含二氧化鈦之觸媒於乙醇轉化成 1,3-丁二烯之研究

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Title:	含二氧化鈦之觸媒於乙醇轉化成 1,3-丁二烯之研究
Other Titles:	Catalysts Based on TiO2 for The Conversion of Ethanol to 1,3-Butadiene
Authors:	高鈺植 KAO,Yu-Zhi
Contributors:	李國禎 LI,KUO-TSENG 化學工程與材料工程學系
Keywords:	二氧化鈦;乙醇;丁二烯 TiO2;Ethanol;1,3-butadiene
Date:	2019
Issue Date:	2019-12-16T02:20:00Z (UTC)
Abstract:	本研究是以含二氧化鈦之金屬氧化物觸媒為主體催化乙醇轉化成丁二烯之反應，探討添加物與其含量對於二氧化鈦觸媒催化乙醇轉化率、丁二烯產率和選擇率之影響，改變的反應條件包括反應溫度及觸媒之重量，以找出觸媒最佳的反應條件。將 ZrO2 與 TiO2 共沉澱製備不同比例的 TiO2-ZrO2 金屬氧化物觸媒，以找出最佳性能的觸媒，結果以沉澱法製備的 TiO2 觸媒為最佳，且顯著地優於商業化二氧化鈦觸媒。藉由改變反應溫度(在 340℃~400℃之間)、添加不同濃度之促進劑，及使用不同觸媒重量(分別為 0.1g、0.2g、0.4g、0.6g、0.8g)等變因，尋找出最佳觸媒組合及乙醇轉化成丁二烯之最佳條件。反應溫度對乙醇轉化成丁二烯反應相當重要。使用 TiO2 觸媒，在一大氣壓下，最佳反應溫度為 360℃，當連續反應時間為 10 分鐘時，可得到之最高丁二烯產率為 9.68%、選擇率為 23.61%，轉化率為 40.98%。以自製 TiO2 觸媒與商用TiO2 觸媒比較，得知觸媒的酸鹼性質對反應有關鍵性的影響。含浸 0.1wt%的 B2O3 促進劑於 TiO2 上之觸媒(0.1%B2O3/TiO2)，在相同之反應條件溫度，可得到之最佳丁二烯產率為 12.30%、選擇率為 34.12%，轉化率為 36.05%。乙醇轉化成丁二烯反應會產生碳化物質沉積在觸媒表面上，造成觸媒的失活。第三次再生後之觸媒反應較第一次使用新鮮觸媒之反應轉化率降低 11.66%，代表再生觸媒表面仍有未完全燒除的碳。將 0.1%B2O3/TiO2 觸媒與 TiO2 觸媒於不同濃度及溫度下反應，進行動力學分析，乙醇轉化成丁二烯之反應可視為一級反應，其活化能分別為 52.9 kJ/mole和 71.8 kJ/mole。 This study used several TiO2-based catalysts to catalyze the conversion of ethanol to 1,3-butadiene. TiO2-ZrO2 mixed metal oxides with different Ti/Zr molar ratios were prepared by a co-precipitated method, and TiO2 exhibited the best performance. We also found that self-prepared TiO2 exhibited better performance than commercial TiO2 catalyst. The effects of additives (B2O3 and K2O) and their contents on the performance of TiO2 catalyst were investigated in a temperature range of 340℃ - 400℃ and in a catalyst weight range of 0.1g - 0.8g. Ethanol conversion was very sensitive to temperature with the use of self-prepared TiO2, the maximum butadiene yield of 9.68% (with an ethanol conversion of 40.98%) was obtained at 360℃ and 10mins time on stream. With the use of 0.1wt%B2O3/TiO2 catalyst, the maximum butadiene yield of 12.30% (with an ethanol conversion of 36.05%) was obtained under the same reaction conditions. Kinetic studies of 0.1% B2O3/TiO2 and TiO2 catalysts, indicating that ethanol conversion to 1,3-butadiene could be treated as the first order irreversible reaction, with activation energies of 52.9 kJ/mole and 71.8 kJ/mole, respectively. In order to understand the relationship between catalyst physical properties and their catalytic performances, catalysts were characterized with field emission electron microscopy (FE-SEM), energy dispersive spectrometer (EDS), X-ray powder diffraction (XRD), specific surface area and pores analyzer (BET),pyridine absorbed or CO2 absorbed–Fourier transform infrared spectroscopy (Pyridine-IR or CO2-IR), n IV butylamine absorbed-thermal gravimetric analysis (n-butylamine-TGA), inductively coupled plasma with atomic emission spectroscopy (ICP-AES). Self-prepared TiO2 catalyst exhibited larger surface area and more acid-base sites than the commercial TiO2 catalyst. The addition of B2O3 increased acid site amounts, resulted in the enhancement of catalytic performance. EDS analysis results indicated that spent TiO2 catalyst contained 12.91wt% carbon. After the regeneration process, the catalyst still had 4.04wt% carbon, indicating that regeneration process couldn’t burn off the carbon completely, resulting in the decrease of conversion and yield, compared to the fresh catalyst.
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