臺灣博碩士論文加值系統

本研究於Cu/ZnO/Al2O3觸媒製備過程中導入電漿改質程序，以氫氣、氧氣電漿改質鍛燒後之Cu/ZnO/Al2O3觸媒，並嘗試以電漿取代傳統熱鍛燒步驟。電漿改質與電漿鍛燒之觸媒透過BET、XRD、Cu0 surface area、ICP-AES、TGA、FE-SEM分析了解電漿處理程序前後觸媒物化性質的變化；電漿改質與電漿鍛燒程序的同時利用OES電漿放射光譜觀察電漿中物種組成，推測觸媒於電漿環境下可能的反應機制。觸媒經電漿處理後用於合成氣轉化二甲醚反應(STD reaction)以瞭解各觸媒活性差異。 電漿改質鍛燒後觸媒，BET全比表面積均比熱鍛燒觸媒小些，晶相上則無太大差異，由ICP-AES分析結果發現電漿改質有效去除觸媒殘餘不純物，金屬銅比表面積亦略為提升。觸媒活性提升以O2-CP60觸媒最大，CO轉化率達70 %，DME產率2.3 g-DME/g-cat*h大於Blank-C觸媒的1.08 g-DME/g-cat*h；電漿鍛燒觸媒從ICP-AES分析發現隨電漿鍛燒時間的增加，觸媒不純物有漸少的趨勢，但含量仍高於Blank-C觸媒，XRD圖譜上亦可觀察到仍有前驅物型態結晶，但CuO晶粒有變小、分散性增加的現象。O2-PC240觸媒於STD反應活性略高於Blank-C觸媒，而H2-PC240觸媒則與Blank-C觸媒相當。 透過實驗數據的回歸，本研究建立了Blank-C與O2-CP60觸媒之反應動力學模型，用以預測不同反應條件之出口組成，同時提供產製二甲醚製程最適化之參考。由動力學模型計算目前製程之最佳化參數，反應溫度應增加至310℃左右，反應壓力越高壓越利於DME產率，合成氣最佳進料流量在200 sccm，H2/CO最佳比例約在2.2至2.4之間。

In this work, a novel radio frequency (RF) glow discharge plasma modified Cu/ZnO/Al2O3 catalysts were prepared by conventional coprecipitation method, with the goal to improve its performance on the dimethly ether synthesis from syngas. Not only plasma modified process, the feasibility of using plasma to replace traditional calcination process were also investigated. To further understand the interplay between plasma species and catalyst surface, we used optical emission spectroscopy (OES) as a diagnostic tool to observe the concentration of active species in the plasma. The results show that although the catalysts’ BET surface areas after plasma modification or plasma calcination were lower than the traditional-calcined and non-calcined catalyst, but the copper surface area and metal dispersion of the catalysts increased after plasma modification. By the cross examination between OES diagnostics and ICP/AES analysis, we confirmed that plasma is responsible for the decomposition of carbonates and impurity which contented in the catalyst. The catalytic performances of H2, O2 plasma modified catalysts (after calcination) are better than traditional-calcined catalyst. Moreover, the catalyst activity enhanced after O2 plasma calcination which compared with traditional-calcined catalyst, due to the remarkable decrease of the copper oxide crystalline size according to XRD analysis. A kinetic model were also established for the dimethly ether synthesis from syngas over the catalyst. The kinetic parameters of the model reactions were determined by regression from experimental data. The kinetic model was found to predict well on the product flowrate and reactant conversion of syngas to DME (STD) reaction under different conditions (temperature, pressure, syngas feed ratio, etc.), which is required for future reactor design and optimization of DME synthesizing process.

