臺灣博碩士論文加值系統

對苯二甲酸的製程的廢水中含有許多有機汙染物，其中苯甲酸為無法回收再利用之物質。且廢水經處理後仍有低濃度之苯甲酸存在，本研究以150毫升之樣本廢水，使用超音波/過氧化氫處理有機廢水中的苯甲酸，依照不同超音波輸出功率、雙氧水添加量、起始苯甲酸濃度、起始酸鹼值改變等，進行固定時間處理效能的探討。降解實驗過程中苯甲酸濃度使用HPLC進行量測，實驗數據並以一階、擬一階、二階及多步驟動力學分析及求取動力學參數。
經過兩小時的處理結果顯示，單獨超音波處理效果並不理想，移除率最高約17%。而苯甲酸的移除率隨著過氧化氫添加量增加而有明顯增加，但添加過量時，移除率反而下降，初始苯甲酸濃度提高降解率也隨著下降。pH值在酸性情況下，最好的移除率約30%。最佳操作條件為苯甲酸初始濃度50ppm、過氧化氫添加量一倍莫爾比、pH值在酸性下進行處理。此外，由動力學分析結果，得知此一降解處理系統較符合多步驟階動力學模式。

Benzoic acid is one of main organic pollutants in wastewater produced from Terephthalic acid manufacture process since it cannot be recycled into process for reuse. However, there still exist low concentration of benzoic acid after the wastewater treatment process. In this study, 150 ml of benzoic acid wastewater were treated by ultrasonic with hydrogen peroxide. The treatment efficiencies were compared by different operation conditions including ultrasonic output power, hydrogen peroxide usage, initial benzoic acid concentration, initial pH value for two hours of treatment. The concentration of benzoic acid in the degradation experiment was measured by HPLC. The kinetic parameters were determined by first-order, quasi-first-order and second-order kinetic analysis.

The results showed that the performance of ultrasound only is not enough as the removal rate up to about 17%. The removal ratio of benzoic acid increased with the increase of hydrogen peroxide usages, but the removal ratio of benzoic acid decreased with the increase of initial concentration of benzoic acid. In the case of acid conditions, the best removal rate is about 30%. The optimum operating conditions in this study were the initial concentration of benzoic acid was 50ppm, the amount of hydrogen peroxide was doubled molar ratio, and the solution was treated under acidic conditions. In addition, the kinetic analysis results show that this degradation treatment system is more suitable to be described with the multistep dynamic model.

目 錄
致 謝 I
Abstract II
摘要 III
第一章 前言 1
1.1 研究背景 1
1.2 研究目的與範疇 3
第二章 文獻回顧 4
2.1 PTA製程 4
2.2 傳統廢水處理法 12
2.2.1 物理處理法 12
2.2.2 化學處理法 12
2.2.3 生物處理法 12
2.3 高級氧化法 15
2.3.1 光化學催化氧化法 17
2.3.2 濕式催化氧化法 17
2.3.3 超臨界水氧化法 17
2.3.4 Fenton氧化法 18
2.3.5 臭氧類氧化法 19
2.3.6 紫外光/過氧化氫法 19
2.3.7 超音波氧化法 19
2.4 超音波/過氧化氫氧化法之影響因子 26
第三章 實驗 30
3.1 實驗原料與藥品 30
3.2 實驗設備 31
3.3 實驗架構 33
3.4 實驗步驟 33
3.4.1 初步實驗 33
3.4.2 實驗設置 34
第四章 結果與討論 36
4.1 初步實驗結果 37
4.2 苯甲酸降解實驗 40
4.2.1 超音波輸出功率之影響 40
4.2.2 過氧化氫添加量之影響 49
4.2.3 苯甲酸起始濃度之影響 57
4.2.4 反應pH值之影響 65
第五章 結論 73
參考文獻 75






