臺灣博碩士論文加值系統

本研究目的將C5~C9之烷類化合物在鉑觸媒金屬催化下轉換為高價值之含氧油料。目前本實驗室已成它萓璁X成出TS-1（Titanium Silicalite-1）沸石觸媒，並且嘗試以不同的矽來源取代價格較高的TEOS（Tetraethyl orthosilicate），降低商業生產的成本。藉由FT-IR（Fourier Transform Infrared）、XRPD（X-ray Powder Diffraction）、SEM（Scanning Electron Microscopy）、XANES（X-ray Absorption Near Edge Structure）、EXAFS（Extended X-ray Absorption Fine Structure）等特性分析工具，我們可以瞭解TS-1之性質與其結構。
Pt / TS-1觸媒之製備以微濕含浸法與離子交換法，將白金金屬顆粒置放在TS-1上作為催化劑的使用，並利用TEM（Transmission Electron Microscopy）、XANES、EXAFS等分析工具，幫助我們了解白金金屬的顆粒大小及型態。因為含浸法得到的白金金屬顆粒太大(約3nm)，所以我們尋求觸媒製備的改善方法，將白金金屬有效縮小至1nm以下，藉由TEM的觀察，可以確認白金金屬置入TS-1觸媒的微孔道結構中，如此不僅可以抑制反應過程中金屬的聚集，更能使白金在觸媒上能夠發揮選擇性催化之幼纂C
最後，我們實地進行催化測試，利用含浸法得到的Pt / TS-1觸媒在連續式的滴流固定床反應系統，以正辛烷作為液體進料，空氣、氫氣作為氣體進料，WHSV=1、正辛烷/氧氣=1、氫氣/氧氣=3（莫耳比），系統壓力為5及10大氣壓力之操作條件下，以GC-MS（Gas Chromatograph Mass）、GC（Gas Chromatograph）分離並分析產物，結果可以獲得20％以上之轉化率，產品醇及酮類含氧化合物，而醇對酮的選擇率有75％。

The goals of the research are to develop a new process for converting C5-C9 paraffinic compounds to their corresponding alcoholic or ketonic derivatives, valuable oxygen-containing compounds. Catalyst support, TS-1 (Titanium Silicalite-1), has been synthesized successfully by the use different silica sources, e.g. rather expensive TEOS (Tetraethyl orthosilicate) and cheap silica gel. FT-IR (Fourier Transform Infrared), XRPD (X-ray Powder Diffraction), SEM (Scanning Electron Microscopy), XANES (X-ray Absorption Near Edge Structure), and EXAFS (Extend X-ray Absorption Fine Structure) spectroscopy were use to characterize the properties and structure of the synthesized TS-1. Impregnation and ionic exchange method were then used to prepare Pt/TS-1 catalyst. TEM (Transmission Electron Microscopy), XANES, and EXAFS, were used to characterize the Pt/TS1 catalysts. These complementary characterization techniques allow us to explore the genesis of Pt cluster formation and eventually platinum clusters with average particle size less than 1nm were prepared. TEM further confirmed most of the Pt clusters were trapped in the micro-tunnel of TS-1. The prepared catalysts were then tested by partially oxidation reaction of octane. The reactions were carried out at 5 atm and 250℃ with WHSV of 1.0. GC-MS (Gas Chromatograph Mass) and GC (Gas Chromatograph) characterized both the gas and liquid effluents indicated that the conversion is higher than 20% and the selectivity to alcoholic and/or ketonic compounds is about 75%.

中文摘要…………………………….....………………………………Ⅰ
Abstract………………………………………………………….…..…III
目錄………………………………………………………………….…Ⅳ
圖目錄………………………………………………………..…….…VIII
表目錄…………………………………………………….…………..XIII

第一章 研究之背景及目的…………………..….….………………..…1
1.1 序論…………………………………………...……………….….1
1.1.1 研究背景及目的…………………………..……………..1
1.1.2 專利製程說明………………………..…………………..4
1.2 文獻回顧……….……………………………………………..…..6
1.2.1 沸石介紹…………………………………………………6
1.2.2 沸石結構…………………………………………………6
1.2.3 沸石的應用………….……………………..…………….7
1.2.4 MFI沸石簡介…………………………………………….7
1.2.5沸石的形成與成長……………………………………….9
1.2.6 TS-1材料特性簡介……………………………………...13