總目錄
摘要 ........................................................................................................................ I
Abstract ............................................................................................................... II
誌謝 ..................................................................................................................... III
總目錄 ................................................................................................................. IV
表目錄 ................................................................................................................ VII
圖目錄 ................................................................................................................. IX
第一章 前言 ...................................................................................................... 1
1-1 研究源起 .............................................................................................. 1
1-2 研究內容 .............................................................................................. 2
第二章 文獻回顧 .............................................................................................. 3
2-1 二甲醚應用與發展現況 ....................................................................... 3
2-1.1 二甲醚性質與應用 .................................................................... 3
2-1.2 二甲醚發展現況 ........................................................................ 6
2-2 二甲醚合成與觸媒製備 ....................................................................... 8
2-2.1 二甲醚合成反應概述 ................................................................ 8
2-2.2 觸媒開發與反應機制探討 ...................................................... 10
2-3 電漿簡介 .............................................................................................. 13
2-3.1 電漿原理 .................................................................................. 13
2-3.2 低壓電漿 .................................................................................. 16
2-4 電漿改質觸媒研究近況 ..................................................................... 20
第三章 研究方法與儀器原理 ........................................................................ 27
3-1 研究目的 .............................................................................................. 27
3-2 實驗步驟 .............................................................................................. 29
3-2.1 觸媒製備 .................................................................................. 29
3-2.2 電漿改質系統與改質實驗 ...................................................... 30
3-2.3 合成氣轉化二甲醚 .................................................................. 34
3-3 儀器原理 .............................................................................................. 36
3-3.1 比表面積分析儀 ...................................................................... 36
3-3.2 感應耦合電漿原子放射光譜儀 .............................................. 38
3-3.3 熱重分析儀 .............................................................................. 39
3-3.4 X射線繞射儀 ............................................................................ 40
3-3.5 氧化亞氮解離吸附測試 .......................................................... 42
3-3.6 場效發射式掃描電子顯微鏡 .................................................. 43
3-3.7 電漿放射光譜儀 ...................................................................... 45
3-3.8 反應動力學模型建立 .............................................................. 47
第四章 結果與討論 ........................................................................................ 50
4-1 觸媒物性鑑定...................................................................................... 50
4-1.1 BET 觸媒全表面積量測 .......................................................... 50
4-1.2 金屬銅表面積量測 .................................................................. 53
4-1.3 ICP-AES 觸媒元素組成分析 .................................................. 54
4-1.4 XRD 晶相分析 ......................................................................... 57
4-1.5 觸媒熱重分析 .......................................................................... 60
4-1.6 FE-SEM 分析 ........................................................................... 62
4-1.7 OES電漿放射光譜分析 ........................................................... 67
4-2 觸媒活性測試...................................................................................... 70
4-2.1 電漿改質鍛燒後觸媒活性測試 .............................................. 70
4-2.2 電漿鍛燒觸媒 .......................................................................... 78
