臺灣博碩士論文加值系統

本論文旨在討論以含氯活性碳為載體所製備的Ni/C-Cl觸媒特性，所使用的含氯活性碳，以鹽酸及次氯酸鈉反應產生氯氣，讓活性碳吸附製成，所製備的觸媒以SEM-EDX、TPD、X-ray及APT滴定等方式鑑定其物性及化性，並以連續流動式微反應器測定其甲醇羰基化活性。

在觸媒的鑑定中發現Ni/C-Cl觸媒比Ni/C觸媒具有更多的鹼性官能基，且能吸附更多的反應物（甲醇和一氧化碳），反應後的Ni/C-Cl亦能吸附更多的甲基碘，這些因素卻使得Ni/C-Cl觸媒的反應活性較Ni/C為高。不過當反應溫度超過270℃時，Ni/C-Cl上的氯和碘會大量流失，使得反應活性不再比Ni/C好，變得跟Ni/C觸媒十分相似。
在活性碳以吸附氯改質時，以不同吸附溫度改質的活性碳製備的觸媒，進行甲醇羰基化反應，其活性並無明顯差異。

The goal of this research is to explore the catalytic properties of a novel Ni/C-Cl catalyst prepared from chlorine containing activated carbon. The carbon is prepared by adsorbing chlorine generated from hydrochloric acid and sodium hypochloride. The properties of the catalyst thus prepared are then characterized by SEM-EDX, TPD, XRD and ATP. The activity of the catalyst in the carbonylation of methanol is measured in a continuous flow micro-reactor.

Comparing to Ni/C catalyst, Ni/C-Cl catalyst has more basic functional groups on its surface, and can adsorbs more reactants (methanol and carbon monoxide). After being on stream for a certain time, Ni/C-Cl catalyst also contains more methyl iodide than Ni/C. These factors make Ni/C-Cl has higher activity than Ni/C. The chlorine in Ni/C-Cl catalyst will disappear at a reaction temperature above 270 oC. The disappearance makes the activity of the Ni/C-Cl catalyst similar to that of Ni/C. Finally, the Ni/C-Cl catalysts prepared from the carbon of varied chlorinating temperature show about the same activity in the carbonylation of methanol.

中文摘要………………………………………………………………..Ⅰ
英文摘要………………………………………………………………..Ⅱ
致謝……………………………………………………………………..Ⅲ
目錄……………………………………………………………………..Ⅳ
圖目錄…………………………………………………………………..Ⅵ
表目錄…………………………………………………………………..Ⅷ
第一章 緒論……………………………..………………………………1
第二章 文獻回顧………………………………………………………..6
2.1 甲醇羰基化反應................................................................................6
2.2 均勻相觸媒........................................................................................9
2.3 非均勻相觸媒……………………………………..………………18
2.4 活性碳…..........................................................................................27
2.4.1 活性碳的製造….......................................................................27
2.4.2 活性碳的表面化學結構……………...………………………29
2.4.3 活性碳的微細結構………………………………..………….32
第三章 實驗............................................................................................33
3.1 實驗氣體、藥品與儀器設備…………………………….………...33
3.1.1 實驗氣體………………………………………...……………33
3.1.2 實驗藥品…………………………………………….………..34
3.1.3 實驗儀器設備………………………………………………...36
3.2 觸媒的製備………………………….……………..……………37
3.3 觸媒的鑑定……….…………………………………..…………39
3.3.1 能量分散光譜儀（EDX）……………………………………...39
3.3.2 X-ray繞射儀（XRD）...……..……………………………….42
3.3.3 酸鹼官能基滴定………………...……..…………….……….44
3.3.4 程式升溫脫附（TPD）………………..……………………...45
3.4 觸媒的反應活性測試......................................................................49
第四章 結果與討論…………………………………………...……….53
4.1 觸媒的鑑定………………………………………….…………….53
4.1.1 能量分散光譜儀（EDX）分析…………..……...……………53
4.1.2 X-ray繞射儀（XRD）分析……….………………………….56
4.1.3 表面積官能基測定…………………………………...………58
4.1.4 程式升溫脫附（TPD）………………………………………...59
4.2甲醇羰基化活性…………………..……………………..………..62
4.2.1 反應溫度的影響…………………………………….………..62
4.2.2 觸媒的穩定性………………………………………………...66
4.2.3 氯吸附溫度的效應…………………………...………………69
4.2.4 反應物甲醇及一氧化碳分壓的影響……...…………………72
第五章 結論............................................................................................78
參考文獻..................................................................................................79
作者簡介………………………………………………………………..85

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