圖目錄
圖1.1.1近年聚酯纖維產量報告圖（台灣區人造纖維製造工業同業公會） 2
圖.2.1.1粗對苯二甲酸製程流程圖 7
圖 2.1.2精對苯二甲酸製程流程圖 8
圖2.1.3 對苯二甲酸製程其反應中間體 9
圖2.1.4對羧基苯甲醛由觸媒催化行加氫反應成對甲基苯甲酸 9
圖2.3.1 芬頓處理法 18
圖2.3.2 超音波頻率圖 20
圖2.3.3液相系統聲化學反應圖 21
圖2.3.4 探針式反應器 23
圖2.3.5水域式反應器 24
圖2.3.6 平板式反應器 25
圖3.2.1實驗設置及HPLC示意圖 32
圖4.1.1苯甲酸檢量線 38
圖4.1.2以超音波、雙氧水、超音波/過氧化氫降解苯甲酸剩餘比與時間關係圖 39
圖4.2.1不同超音波輸出功率之降解苯甲酸濃度與時間關係圖 42
圖4.2.2降解苯甲酸之反應動力學常數k與超音波輸出功率關係圖 43
圖4.2.3不同超音波輸出功率降解苯甲酸之剩餘比與時間關係圖(一階動力學) 44
圖4.2.4不同超音波輸出功率降解苯甲酸之剩餘比與時間關係圖(擬一階動力學) 45
圖4.2.5不同超音波輸出功率降解苯甲酸之剩餘比與時間關係圖(二階動力學) 46
圖4.2.6不同超音波輸出功率降解苯甲酸之剩餘比與時間關係圖(多步驟動力學) 47
圖4.2.7不同過氧化氫添加量之降解苯甲酸濃度與時間關係圖 50
圖4.2.8降解苯甲酸之反應動力學常數k與不同過氧化氫添加量關係圖 51
圖4.2.9不同過氧化氫添加量降解苯甲酸之剩餘比與時間關係圖(一階動力學) 52
圖4.2.10不同過氧化氫添加量降解苯甲酸之剩餘比與時間關係圖(擬一階動力學) 53
圖4.2.11不同過氧化氫添加量降解苯甲酸之剩餘比與時間關係圖(二階動力學) 54
圖4.2.12不同過氧化氫添加量降解苯甲酸之剩餘比與時間關係圖(多步驟動力學) 55
圖4.2.13不同苯甲酸起始濃度(25、50、75、100ppm)之降解苯甲酸濃度與時間關係圖 58
圖4.2.14降解苯甲酸之反應動力學常數k與苯甲酸初始濃度關係圖 59
圖4.2.15不同苯甲酸起始濃度降解苯甲酸之剩餘比與時間關係圖(一階動力學) 60
圖4.2.16不同苯甲酸起始濃度降解苯甲酸之剩餘比與時間關係圖(擬一階動力學) 61
圖4.2.17不同苯甲酸起始濃度降解苯甲酸之剩餘比與時間關係圖(二階動力學) 62
圖4.2.18不同苯甲酸起始濃度降解苯甲酸之剩餘比與時間關係圖(多步驟動力學) 63
圖4.2.19不同pH值之降解苯甲酸濃度與時間關係圖 66
圖4.2.20降解苯甲酸之反應動力學常數k與pH值關係圖 67
圖4.2.21不同pH值降解降解苯甲酸之剩餘比與時間關係圖(一階動力學) 68
圖4.2.22不同pH值降解苯甲酸之剩餘比與時間關係圖(擬一階動力學) 69
圖4.2.23不同pH值降解苯甲酸之剩餘比與時間關係圖(二階動力學) 70
圖4.2.24不同pH值降解苯甲酸之剩餘比與時間關係圖(多步驟動力學) 71



表目錄
表2.1.1 PTA製程中產生的芳香族有機酸之物理之特性 6
表2.1.2 PTA製程廢水組成實例表 10
表 2.1.3 PTA製程廢水組成實例表 11
表2.2.1各種非高級氧化處理法與其優缺點 14
表2.2.2 常見氧化劑的相對氧化能力 16
表3.1.1 實驗藥品與提供廠商 30
表3.2.1實驗設備、型號與提供廠商 31
表4.2.1 反應速率常數k和R2 48
表4.2.2 反應速率常數k1、k2和R2 48
表4.2.3 反應速率常數k和R2 56
表4.2.4 反應速率常數k1、k2和R2 56
表4.2.4反應速率常數k和R2 64
表4.2.5反應速率常數k1、k2和R2 64
表4.2.6反應速率常數k和R2 72
表4.2.7反應速率常數k1、k2和R2 72

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