第二章 觸媒合成、反應性能測試及特性分析…….…..……….……14
2.1 實驗流程……..………………………………….………...….…14
2.2 實驗所用藥品…………..……………………………………….15
2.3觸媒合成與製備………………………………………………….16
2.3.1專利方法製備製備TS-1…………………………..……16
2.3.2 Hi-Sil製備TS-1……………………..…………….…….17
2.3.3微濕含浸法製備Pt / TS-1……………………………….17
2.3.4 離子交換法製備Pt / TS-1……………………..………20
2.4 催化實驗設備…………………….……………..…….............…20
2.5 反應性能測試…………………………….……………...………22
2.6特性分析儀器…………………………………………………….23
2.6.1 程溫還原…………………………………….......……….23
2.6.2 程溫氧化…………………………………......……..……27
2.6.3 一氧化碳化學吸附分析………………………..…...…...28
2.6.4 X光吸收光譜分析…………………...……….…..…….29
2.6.5 粉末X光繞射…………………..………………………..40
2.6.6 快速傳立葉轉換—紅外線光譜分析……………........…42
2.6.7 氣相色層分析儀………………......…………………..…45
2.6.8 氣相層析併質譜測定法…………………..………..…....49
2.6.9 掃描式電子顯微鏡………....….…..……….…….……...50
2.6.10 穿透式電子顯微鏡………………..……………………51
2.6.11 能量散佈分析儀…………………..…....………………53
第三章 結果與討論………………………………………………..…..56
3.1 Pt / TS-1合成與特性分析....…………………………………….56
3.1.1 紅外線光譜分析……………………..……..….….……..56
3.1.2 粉末X-Ray繞射………………………..…….………….57
3.1.3 掃描式電子顯微鏡…………………………..…………..64
3.1.4 穿透式電子顯微鏡與能量散佈分析儀……………..…..69
3.1.5 X光吸收光譜分析（XANES部分）…………………..79
3.1.6 X光吸收光譜分析（EXAFS部分）…………….……..82
3.2 改善Pt / TS-1金屬顆粒大小之研究……………….……….......84
3.2.1 離子交換法………..……………………......……….…...84
3.2.2 改善金屬顆粒大小之研究………………………….….....86
3.2.3 研究顆粒聚集之過程……………………………………..90
3.3 氯氧法（Oxychlorination）……………………….…………….97
3.4 觸媒性能測試………………………………….......…………..100
3.4.1 操作條件與產品之鑑定與定量（反應A）……………100
3.4.2 操作條件與產品之鑑定與定量（反應B）……………111
3.4.3 廢觸媒特性分析與討論…………….……….....………123
第四章 總結與未來展望. ……………………………………..……..127
4.1 總結…………………………………………...……………..…127
4.2 未來展望……………………………………………...…..……129
4.2.1 以其它材料合成TS-1…………………….…………….130
4.2.2 TS-1結構之解析…………………...………………….131
4.2.3 金屬與TS-1交互作用與製備………………...………..131
4.2.4 催化測試……………………......………………....……132
參考文獻………………………………………………………………133
自述…………………………………..………………………………..143




