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DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 鄭淑芬(Soofin Cheng) | |
dc.contributor.author | Ku-Hsiang Sung | en |
dc.contributor.author | 宋古翔 | zh_TW |
dc.date.accessioned | 2021-06-16T10:19:52Z | - |
dc.date.available | 2015-08-20 | |
dc.date.copyright | 2013-08-20 | |
dc.date.issued | 2013 | |
dc.date.submitted | 2013-08-16 | |
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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/60500 | - |
dc.description.abstract | 生質柴油的製備是以動植物性油脂或回收食用油為原料,與短碳鏈醇 (一般是甲醇) 在觸媒的催化下進行轉酯化反應所得到的單鏈酯類。雖然生質柴油被視為極具發展潛力的替代性能源且各國生質柴油的生產力也逐年增加,但近年來生質柴油產量的增加速率並不如預期,其原因可能是無法有效降低生質柴油的生產成本。由於轉酯化反應大約會產生10 wt% 的甘油,因此若可以利用甘油生產其他具有經濟價值的化學品便可降低生質柴油的生產成本。在以甘油為起始物的眾多反應中以甘油氣相脫水生成丙烯醛最具有經濟價值。
鎢鋯氧化物在甘油脫水生成丙烯醛反應中具有很高的活性,但是會因反應中產生的積碳而快速失活,因此本研究希望藉由摻混氧化铌來減緩觸媒的失活現象。根據氨氣程溫脫附技術的量測結果可知摻混氧化铌的鎢鋯氧化物觸媒屬於中弱酸的酸性。另外,根據二氧化碳程溫脫附技術的量測結果可知摻混氧化铌可以有效地降低觸媒表面的鹼含量,推測可能是因為氧化铌覆蓋二氧化鋯載體上的鹼性位子,而減緩觸媒的失活現象。實驗結果以氧化铌的重量比為氧化鎢加上氧化鋯重量的3% 並在450oC下煆燒的觸媒 (3–NbWOx/ZrO2–450) 具有最佳的催化活性表現。在反應第二十四小時甘油轉化率為81%,丙烯醛選擇率可以維持在70% 左右,且3–NbWOx/ZrO2–450觸媒可以藉由煆燒有效地恢復觸媒活性。 | zh_TW |
dc.description.abstract | Biodiesels are fatty acid alkyl esters synthesized by transesterification of triglycerides with excess amounts of short chain alcohols, such as methanol, ethanol and propanol. The increasing production of biodiesels has resulted in over production of glycerol. The cost of biodiesels will be lowered down if glycerol can be used as a feedstock to produce high valued chemicals. Among different processes, the gas-phase dehydration of glycerol to form acrolein is considered to have great economical value.
Tungstated zirconia has been found to be efficient catalysts for dehydration of glycerol to form acrolein. However, severe catalyst deactivation over tungstated zirconia was observed due to coke deposition. The aim of this study is to modify the WO3/ZrO2 catalysts by doping small amounts of Nb to decrease the catalytic decay. The acidic strengths of the catalysts measured by NH3-TPD were in the range of weak to moderate. The results of CO2-TPD measurements indicated the doping WO3/ZrO2 with small amounts of Nb can reduce the basic amount by coverd the basic sites of ZrO2 and further increase the stability. The optimal glycerol conversion of 81% and acrolein selectivity of 70% were obtained after 24 h time-on-stream over NbWOx/ZrO2 catalyst with Nb2O5/(WO3 + ZrO2) weight ratios of 3%. The spent catalysts could be easily regenerate by calcination and the catalytic activities were well retained. | en |
dc.description.provenance | Made available in DSpace on 2021-06-16T10:19:52Z (GMT). No. of bitstreams: 1 ntu-102-R00223108-1.pdf: 2207264 bytes, checksum: e864c87885fe53bc9b5c22d7f4cb0740 (MD5) Previous issue date: 2013 | en |
dc.description.tableofcontents | 目錄
