臺灣博碩士論文加值系統

本研究在兼顧吸附處理成效及較低成本費用之原則為首要考量，基於資源永續回收再利用之理念，結合生物污泥之特性及吸附基本理論，嘗試以乾燥後之廢棄生物污泥予以破碎造粒，並配合適當調理水之浸漬條件以恢復吸附活性，製成生物吸附粒劑用以吸附處理低濃度之銅離子廢水，經吸附之銅離子-生物粒劑以脫附劑洗出銅離子，進而評估生物吸附粒劑循環再利用之可行性。
本研究係以批次及連續流之方式進行生物吸附粒劑之吸脫附試驗，污泥之種類分為P-污泥(添加polymer污泥) 與NP-污泥(未添加polymer污泥)，其中主要探討控制因素包括：吸附時間、銅離子濃度、調理條件等項。由研究結果顯示，於批次試驗時，經由調理之污泥其吸附效率比未調理污泥佳，而風乾污泥與P-污泥對銅離子之吸附效率皆較烘乾污泥與NP-污泥佳；然而，隨著污泥調理時間與其對銅離子吸附時間之增加，Cu-污泥之銅離子脫附效率卻相對的降低，其可能是因為當調理及吸附時間越久其與重金屬之化學結合也越強，而影響脫附效率。另外，TOC之溶出以烘乾污泥較風乾污泥明顯，P-污泥吸附銅離子時之TOC溶出則稍大於NP-污泥，由此可知，P-污泥(風乾)為較佳之生物吸附粒劑，而污泥於調理過程中其TOC已局部溶出，可再進生物處理，故調理污泥進行吸附銅離子時不致造成TOC與銅離子共存之後續處理問題。另外，隨著再利用次數之增加，其銅離子之吸脫附效率於吸脫附次數第4次之後其效率便呈現下降之趨勢，其主要因銅離子吸附累積之現象而減少其吸脫附效果，因此再利用之次數以少於4次為宜。連續流試驗之結果顯示，當銅離子濃度為50ppm，其吸附時間達16.5小時銅離子濃度升至3mg/L(放流水標準)。總之生物吸附粒劑具有去除廢水中重金屬之特性，配合脫附回收處理，可達資源回收再利用之目的。

Biosorbent produced from dried waste biosolid was applied to adsorb copper ions in wastewater. The main point of using biosorbent is its high adsorption efficiency and low cost as well as the reuse of bio-waste. The dried waste biosolid was smashed to granules, and recuperated properly in water to resume the activity of adsorbent. After the adsorption process, desorption agent was used to extract the copper ions from the biosorbent and the possibility of resue it was assessed.
In the study, adsorption and desorption of biosorbent in both batch and continuous experiments were tested, two kinds of the sludge P-Sludge (polymer added) and NP-Sludge (nonpolymer added) were used. Among them we probe into the factor of controlling, such as adsorption time, copper concentration, recuperating the condition,etc. Shown as the result, the adsorption efficiency of recuperated sludge was better than that of not recuperated. The oven-dried sludge and P-Sludge were more effective in absorbing copper than air-dried and NP-Sludge. However, copper adsorption efficiency increased for increaseed adsorption time and recuperative time, but the efficiency of copper desorption decreased, which may due to the longer reaction time for stronger adsorption. Nevertheless the release of organic compounds (TOC, total organic compounds) from the sludge was studied. The amount of organic compounds leached form oven-dried sludge was higher than that of air-dried sludge. Also, the amount of TOC from P-Sludge was higher than from NP-Sludge. Thus it probably means that P-Sludge (air-dried) is the better biosorbent than NP-sludge. In addition, the adsorption and desorption efficiencies for copper appeared to decrease after 4 times, indicating some copper still accumulated in sludge after extraction, and the reuse of the sludge for copper adsorption should be less than four times. The result also shows that when the copper concentration was 50mg/L for continuous flow process, the adsorption time of sludge for copper lasted up to 16.5 hours and the copper concentration in effluent could still meet EPA requirement of 3mg/L, so it can be applied to real field. In a word, from the point of recycle and reuse, it is definitely worth using the biosorbent to remove copper ions from solution and reuse the desorbed copper.

