此研究使用0.1 wt% Pt/Al2O3 與Pt/TiO2-ZrO2觸媒，在bench scale固定床反應器內進行氫化反應，其溫度為200-250 ℃、壓力為450 psi、H2/HC=6。由四氫萘的擬一次反應式求得反應速率常數，來比較氫化活性。結果顯示Pt/TiO2-ZrO2觸媒在含硫及不含硫條件下，均擁有較高的氫化活性。我們改變硫含量，由0 ppm 至50 ppm，發現反應速率常數和硫含量成反比，藉由Langmuir-Hinshelwood 模型，我們解釋現象並進一步求得硫的吸附平衡常數，Pt/TiO2-ZrO2與Pt/Al2O3的平衡常數分別為7×106 和2×107。另外在含硫條件下仍遵守亞倫尼亞 (Arrhenius) 方程式，由含硫及不含硫條件下的外顯活化能 (Apparent Activity Energy)，我們進一步求得硫的吸附熱(Heat of adsorption of sulfur)，Pt/TiO2-ZrO2與Pt/Al2O3的吸附熱分別為-19.4 kJ/gmol和-41.0 kJ/gmol。相對反應速率常數顯示Pt/TiO2-ZrO2觸媒擁有較高的抗硫性，由硫的吸附平衡常數與硫的吸附熱可以得知，吸附於擔載TiO2-ZrO2的白金的硫較容易脫附。可能因為其TiO2-ZrO2擔體的酸性引發白金的缺電子性，以及擔體可產生較多溢流的氫。此外，Pt/TiO2-ZrO2在15 ppm含硫進料進行反應時，產物中含硫量不到1 ppm，顯示其不但擁有高抗硫性還有脫硫的功能。

Hydrogenation of tetralin over Pt/Al2O3 and Pt/TiO2-ZrO2 were executed in a bench scale fixed bed reactor under 160-270 °C and 450 psi in the presence or absence of sulfur compounds in feed. The activity was compared by the rate constant of hydrogenation of tetralin, which was considered to follow a first-order kinetic model. In the range of sulfur content from 0 ppm to 30 ppm, the rate constant (kS) inversely proportion to the sulfur content (CS) was observed. Thus, a method to obtain sulfur adsorption equilibrium (KS) was developed by Langmuir-Hinshelwood model. The sulfur adsorption equilibrium constant of Pt/TiO2-ZrO2 and Pt/Al2O3 were 7×106 and 2×107, respectively. Moreover, the heat of adsorption of sulfur could be obtained from the apparent activity energy in the presence and absence of sulfur. The heat of adsorption of Pt/TiO2-ZrO2 and Pt/Al2O3 were -19.4 and -41.0 kJ/gmol, respectively. The results showed that the sulfur desorbed easier while platinum supported on TiO2-ZrO2. Meanwhile, less than 1 ppm sulfur was detected in the product of hydrotreating a 15 ppm S feedstock over Pt/TiO2-ZrO2. These results suggest that Pt/TiO2-ZrO2 exhibits not only a high sulfur tolerance hydrogenation catalyst but also possesses the desulfurization ability.

目錄
第一章 緒論與文獻回顧 4
1.1芳香烴飽和、抗硫性研究必要性 4
1.2 擬一次反應速率式的成立 8
□ 考慮氫溢流 (Hydrogen spillover) 的氫化反應 9
□ 活化能的計算 10
1.3 觸媒增加氫化活性方法 11
一，高分散度的鉑。 11
二，沸石基材的觸媒，雙分散金屬相的形成增加了氫化活性。 11
三，觸媒的酸性，可以增加氫化能力。 12
1.4 SMSI效應 13
□ SMSI的現象 13
□ 發生SMSI的理由 14
□ 造成SMSI特殊性質的原因 15
□ SMSI對萘氫化反應的影響 15
□ SMSI對抗硫性的影響 15
1.5 貴金屬的抗硫性 17
□ 貴金屬的毒化 17
□ 貴金屬的抗硫性 18
1.6 擔體的性質TIO2-ZRO2 21
□ TiO2-ZrO2的比表面積與酸鹼性質 21
□ TiO2-ZrO2的XRD(X-ray diffraction)性質 22
□ TiO2-ZrO2的氫化性質 23
第二章 藥品儀器與實驗步驟 25
2.1觸媒的製備 25
□ Sol-gel原理： 25
□ 共沉澱法製備TiO2-ZrO2擔體 25
□ 初濕含浸法擔載Pt ( Incipient Wetness Method ) 26
2.2反應條件 27
2.3反應器的架設 28
□ 反應管內觸媒設置 28
□ 反應系統設置 28
2.4 程序升溫還原(TPR)與程序升溫脫附(TPD) 29
2.5 數據分析方法 30
□ 氣相層析分析 30
□ 轉化率的計算 31
第三章 反應條件檢測 32
3.1 平衡轉化率 32
3.2內部質傳 32
3.3外部質傳 33
第四章 共沉澱法合成TIO2-ZRO2的性質 34
4.1 觸媒的性質 34
4.3 孔洞分佈圖(PORE DISTRIBUTION) 35
4.4 觸媒的X光繞射圖形(X-RAY DIFFRACTION PATTERN) 35
4.5 程序升溫還原TPR(TEMPERATURE PROGRAMMED-REDUCTION) 37
第五章 四氫萘的氫化反應動力學探討 40
5.1含10 PPM S進料下，觸媒穩定性 40
5.2 擬一次反應速率式的成立 42
5.3 溫度對抗硫性的影響 44
5.4 不同硫含量對觸媒活性的影響 47
5.5 反應速率常數與硫含量的關係 48
□ 利用Enzyme的模型解釋kS與CS的關係 48
□ 使用Langmuir-Hinshelwood模型去探討kS與CS的關係 49
□ 硫含量與硫阻力 (Sulfur Resistance) 的關係 50
第六章 觸媒氫化活性比較 51
6.1 於不含硫條件下的氫化活性比較 51
6.2 觸媒的抗硫性比較 53
6.3 抗硫性與脫硫性 57
第七章 結 論 59
第八章 未來展望 60
8.1 PT/TIO2-ZRO2觸媒作為HDS觸媒 60
8.2 觸媒修飾方面 60
□ 使用Pd-Pt雙金屬觸媒 60
□ 增進觸媒比表面積、孔洞體積與孔徑 60
□ 調節 SMSI 效應 60

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