謝誌 I 中文摘要 II Abstract III 目錄 IV 表目錄 VI 圖目錄 VIII 第一章 緒論 1 1–1 研究背景 1 1–2 甘油脫水觸媒、反應機制及產物分布 5 1–2–1 雜多酸 (heteropoly acids) 12 1–2–2 沸石 (zeolite) 16 1–2–3 混和金屬氧化物 (Mixed metal oxide) 20 1–3 鎢鋯氧化物的研究與發展 25 1–4 研究目標 28 第二章 實驗部分 29 2–1 化學藥品 29 2–2 觸媒的製備 31 2–2–1 鎢鋯氧化物製備 31 2–2–2 鎢鋯金屬氧化物摻混氧化铌觸媒製備 31 2–3 觸媒材料的鑑定 32 2–4 催化反應 40 2–5 產物鑑定 42 第三章 觸媒的鑑定 44 3–1 鎢鋯氧化物觸媒 44 3–1–1 鎢鋯氧化物觸媒之物理性質鑑定 44 3–1–2 鎢鋯氧化物觸媒之酸鹼性測量 50 3–2 鎢鋯氧化物摻混氧化铌觸媒 53 3–2–1鎢鋯氧化物摻混氧化铌觸媒之物理性質鑑定 53 3–2–2鎢鋯氧化物摻混氧化铌觸媒之酸鹼性測量 56 第四章 催化反應 61 4–1 鎢鋯氧化物觸媒之催化活性表現 61 4–2 鎢鋯氧化物摻混氧化铌觸媒之催化活性表現 67 4–3 不同觸媒量之鎢鋯氧化物與鎢鋯氧化物摻混氧化铌觸媒之催化活性表現 72 4–4 鎢鋯氧化物摻混氧化铌觸媒之重複使用 75 第五章 結論 78 第六章 參考文獻 79 表目錄 Table 1–1 The price of products derived from glycerol. 4 Table 1–2 Catalytic performance of solid acid–base catalysts for the gas–phase dehydration of glycerol at 310oC and glycerol GHSV = 80 h-1[23]. 8 Table 1–3 Reaction of glycerol over several solid acid catalysts at 325oC. Data on conversion and selectivity are mean values in the initial reaction period for 5 h[27]. 13 Table 1–4 Reaction of glycerol over silica–supported silicotungstic acid catalysts[27]. 13 Table 1–5 Catalyst performance in dehydration of glycerol over HPWs[28]. 15 Table 1–6 Physicochemical properties of ZSM–5 catalysts[34]. 17 Table 1–7 Distribution of product for the vapor–phase dehydration of glycerol over the rare earth pyrophosphates catalysts[36]. 20 Table 1–8 Product distribution over the investigated binary metal oxide catalysts at 315oC and TOS = 9–10 h[37]. 21 Table 1–9 Catalytic performances of the ZrNbO catalysts. Reaction temperature 300oC, glycerol aqueous solution (20 wt%) flow rate 3.8 g h-1, inert gas flow rate 75 mL min-1[39]. 23 Table 1–10 BET surface area and chemical composition of oxidized WZ samples prepared by impregnation and PVA–assisted coprecipitation[49]. 27 Table 1–11 Effect of calcination on the pore system of WO3/ZrO2 catalysts[50]. 28 Table 1–12 Dependence of glycerol conversion and product selectivity observed for the dehydration of 20 wt% aqueous glycerol solution at 280oC of WO3/ZrO2 catalysts with different WO3 amounts[50]. 28 Table 2–1 Temperature program for product analysis. 42 Table 3–1 Textural properties of WO3/ZrO2 catalysts calcined at different temperatures. 46 Table 3–2 Results of NH3–TPD and CO2–TPD measurements on WO3/ZrO2 catalysts calcined at different temperatures. 52 Table 3–3 Textural properties of WO3/ZrO2–450 and NbWOx/ZrO2 catalysts. 54 Table 3–4 Results of NH3–TPD and CO2–TPD measurements on WO3/ZrO2–450 and NbWOx/ZrO2 catalysts. 57 Table 4–1 Product distribution of WO3/ZrO2 catalysts at different temperatures. 63 Table 4–2 Analysis of NH3–TPD measurement on WO3/ZrO2 catalysts calcined at different temperatures. 65 Table 4–3 Product distribution of the WO3/ZrO2–450 and NbWOx/ZrO2–450 catalysts with different Nb2O5 weight ratios to (WO3+ZrO2). 70 Table 4–4 Results of NH3–TPD measurements on WO3/ZrO2 and NbWOx/ZrO2 catalysts with specific surface area. 71 Table 4–5 Product distribution of 3–NbWOx/ZrO2–450 catalyst after regeneration. 77 圖目錄 Scheme 1–1 The transesterification of vegetable oils to yield the so–called biodiesels[1]. 1 Fig. 1–1 Distribution of the glycerol consumption by sector/application[3]. 2 Scheme 1–2 Selected glycerol valorisation target molecules[3]. 3 Scheme 1–3 Catalytically–assisted selective oxidation of propene. 4 Scheme 1–4 Dehydration of glycerol to acrolein. 5 Scheme 1–5 Possible reaction pathways for acetol formation on basic sites of Na–doped catalysts[24]. 7 Fig. 1–2 Effect of the catalyst calcination temperature on (A) glycerol conversion and (B) acrolein selectivity at ( ● ) TOS = 1–2 h and ( ▲ ) TOS = 9–10 h[26]. 