中文摘要 ………………………………………………………… Ⅰ
英文摘要 …………………………………………………………… Ⅱ
致 謝 ……………………………………………………………. Ⅲ
目 錄 ……………………………………………………………. Ⅳ
表目錄 ……………………………………………………………. Ⅶ
圖目錄 ……………………………………………………………. Ⅷ
一、 前言……………………………………………………… 1
1-1 研究動機及目的………………………………………… 1
1-2 研究內容………………………………………………… 2
二、 文獻回顧………………………………………………… 3
2-1 生物污泥之來源及性質………………………………… 3
2-2 重金屬之來源及處理概況……………………………… 4
2-2-1重金屬之來源……………………………………... 4
2-2-2重金屬廢水之處理概況…………………….. 5
2-3 吸附原理及影響因子…………..……………………….. 6
2-3-1吸附機制………………………............................... 6
2-3-2吸附種類…………………………………………... 7
2-3-3吸附模式…………………………………………... 9
2-3-4影響吸附反應之因子……………………………... 11
2-4 微生物應用於重金屬之吸附及影響…………………… 14
2-4-1生物處理系統之微生物及重金屬之影響……….. 14
2-4-2生物處理系統之乾污泥於重金屬之應用……….. 18
2-4-3生物處理系統之EPS於重金屬之應用………….. 23
2-5 小結……………………………………………………… 26
三、 實驗設備、材料與方法…………………………………. 28
3-1 實驗材料………………………………………………… 29
3-1-1生物污泥…………………………………………... 29
3-1-2實驗材料…………………………………………... 30
3-1-3實驗設備…………………………………………... 31
3-2 實驗流程………………………………………………… 31
3-3 實驗方法………………………………………………… 33
3-3-1樣品備置…………………………………………... 33
3-3-2生物污泥之基本特性分析………………………... 33
3-3-3吸脫附效能之評估………………………………... 37
3-3-4連續流試驗……………………………………….. 38
3-3-5污泥之再利用試驗………………………………... 40
四、 結果與討論……………………………………………… 41
4-1 污泥基本特性分析……………………………………… 41
4-1-1 pH值、含水率與密度……………………………. 41
4-1-2重金屬總量分析…………………………………... 42
4-1-3污泥之表面結構FTIR之分析……………………. 42
4-1-4表面積之測定……………………………………... 44
4-1-5表面結構之顯微鏡觀察…………………………... 45
4-1-4小結………………………………………………... 47
4-2 批次試驗………………………………………………… 48
4-2-1未調理污泥之批次試驗…………………………... 48
4-2-2調理時間之吸附效能評估……………………….. 67
4-2-3污泥分離EPS之吸附現象與特性分析………….. 74
4-2-4 pH及TOC之分析……………………………….. 81
4-2-5小結……………………………………………….. 93
4-3 連續流試驗……………………………………………... 94
4-3-1調理污泥對Cu吸附效率之影響………………… 94
4-3-2調理污泥對Cu脫附效率之影響………………… 98
4-3-3小結……………………………………………….. 101
4-4 污泥再利用……………………………………………... 102
4-4-1吸附現象之探討………………………………….. 102
4-4-2表面結構之FTIR及SEM之分析………………. 103
4-4-3污泥再利用之情形……………………………….. 111
4-4-4小結……………………………………………….. 113
五、 結論與建議……………………………………… 114
5-1結論…………………………………………………. 114
5-2建議…………………………………………………. 116
參考文獻 …………………………………………………………... 117
附錄一 …………………………………………………………... 121
附錄二 …………………………………………………………... 128
表2-1 典型生物污泥物化特性……………………................... 4
表2-2 銅之來源及工業用途…………………………………... 5
表2-3 物理吸附與化學吸附之比較表………………………... 9
表2-4 污泥之成分分析表……………………………………... 15
表2-5 污泥於吸附銅前與後之FTIR分析圖譜分析表……… 22
表2-6 各種吸附劑之最大吸附特性與Qm值分析表…………. 25
表2-7 EPS之FTIR分析圖譜分析表…………………………. 27
表4-1 污泥之pH值、含水率及密度分析……………………. 41
表4-2 P-污泥與NP-污泥重金屬含量分析表………………… 42