4-3 合成氣轉化二甲醚之反應動力學模擬 ............................................. 85
4-3.1 合成氣轉化二甲醚實驗結果 .................................................. 85
4-3.2 動力學模型回歸結果 .............................................................. 90
4-3.3 模型預測與二甲醚製程最適化 .............................................. 96
第五章 結論與建議 ...................................................................................... 106
5-1 結論 .................................................................................................... 106
5-2 建議 .................................................................................................... 108
參考文獻 ........................................................................................................... 109
自述 ................................................................................................................... 116

表目錄
表 2- 1 二甲醚與其他燃料之性質比較 ............................................................ 5
表 2- 2 觸媒前驅物分解溫度整理 .................................................................. 12
表 2- 3 電漿改質觸媒文獻整理 ...................................................................... 26
表 3- 1 實驗設備及型號................................................................................... 32
表 3- 2 實驗用氣體與藥品種類、濃度及來源 .............................................. 33
表 3- 3 分析儀器設備規格及型號 .................................................................. 33
表 3- 4 電漿改質／鍛燒觸媒參數 .................................................................. 33
表 3- 5 理論反應級數範圍 .............................................................................. 49
表 3- 6 帄衡常數與溫度關係 .......................................................................... 49
表 4- 1 電漿改質鍛燒後觸媒之比表面積與孔洞體積、大小 ...................... 51
表 4- 2 電漿處理取代鍛燒之觸媒比表面積與孔洞體積、大小 .................. 52
表 4- 3 電漿改質鍛燒後觸媒之金屬銅表面積與分散性 .............................. 53
表 4- 4 不同電漿改質程序之金屬元素組成 .................................................. 55
表 4- 5不同電漿改質程序之金屬元素組成 ................................................... 56
表 4- 6 各溫度下反應之碳帄衡計算結果 ...................................................... 72
表 4- 7 碳帄衡誤差計算結果 .......................................................................... 72
表 4- 8 碳帄衡誤差計算結果 .......................................................................... 79
表 4- 9 Blank-C觸媒於流量200 sccm實驗之元素帄衡計算 ....................... 86
表 4- 10 Blank-C觸媒於流量300 sccm實驗之元素帄衡計算 ..................... 86
表 4- 11 Blank-C觸媒於流量400 sccm實驗之元素帄衡計算...................... 86
表 4- 12 O2-CP60觸媒於流量200 sccm實驗之元素帄衡計算..................... 87
表 4- 13 O2-CP60觸媒於流量300 sccm實驗之元素帄衡計算..................... 87
表 4- 14 O2-CP60觸媒於流量400 sccm實驗之元素帄衡計算..................... 87
表 4- 15 回歸結果-反應常數與活化能 ........................................................... 91
表 4- 16 回歸結果-反應級數 ........................................................................... 91
表 4- 17 不同反應溫度之帄衡轉化率與選擇率 ............................................ 97
表 4- 18 不同壓力之帄衡轉化率與選擇率 .................................................... 97
表 4- 19 不同進料配比(H2/CO)之帄衡轉化率與選擇率 ............................... 97
表 4- 20 Blank-C觸媒於240℃、不同進料比例反應，轉化率與選擇率變化 ................................................................................................................... 105

圖目錄
圖 2- 1 二甲醚應用示意圖 ................................................................................ 4
圖 2- 2 NKK 直接合成二甲醚程序示意圖 ....................................................... 7
圖 2- 3 二甲醚與其他燃料效率比較 ................................................................ 7
圖 2- 4 一步法/兩步法合成二甲醚示意圖 ....................................................... 8
圖 2- 5 CuO/ZnO/Al2O3觸媒結構型態 左：桿狀結構，右：塊狀堆疊 ...... 11
圖 2- 6 SIMS圖譜 左：觸媒還原後，右：還原後通入合成氣吸附 ........... 11
圖 2- 7 CH2於Cu上氫化，遷移至Zn上反應示意圖 ................................... 12
圖 2- 8 電漿反應機制示意圖 .......................................................................... 15
圖 2- 9 直流式電漿中電流與電壓關係圖 ...................................................... 17
圖 2- 10 交流式電漿生成機制示意圖 ............................................................ 18
圖 2- 11 RF 電漿反應器類型 ........................................................................... 19
圖 2- 12 微波電漿反應器示意圖 .................................................................... 19
圖 2- 13 Pd/HZSM-5觸媒活性、穩定性比較................................................. 21
圖 2- 14 TEM影像 左上：NiO/Ta2O5-C，左下：NiO/ZrO2-C .................... 23
圖 2- 15 金屬-擔體介面結構差異示意圖 ....................................................... 23
圖 2- 16 電漿改質觸媒之可能反應機制示意圖 ............................................ 24