9 Scheme 1–6 Glycerol dehydration mechanism proposed by Tsukuda et al.[27] and further completed by Chai et al.[23]. 10 Scheme 1–7 Reaction mechanism over acid catalysts, as proposed by Alhanash et al.[28] 11 Fig. 1–3 The Keggin structure for H3PW12O40. 12 Fig. 1–4 Time courses of (A) glycerol conversion and (B) acrolein selectivity over ZrO2–AN–650 ( ♦ ), 5PWZ–AN–650 ( ● ), 15PWZ–AN–650 ( ▲ ), 30PWZ–AN–650 ( □ ) and PW–650 catalysts ( ◊ ). Reaction conditions: catalyst volumn 0.63 ml, 36.2 wt% glycerol solution at the feed rate of 30 mL/min in the N2 flow, GHSV = 400 h-1[30]. 14 Fig. 1–5 The framework structure of zeolites. 16 Fig. 1–6 FT–IR spectra of ZSM–5 after pyridine adsorption[34]. 17 Fig. 1–7 Glycerol conversion and acrolein yield over HZSM–5 with time–on–stream. The feed composition: 8.3 mol% C3H8O3,76.3 mol% H2O in He, T = 315oC, the molar flow rate of glycerol = 23.4 mmol/h. The weight of the catalyst = 0.30 g[34]. 18 Fig. 1–8 Glycerol conversion and acrolein selectivity over time for nanocrystalline HZSM–5 (90) catalyst at 320oC at different GHSV: (a) using 35 wt% glycerol aqueous solution as feed, and (b) using 50 wt% glycerol aqueous solution as feed[35]. 19 Fig. 1–9 Time course of: (a) glycerol conversion, and (b) acrolein selectivity over HZSM–5 catalyst with different Si/Al molar ratios[35]. 19 Fig. 1–10 Deactivation curve of a 13.9 wt% WO3/TiO2 catalyst in terms of conversion under the presence and absence of oxygen[38]. 22 Fig. 1–11 Evolution of glycerol conversion and selectivity to acrolein as a function of time on stream at 300oC for the ZrNbO–12 catalyst[39]. 23 Fig. 1–12 Schematic drawing of the molecular structures present on supported niobia catalysts[40]. 24 Fig. 1–13 Evolution of octahedral WOx species on ZrO2 surfaces with increasing WOx surface density[48]. 26 Fig. 2–1 Powder X–ray diffraction. 32 Fig. 2–2 Temperature program for NH3–TPD measurement. 37 Fig. 2–3 The equipment for pyridine adsorption. 38 Fig. 2–4 Temperature program for pyridine–IR measurement. 39 Fig. 2–5 Effect of reaction temperature on glycerol conversion and acrolein selectivity using 19 wt% WO3/ZrO2 catalyst[50]. 40 Fig. 2–6 Catalytic reaction system. 41 Fig. 2–7 The product distribution analyzed by GC. 43 Fig. 3–1 XRD patterns for WO3/ZrO2 catalysts calcined at different temperatures: (a) WO3/ZrO2–400 (b) WO3/ZrO2–450 (c) WO3/ZrO2–500 (d) WO3/ZrO2–600 (e) WO3/ZrO2–700 (f) WO3/ZrO2–800. 45 Fig. 3–2 Nitrogen adsorption–desorption isotherms of WO3/ZrO2 catalysts calcined at different temperatures: (a) WO3/ZrO2–400 (b) WO3/ZrO2–450 (c) WO3/ZrO2–500 (d) WO3/ZrO2–600 (e) WO3/ZrO2–700 (f) WO3/ZrO2–800. 46 Fig. 3–3 IR spectra of WO3/ZrO2 catalysts calcined at different temperatures: (a) WO3/ZrO2–400 (b) WO3/ZrO2–450 (c) WO3/ZrO2–500 (d) WO3/ZrO2–600 (e) WO3/ZrO2–700 (f) WO3/ZrO2–800. 47 Fig. 3–4 IR spectra of WO3/ZrO2 catalysts calcined at different temperatures and ZrO2 : (a) WO3/ZrO2–400 (b) WO3/ZrO2–450 (c) WO3/ZrO2–500 (d) WO3/ZrO2–600 (e) WO3/ZrO2–700 (f) WO3/ZrO2–800 (g) ZrO2. 48 Fig. 3–5 Raman spectra of WO3/ZrO2 catalysts calcined at different temperatures、ZrO2 and m–WO3 : (a) ZrO2 (b) WO3/ZrO2–400 (c) WO3/ZrO2–450 (d) WO3/ZrO2–500 (e) WO3/ZrO2–600 (f) WO3/ZrO2–700 (g) WO3/ZrO2–800 (h) m–WO3. 