表4-3 Freundlich與Langmuir之常數比較表………………… 61
表4-4 污泥分離EPS之重量損失表………………………….. 74
表4-5 污泥分離EPS之單位負荷之比較表………………….. 75
圖2-1 氨基酸於酸鹼之不同情行下之官能機構造圖………... 15
圖2-2 污泥於吸附銅前與後之FTIR分析圖譜………………. 22
圖2-3 污泥中EPS之顯微鏡掃描圖(1000x)………………….. 23
圖2-4 EPS之FTIR分析圖譜…………………………………. 26
圖3-1 實驗設計階段圖………………………………………... 29
圖3-2 污水廠之廢水處理流程圖……………………………... 30
圖3-3 實驗程序流程圖………………………………………... 32
圖3-4 前處理流程圖…………………………………………... 33
圖3-5 污泥之基本理化分析流程圖…………………………... 34
圖4-1 P-污泥之表面結構FTIR分析…………………………. 43
圖4-2 NP-污泥之表面結構FTIR分析……………………….. 44
圖4-3 調理時間之表面積分佈情形…………………………... 45
圖4-4 表面結構之顯微鏡觀察影像觀察圖(a)0hr, (b)4hr, (c)8hr,(d)16hr…… 46
圖4-5 吸附時間對吸附效率之影響…………………………... 50
圖4-6 污泥量對銅離子之污泥單位負荷量之影響…………... 51
圖4-7 重金屬濃度對吸附效率之影響………………………... 53
圖4-8 污泥粒徑對銅離子吸附效率之影響…………………... 54
圖4-9 脱附時間對銅離子脫附效率之影響…………………... 55
圖4-10 脱附時間對TOC之溶出情形之影響…………………. 57
圖4-11 吸脫附效率之變化趨勢圖……………………………... 60
圖4-12 等溫吸附曲線圖………………………………………... 61
圖4-13 P-污泥吸附銅離子前後之FTIR分析圖譜……………. 63
圖4-14 NP-污泥吸附銅離子前後之FTIR分析圖譜………….. 63
圖4-15 P-污泥之SEM微化學分析圖(1500X)，(a)P-污泥(烘乾), (b)P-污泥-Cu(烘乾), (c)P-污泥(風乾), (d)P-污泥-Cu(風乾)……………… 65
圖4-16 NP-污泥之SEM微化學分析圖(1500X)，(a)NP-污泥(烘乾), (b)NP-污泥-Cu(烘乾), (c)NP-污泥(風乾), (d)NP-污泥-Cu(風乾)…………… 66
圖4-17 調理時間之吸脫附效率變化趨勢圖…………………... 69
圖4-18 調理時間對吸附效率之變化趨勢……………………... 70
圖4-19 調理污泥吸附單位負荷之分析圖……………………... 72
圖4-20 調理時間對脫附效率之變化趨勢…………………….. 73
圖4-21 分離後殘餘污泥之負荷量分析圖……………………... 77
圖4-22 P-污泥於不同狀態下表面官能基之FTIR分析圖譜…. 78
圖4-23 NP-污泥於不同狀態下表面官能基之FTIR分析圖譜.. 79
圖4-24 P-污泥之EPS吸附銅離子後之FTIR分析圖譜……… 80
圖4-25 NP-污泥之EPS吸附銅離子後之FTIR分析圖譜……. 81
圖4-26 銅離子吸附時其TOC溶出濃度之變化趨勢圖………. 83
圖4-27 銅離子脫附時其 TOC溶出濃度之變化趨勢圖……… 84
圖4-28 調理時間之調理水pH分佈情形……………………… 85
圖4-29 調理時間之調理水TOC溶出情形……………………. 87
圖4-30 調理時間對吸附銅離子時pH之變化趨勢圖………… 88
圖4-31 調理時間對吸附銅離子時TOC溶出分佈情形………. 90
圖4-32 調理時間對脫附銅離子時TOC溶出分佈情形……….. 92
圖4-33 調理污泥與銅離子濃度100ppm之吸附曲線圖……… 95
圖4-34 調理污泥與銅離子濃度200ppm之吸附曲線圖……… 96
圖4-35 不同濃度對剩餘銅離子濃度之影響…………………... 97
圖4-36 滲流量對吸附TOC之影響…………………………… 98
圖4-37 脫附方式對脫附效率之影響…………………………... 99
圖4-38 脫附方式對脫附TOC之影響…………………………. 100
圖4-39 污泥再利用之分佈情形………………………………... 103
圖4-40 利用HNO3脫附劑之FTIR分析圖譜…………………. 104
圖4-41 利用HNO3脫附劑之SEM分析圖譜(6000X)…………. 105
圖4-42 利用HCL脫附劑之FTIR分析圖譜…………………… 106
圖4-43 利用HCL脫附劑之SEM分析圖譜(6000X)…………. 106
圖4-44 利用H2SO4脫附劑之FTIR分析圖譜………………….. 107
圖4-45 利用H2SO4脫附劑之SEM分析圖譜(6000X)………… 108
圖4-46 利用CH3COOH脫附劑之FTIR分析圖譜…………… 109
圖4-47 利用CH3COOH脫附劑之SEM分析圖譜(6000X)…… 109
圖4-48 利用Citrate-Na脫附劑之FTIR分析圖譜…………….. 110
圖4-49 利用Citrate-Na脫附劑之SEM分析圖譜(6000X)……. 111
圖4-50 污泥再利用之吸附脫情形……………………………... 112

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