臺灣博碩士論文加值系統

利用小型高壓固定床反應系統，進行奈在鉑擔體觸媒上的氫化反應研究。實驗結果顯示：觸媒的催化活性與擔體種類及還原前處理程序有著密切關係。在503 K-543K的反應溫度範圍內，氫化反應級數與擔體種類無關，而為奈的一次反應。比較各鉑擔體觸媒的反應速率常數，以低溫還原的Pt/TiO2-ZrO2觸媒的氫化活性最高。各鉑擔體觸媒經高溫還原處理後，除Pt/TiO2-ZrO2 (1:1)外，觸媒的氫化學吸附均比低溫還原處理者低，其原因為ZrO2具有穩定效果，可阻止TiOx遷移至鉑表面。然而，Pt/TiO2-ZrO2 (1:1)觸媒的氫化學吸附變化量幾乎不受還原溫度的影響，但其氫化活性卻也明顯下降。顯示Pt/TiO2-ZrO2 (1:1)觸媒於高溫還原處理後，仍會發生SMSI狀態，只是其造成SMSI狀態的原因不同於Pt/TiO2觸媒-幾何效應，而是鉑金屬與擔體間的電子干擾所致。
本研究以貴重金屬鉑承載在TiO2和TiO2-ZrO2上，做為苯／甲苯的氫化反應觸媒，希望藉由SMSI效應來修飾觸媒活性，尋求最適當的苯／甲苯選擇性氫化反應條件。在本實驗的反應條件下，苯／甲苯的氫化為零級反應，其中苯／甲苯乃吸附在擔體上，而氫氣則吸附在鉑金屬上，兩者於擔體和金屬的交界面上進行反應。以Pt/TiO2-ZrO2進行選擇性氫化反應，其最適當的還原溫度為623 K；Pt/TiO2則為523 K。適度的SMSI效應可將TiO2還原並遷移至鉑表面上，雖會降低氫氣在鉑表面的吸附量，但亦可增加擔體和金屬界面的反應活性點，所以仍可維持不錯的氫化活性。SMSI效應對苯／甲苯吸附力的影響程度乃苯大於甲苯，因此造成二者氫化反應的表觀活化能差距變大，達到選擇性氫化的效果。實驗結果亦發現擔體的酸鹼性對選擇性氫化也有影響，酸鹼共軛的TiO2-ZrO2擔體較弱鹼性的TiO2擔體具有更高的活性和選擇性，是一較適當的選擇性氫化觸媒。

Vapor-phase naphthalene hydrogenation over various supported Pt catalysts was studied in a continuous fixed-bed micro-reactor. Experimental results indicated that the catalytic activity of the catalyst strongly depended on the nature of the support and the pre-reduction temperature. Reaction order was independent of the supports as the reaction was pseudo-first-order with respect to naphthalene in the temperature range studied. By comparing the apparent rate constants over various supported Pt catalysts, Pt supported on TiO2-ZrO2(1/1) reduced at a low temperature, showed the highest activity.For higher pre-reduction temperatures, Pt/TiO2-ZrO2(1:1) exhibited the least suppression of H2 uptake, due to a stabilization effect exerted by ZrO2, which prevents the migration of TiOx moieties and the blockage of the Pt surface. However, the apparent depression of the hydrogenation activity of high temperature reduced Pt/TiO2-ZrO2(1:1) was significantly greater than the suppression of its hydrogen uptake. Furthermore, the decreasing value of the hydrogenation activity relative to the hydrogen uptake, demonstrates electron perturbation between the support and the Pt metal.

封面
目錄
謝誌
中文摘要
英文摘要
目錄
表目錄
圖目錄
第一章 緒論
1.1 前言
1.2 芳香烴氫化反應的重要性與製程
1.3 氫化觸媒
1.4 強金屬擔體作用力(SMSMI)
1.5 研究動機與目地
1.6 參考文獻
第二章 觸媒與實驗設備
2.1 觸媒的製備
2.1.1 TiO2-ZrO2
2.1.2 金屬擔體觸媒
2.2觸媒的特性分析
2.2.1 X-射線繞射分析
2.2.2 表面積測定
2.2.3 金屬氧化物之酸鹼性測定
2.2.4 氫氣化學吸附
2.2.5 程溫還原
2.3觸媒活性測試
2.4參考文獻
第三章 不同擔體鉑觸媒之性質
3.1 前言
3.2 TiO2和TiO2-ZrO2之性質
3.3 程溫還原在不同擔體鉑觸媒的研究
3.4 還原溫度在不同擔體鉑觸媒氫之吸附之影響
3.5 結論
3.6 參考文獻
第四章 SMSI 效應對?在鉑擔體觸媒上氫化反應特性之影響
4.1 前言
4.2 ?的氫化反應動力學
4.3 不同擔體所製鉑擔體觸媒氫化之比較
4.4 ZrO2含量對鉑擔體觸媒效應之影響
4.5 結論
4.6 參考文獻
第五章 利用SMSI效應修飾鉑擔體觸媒進行選擇性氫化反應之探討
5.1 前言
5.2 SMSI效應對雙環芳香烴氫化程度之影響
5.3 SMSI效應對苯/甲苯氫化能力之比較
5.4 結論
5.5 參考文獻
第六章 未來展望
附錄

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