒會隨 G/N 上升而成長，而pH = 6 及 10有較明顯的團聚現象。過渡金屬摻雜後的觸媒，產物以 CuO 的晶相為主，合成的產物多以網狀及多孔的結構存在，利用穿透式顯微鏡可看出此種結構為小於50 nm的顆粒團聚而成。經由 Scherrer equation 計算得知晶格大小介在 10 ~ 25 nm 之間，而比表面積測定上差異並不大，比表面積在較高的過渡金屬摻雜比會有上升的現象，Fe/Cu = 10-2 比表面積上升到 8.6 m2/g，Mn/Cu = 10-2 會上升到 11.8 m2/g。
在光催化實驗裡，光催化實驗參數：NP9EO = 100 mg/L、pH = 6、UV light = 254 nm、light intensity = 2.5 W/m2，測試膠體前驅物合成條件在G/N = 0.3 且 pH = 2 及 10的兩組觸媒，以條件在 pH = 10的催化能力較強，對 NP9EO的分解效率達82.47 %，明顯看出 Cu2O 可以提升整個觸媒催化去除 NP9EO 的效率。在過渡金屬元素摻雜研究裡，發現摻雜後普遍對 NP9EO 降解的效率變差，摻雜後能隙變低導致觸媒氧化還原能力下降。其中過渡金屬與 Cu 摻雜比例為 10-4 時，在雙氧水濃度為 0.1 M 且觸媒劑量 0.3 g/L 下，對 NP9EO 的去除效率較好，摻雜 Fe 的去除率達 74.58 %，摻雜 Mn 的去除率達 82.91 %。而在雙氧水濃度為 0.1 M及觸媒劑量0.1 g/L 下，去除效率較佳的過渡金屬摻雜比為 5×10-4 及 10-2。 TOC降解率比 NP9EO 低，大約介於10 ~ 30 % 左右，主要是因為 NP9EO斷鏈後形成的中間產物或副產物皆為有機碳的來源。

Nonylphenol polyethoxylate (NP9EO) is the most commonly used nonionic surfactant, but the microbial degradation of NP9EO would generate nonylphenol which is a persistent pollutant and classified as environmental hormones. The study was separated into two parts: preparation of photocatalyst and photocatalytic application. The synthesized photocatalyst was generated by combustion method with synthesis gel type precursor prepared by different glycine/nitrate ratio in solution with different pH of 2, 6 and 10, and the combustion synthesis method were also applied for modification of catalyst using iron and manganese doped with copper oxide. Finally, the synthetic catalyst was used for the degradation experiment of organic pollutant NP9EO.
The crystalline phase of material generated from G/N = 0.3 and pH = 2 was mainly CuO, and the CuO can be reduced to Cu2O or Cu with increase of pH or G/N. More Cu2O and Cu were generated since glycine and ammonia were served as a reducing agent. Synthetic particles grew with increase of G/N, and there was an obvious agglomeration with pH 6 and 10. The crystalline phase of products generated from doping the transition metals was mainly CuO, which was observed with TEM. The CuO structure was agglomerated with particles smaller than 50 nm, and were mostly reticulated and porous. The size of crystal lattice calculated by the Scherrer equation was between 10 ~ 25 nm. When Fe/Cu=10-2, the specific surface area increased to 8.6 m2/g and increased to 11.8 m2/g when Mn/Cu=10-2.
The experimental condition of photocatalytic was set as NP9EO = 100 mg/L, pH = 6, UV light = 254 nm and light intensity = 2.5 W/m2 with two catalysts of G/N = 0.3 and pH 2 and 10 respectively. The results show, the removal was higher with pH = 10, and the decomposition efficiency of NP9EO was 82.47 %. Apparently, Cu2O can improve the NP9EO removal efficiency more than CuO. In experiments of doping the transition metal elements, the efficiency of NP9EO degradation decrease after doping, and the lower band gap resulted in lower ability in oxide reduction of catalyst. While the ratio of transition metal doped with Cu was 10-4 with concentration of 0.1 M hydrogen peroxide and catalyst dosage 0.3 g/L, the removal efficiency for NP9EO was much better, the removal rates for iron and manganese doped catalysts were 74.58 % and 82.91 %, respectively. The optimized transition metal doped ratios for removal efficiency for iron and manganese were 5×10-4 and 10-2 with H2O2 of 0.1 M and catalyst dosage of 0.1 g/L. TOC removal efficiency (between 10 ~ 30 %) was lower than NP9EO due to by-products from decomposition of NP9EO still are the source of organic carbon.