圖 2- 17 流體化床電漿反應器 ........................................................................ 25
圖 2- 18 CO程溫脫附 (1) Fe/Cu/Si-C (2) Fe/Cu/Si-CP (3) Fe/Cu/Si-PC[47] 25
圖 3- 1 研究流程圖 ........................................................................................... 28
圖 3- 2 直立式直管電漿反應器示意圖 .......................................................... 31
圖 3- 3 直立式直管電漿反應器實體圖 .......................................................... 32
圖 3- 4 合成氣轉化二甲醚實驗設備圖 .......................................................... 34
圖 3- 5 氣體分子於孔洞表面吸附行為 .......................................................... 37
圖 3- 6 Perkin Elmer Optima 2100 DV ............................................................. 38
圖 3- 7 TA Instruments TGA-Q500 ................................................................... 39
圖 3- 8 晶格繞射示意圖................................................................................... 41
圖 3- 9 Panalytical X’Pert Pro ........................................................................... 41
圖 3- 10 SEM構造示意圖 ................................................................................ 44
圖 3- 11 電漿放射光譜儀示意圖 ..................................................................... 46
圖 4- 1 電漿取代鍛燒之觸媒之XRD圖 ........................................................ 58
圖 4- 2 電漿改質鍛燒後觸媒之XRD圖 ........................................................ 59
圖 4- 3 電漿取代鍛燒觸媒之熱重分析 .......................................................... 61
圖 4- 4 電漿改質鍛燒後觸媒之熱重分析 ...................................................... 61
圖 4- 5 電漿鍛燒觸媒與未鍛燒觸媒、熱處理鍛燒觸媒之SEM圖， ........ 63
圖 4- 6 電漿改質鍛燒後觸媒之SEM圖，放大倍率30 k ............................ 64
圖 4- 7 電漿鍛燒觸媒與未鍛燒觸媒、熱處理鍛燒觸媒之SEM圖， ........ 65
圖 4- 8 電漿改質鍛燒後觸媒之SEM圖，放大倍率80 k ............................ 66
圖 4- 9 純氫氣電漿與氫氣電漿改質觸媒之OES光譜 ................................. 68
圖 4- 10 純氫氣電漿與氫氣電漿鍛燒觸媒之OES光譜 ............................... 68
圖 4- 11 純氧氣電漿與氧氣電漿改質觸媒之OES光譜 ............................... 69
圖 4- 12 純氧氣電漿與氧氣電漿鍛燒觸媒之OES光譜 ............................... 69
圖 4- 13 Blank-C觸媒之反應物轉化率、二甲醚選擇率與反應溫度作圖... 73
圖 4- 14 H2-CP60觸媒之反應物轉化率、二甲醚選擇率與反應溫度作圖 .. 73
圖 4- 15 H2-CP120觸媒之反應物轉化率、二甲醚選擇率與反應溫度作圖 74
圖 4- 16 H2-CP180觸媒之反應物轉化率、二甲醚選擇率與反應溫度作圖 74
圖 4- 17 O2-CP60觸媒之反應物轉化率、二甲醚選擇率與反應溫度作圖 .. 75
圖 4- 18 不同觸媒各溫度下之CO帄均轉化率 ............................................. 75
圖 4- 19 不同觸媒各溫度下之H2帄均轉化率 .............................................. 76
圖 4- 20 不同觸媒各溫度下之二甲醚帄均產率 ............................................ 76
圖 4- 21 各觸媒於STD反應之二甲醚選擇率 ............................................... 77
圖 4- 22 各觸媒於STD反應之甲醇選擇率 ................................................... 77
圖 4- 23 各觸媒於STD反應之二氧化碳選擇率 ........................................... 78
圖 4- 24 Blank-NC觸媒之反應物轉化率與反應溫度作圖 ............................ 80
圖 4- 25 Blank-C觸媒之反應物轉化率與反應溫度作圖 ............................... 80
圖 4- 26 H2-PC240觸媒之反應物轉化率與反應溫度作圖 ............................ 81
圖 4- 27 O2-PC240觸媒之反應物轉化率與反應溫度作圖 ............................ 81
圖 4- 28 不同觸媒各溫度下之CO帄均轉化率 ............................................. 82
圖 4- 29 不同觸媒各溫度下之H2帄均轉化率 .............................................. 82
圖 4- 30 不同觸媒各溫度下之二甲醚帄均產率 ............................................ 83
圖 4- 31 各觸媒於STD反應之二甲醚選擇率 ............................................... 83
圖 4- 32 各觸媒於STD反應之甲醇選擇率 ................................................... 84
圖 4- 33 各觸媒於STD反應之二氧化碳選擇率 ........................................... 84
圖 4- 34 Blank-C觸媒各流量之反應物轉化率反應溫度作圖 ....................... 88
圖 4- 35 O2-CP60觸媒各流量之反應物轉化率與反應溫度作圖 .................. 89
圖 4- 36 Blank-C觸媒之動力學模型與實驗出口莫耳流率比較(續上頁) .... 93
圖 4- 37 O2-CP60觸媒之動力學模型與實驗出口莫耳流率比較(續上頁) ... 95
圖 4- 38 模型計算反應物轉化率與實驗和帄衡轉化率作圖 ........................ 96
圖 4- 39 動力學預測溫度與反應物轉化率變化 ............................................ 98
圖 4- 40 動力學預測反應壓力與DME產率、選擇率之影響 ..................... 99
圖 4- 41 動力學模型模擬Blank-C觸媒不同觸媒重之出口物種流率 ......... 99
圖 4- 42 動力學模型模擬O2-CP60觸媒不同觸媒重之出口物種流率 ...... 100
圖 4- 43 模型計算不同觸媒重與產物選擇性變化 ...................................... 100
圖 4- 44 不同進料流率下CO轉化率變化 ................................................... 102
圖 4- 45 不同進料流率下H2轉化率變化..................................................... 102
圖 4- 46 Blank-C觸媒不同進料流率與DME產率影響 .............................. 103
圖 4- 47 O2-CP60觸媒不同進料流率與DME產率影響 ............................. 103
圖 4- 48 增加H2通入比例對轉化率之影響................................................. 104
圖 4- 49 增加H2通入比例對DME產率與選擇性之影響 ......................... 104

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