圖目錄
圖1-1 芳香烴工廠製程流程圖………………………………………...2
圖1-2 MFI沸石結構圖……………………………………….…………8
圖1-3 MFI 結構的孔洞示意圖……………..………………….…...…..8
圖1-4 Burkett為等人所提出Si-ZSM-5的成長機制…………………..9
圖1-5 Kirschhock 等人提出MFI precursor成長圖………..……….....11
圖1-6 Nanoslab 的立體結構圖…………………………………....…..12
圖1-7 Kirschhock等人提出MFI的成長機制…………………………12
圖2-1含浸步驟流程圖………………………………………….….…..19
圖2-2 連續式的滴流固定床反應系統…………………………....…..21
圖2-3 TCD示意圖…………………………………………….………..25
圖2-4單成分金屬還原圖譜………………………………….………..26
圖2-5 TPR設備圖………………………………………………....…...27
圖2-6電磁波譜圖………………………………………………....…...30
圖2-7 X光吸收全幅譜圖……………..………….………….…..….....33
圖2-8 X光吸收光譜……………………………………………..….....34
圖2-9在100K下鉑金屬的L-吸收邊緣區域內之X光吸收光譜…...36
圖2.10 背向散射程序之示意圖……………………………….………37
圖2-11 X光吸收光譜實驗配置圖……….………………………….…40
圖2-12 01C光束配置圖……………………………..………….….…..41
圖2-13 感光器mar345之圖示…………………………………….…..41
圖2-14 XRD繞射圖譜…………………………………………..…..…42
圖3-1 FT-IR圖譜（TS-1使用TEOS做為矽來源）………………….58
圖3-2 FT-IR圖譜（TS-1使用Hi-Sil做為矽來源）………………….59
圖3-3 專利中Silicalite的X-Ray繞射圖譜…………….…………....60
圖3-4專利中TS-1的X-Ray繞射圖譜……………………………….60
圖3-5 X-Ray繞射圖譜（TS-1以TEOS做為矽來源）…….…….….62
圖3-6 X-Ray繞射圖譜（TS-1以Hi-Sil做為矽來源）……..…….…63
圖3-7 SEM圖片（TS-1以TEOS做為矽來源，5000倍放大圖）…….65
圖3-8 SEM圖片（TS-1以TEOS做為矽來源，10000倍放大圖）……...66
圖3-9 SEM圖片（TS-1以Hi-Sil做為矽來源，5000倍放大圖）….…..67
圖3-10 SEM圖片（TS-1以Hi-Sil做為矽來源，10000倍放大圖）…...68
圖3-11 TEM圖片（Pt / TS-1以TEOS做為矽來源）……………..…….70
圖3-12 TEM圖片（Pt / TS-1以TEOS做為矽來源）……………..…….71
圖3-13 EDS圖譜（Pt / TS-1，以TEOS做為矽來源）…………………72
圖3-14 TEM圖片（Pt / TS-1以Hi-Sil做為矽來源）………………..…73
圖3-15 EDS圖譜（Pt / TS-1，以Hi-Sil做為矽來源，
對白色膠狀物質做微區分析）………………...……………….74
圖3-16 EDS圖譜（Pt / TS-1，以Hi-Sil做為矽來源，
對TS-1本體做微區分析）…………………..……………....…76
圖3-17 TEM圖片（Pt / TS-1以Hi-Sil做為矽來源，
觀察位置在非晶相二氧化矽上）…………………....………...77
圖3-18 TEM圖片（Pt / TS-1以Hi-Sil做為矽來源，
觀察位置在非晶相二氧化矽上）………………..…..………...78
圖3-19 XANES圖譜（Anatase結構的標準品）……………………..80
圖3-20 XANES圖譜（不同矽來源之比較圖）…………………..…..81
圖3-21 EXAFS圖譜（不同矽來源之比較圖）…………….……...…83
圖3-22 EXAFS圖譜（Pt / TS-1以離子交換法製備）………………..85
圖3-23 TPO圖譜………………………………………………….....…87
圖3-24 TPR圖譜…………………………………………………….….87
圖3-25 EXAFS譜圖（不同製備方法金屬顆粒大小比較圖）……….89
圖3-26 EXAFS譜圖（離子交換法過程中白金有無改變）………….91
圖3-27 XANES圖譜（In-situ實驗流程）……………………...……..93
圖3-28 EXAFS譜圖（改良製備方法前後之比較）…………………....94
圖3-29 TEM圖片（Pt / TS-1以改善方法後製備之樣品）……………..96
圖3-30 XANES圖譜（新鮮觸媒與氯氧法後的觸媒比較圖）………..98
圖3-31 EXAFS圖譜（新鮮觸媒與氯氧法後的觸媒比較圖）……….99
圖3-32 GC / MS液相產物圖譜（反應A，
操作條件為150℃、5大氣壓力）………………………….….102
圖3-33 GC / MS液相產物圖譜（反應A，
操作條件為200℃、5大氣壓力）………………………….….105
圖3-34 GC / MS汽相產物圖譜（反應A，
操作條件為200℃、5大氣壓力）………………………….….107
圖3-35 液相GC圖（反應A，
操作條件為200℃、5大氣壓力）………………………….….108
圖3-36 汽相GC圖（反應A，
操作條件為200℃、5大氣壓力）………………………….….109
圖3-37 GC / MS液相產物圖譜（反應B，
操作條件為200℃、5大氣壓力）………………………….…..112
圖3-38 GC / MS液相產物圖譜（反應B，
操作條件為250℃、5大氣壓力）………………………….…..114
圖3-39 GC / MS液相產物圖譜（反應B，
操作條件為250℃、10大氣壓力）………………….…….…..118
圖3-40 液相GC圖（反應B，
操作條件為250℃、10大氣壓力）…………………..…….….120


圖3-41 汽相GC圖（反應B，
操作條件為200℃、5大氣壓力）………………………….….121
圖3-42 EXAFS譜圖（新鮮觸媒與兩次反應實驗後
的廢觸媒之比較）………………………..……………....……124
圖3-43 TEM圖片（反應A條件之廢觸媒Pt/TS-1）…………….…..125
圖3-44 TEM圖片（反應B條件之廢觸媒Pt/TS-1）…………….…..126



表目錄
表1-1 中華民國九十六年一月一日起施行之汽油成分標準…….…..4
表2-1 實驗所用藥品…………………………..…………………..….15
表2-2 典型氣相層析管柱之性質與特性………………..………...…46
表2-3 GC儀器設定條件………………………....………………...….48
表2-4 GC / MS儀器設定條件…………..……………………………..49
表3-1 Pt / TS-1元素成分分析表（以TEOS做為矽來源）……………..72
表3-2 Pt / TS-1元素成分分析表（以Hi-Sil做為矽來源）…………….74
表3-3 TS-1本體元素成分分析表（以Hi-Sil做為矽來源）..………….76
表3-4 GC / MS液相產物鑑定結果表（反應A，
操作條件為150℃、5大氣壓力）.……………………..…....…103
表3-5 GC / MS液相產物鑑定表（反應A，
操作條件為200℃、5大氣壓力）..………………………….…106
表3-6 GC / MS汽相產物鑑定表（反應A，
操作條件為200℃、5大氣壓力）.……………………..………107
表3-7 不同操作條件下，產物比較表（反應A）.…………….…….110
表3-8 GC / MS液相產物鑑定表（反應B，
操作條件為200℃、5大氣壓力）.……………………….…….113

表3-9 GC / MS液相產物鑑定表（反應B，
操作條件為250℃、5大氣壓力）..……….…………...……….115
表3-10 GC / MS液相產物鑑定表（反應B，
操作條件為250℃、10大氣壓力）..……………………..…….119
表3-11不同操作條件下，產物比較表（反應B）..………...…..…….122
表4-1未來研究項目整理表..………………………………....…………130

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