摘 要 i
ABSTRACT iii
誌 謝 v
目 錄 vi
圖目錄 ix
表目錄 xii
第一章 緒論 1
1.1 研究緣起 1
1.2 研究目的 2
1.3 研究內容與流程 2
第二章 文獻回顧 4
2.1 壬基苯酚聚乙氧基醇 (NPnEO) 4
2.1.1壬基苯酚聚乙氧基醇之特性與應用 4
2.1.2 壬基苯酚聚乙氧基醇之危害性 7
2.1.3 壬基苯酚聚乙氧基醇相關處理技術 8
2.1.3.1 生物處理法 9
2.1.3.2 氯化消毒法 9
2.1.3.3 超音波照射法 10
2.1.3.4 O3氧化法 10
2.1.3.5 TiO2/UV光觸媒法 11
2.2 合成方法介紹 12
2.2.1 粉體合成之相關技術 12
2.2.2 甘胺酸硝酸鹽合成法 (glycine nitrate process, GNP) 15
2.2.2.1 燃氧比對合成產物之影響 15
2.2.2.2 前驅物pH值對合成反應之影響 17
2.3 光觸媒之應用與技術 19
2.3.1 光觸媒基本理論 19
2.3.2 氧化銅性質與結構 21
第三章 研究內容與方法 24
3.1 研究內容 24
3.1.1 研究概要 24
3.1.2 實驗流程 24
3.1.3 實驗加藥量 28
3.2 實驗材料與設備 29
3.2.1 實驗設備 29
3.2.2 實驗藥品 30
3.3 實驗分析與方法 32
3.3.1 壬基苯酚聚乙氧基醇（NP9EO）分析法 32
3.3.2 總有機碳（TOC）分析法 33
3.3.3 過氧化氫（H2O2）分析法 33
3.4 表面分析儀器與原理 34
3.4.1 掃描式電子顯微鏡（SEM）分析原理 34
3.4.2 穿透式電子顯微鏡（TEM）分析原理 34
3.4.3 比表面積測定（BET）分析原理 35
3.4.4 X-ray 繞射法分析原理 37
3.4.5 化學分析影像能譜儀（ESCA）分析原理 38
第四章 結果與討論 40
4.1 不同 pH 值膠體前驅物之熱重分析 40
4.2 調整不同前驅物 pH 合成觸媒之表面特性分析 44
4.2.1 XRD 分析 44
4.2.2 SEM 及 TEM 圖譜 47
4.3 鐵、錳摻雜氧化銅合成觸媒之表面特性分析 49
4.3.1 XRD 分析 49
4.3.2 SEM 及 TEM 圖譜 50
4.3.3 EDS 及 ESCA 分析 54
4.3.4 比表面積及 XRD 晶格大小計算 56
4.3.5 UV/Vis 能隙變化的評估 56
4.4 合成觸媒對 NP9EO 進行光降解實驗 59
4.4.1 雙氧水照射 UV 降解 NP9EO 之空白實驗 59
4.4.2 未改質氧化銅觸媒降解 NP9EO 之空白實驗 61
4.4.3 不同 pH 值之膠體前驅物合成觸媒之光催化實驗 62
4.4.4 過渡金屬元素改質觸媒光催化測試 64
4.4.5 TOC 降解率之探討 70
第五章 結論與建議 71
5.1 結論 71
5.2 建議 73
參考文獻 74
附件 82

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