49 Fig. 3–6 NH3–TPD thermograms of ammonia on WO3/ZrO2 catalysts calcined at different temperatures: (a) WO3/ZrO2–400 (b) WO3/ZrO2–450 (c) WO3/ZrO2–500 (d) WO3/ZrO2–600 (e) WO3/ZrO2–700 (f) WO3/ZrO2–800. 51 Fig. 3–7 CO2–TPD thermograms of carbon dioxide on WO3/ZrO2 catalysts calcined at different temperatures: (a) WO3/ZrO2–400 (b) WO3/ZrO2–450 (c) WO3/ZrO2–500 (d) WO3/ZrO2–600 (e) WO3/ZrO2–700 (f) WO3/ZrO2–800. 51 Fig. 3–8 XRD patterns for WO3/ZrO2–450 and NbWOx/ZrO2 catalysts: (a) WO3/ZrO2–450 (b) 1–NbWOx/ZrO2–450 (c) 3–NbWOx/ZrO2–450 (d) 5–NbWOx/ZrO2–450. 53 Fig. 3–9 Nitrogen adsorption–desorption isotherms of WO3/ZrO2–450 and NbWOx/ZrO2 catalysts: (a) WO3/ZrO2–450 (b) 1–NbWOx/ZrO2–450 (c) 3–NbWOx/ZrO2–450 (d) 5–NbWOx/ZrO2–450. 54 Fig. 3–10 Raman spectra of WO3/ZrO2 and NbWOx/ZrO2 catalysts: (a) WO3/ZrO2–450 (b) 1–NbWOx/ZrO2–450 (c) 3–NbWOx/ZrO2–450 (d) 5–NbWOx/ZrO2–450 (e) WO3/ZrO2–500. 55 Fig. 3–11 NH3–TPD thermograms of ammonia on WO3/ZrO2–450 and NbWOx/ZrO2 catalysts: (a) WO3/ZrO2–450 (b) 1–NbWOx/ZrO2–450 (c) 3–NbWOx/ZrO2–450 (d) 5–NbWOx/ZrO2–450. 56 Fig. 3–12 CO2–TPD thermograms of carbon dioxide on WO3/ZrO2–450 and NbWOx/ZrO2 catalysts: (a) WO3/ZrO2–450 (b) 1–NbWOx/ZrO2–450 (c) 3–NbWOx/ZrO2–450 (d) 5–NbWOx/ZrO2–450. 57 Fig. 3–13 FT–IR spectra of WO3/ZrO2–450 after pyridine adsorption at various evacuation temperatures: (a) 100oC (b) 200oC (c) 300oC (d) 400oC. 59 Fig. 3–14 FT–IR spectra of 3–NbWOx/ZrO2–450 after pyridine adsorption at various evacuation temperatures: (a) 100oC (b) 200oC (c) 300oC (d) 400oC. 59 Fig. 3–15 FTIR analysis of pyridine adsorption on SiZr5 and SiZr5-315 catalysts, after outgassing at 100 and 200oC[57]. 60 Fig. 4–1 Evolution of glycerol conversion as a function of time on stream at 290oC for the WO3/ZrO2 catalysts calcined at different temperatures. 0.3 g catalyst, GHSV = 1117 h-1, 60 mL/min N2 flow rate. 62 Fig. 4–2 Evolution of selectivity to acrolein as a function of time on stream at 290oC for the WO3/ZrO2 catalysts calcined at different temperatures. 0.3 g catalyst, GHSV = 1117 h-1, 60 mL/min N2 flow rate. 63 Fig. 4–3 Evolution of acrolein yield as a function of time on stream at 290oC for the WO3/ZrO2 catalysts calcined at 400, 450 and 500oC. 0.3 g catalyst, GHSV = 1117 h-1, 60 mL/min N2 flow rate. 64 Fig. 4–4 Deconvoluted areas under NH3–TPD peaks by Magic Plot. (sample: WO3/ZrO2–800) 64 Fig. 4–5 Correlation between mass specific glycerol consumption rate and total area under NH3–TPD desorption peak. 65 Fig. 4–6 Correlation between mass specific glycerol consumption rate and area under different NH3–TPD desorption peaks. 66 Fig. 4–7 Evolution of glycerol conversion as a function of time on stream at 290oC for the WO3/ZrO2–450 and NbWOx/ZrO2–450 catalysts with different Nb2O5 weight ratios to (WO3+ZrO2). 0.3 g catalyst, GHSV = 1117 h-1, 60 mL/min N2 flow rate. 69 Fig. 4–8 Evolution of selectivity to acrolein as a function of time on stream at 290oC for the WO3/ZrO2–450 and NbWOx/ZrO2–450 catalysts with different Nb2O5 weight ratios to (WO3+ZrO2). 0.3 g catalyst, GHSV = 1117 h-1, 60 mL/min N2 flow rate. 69 Fig. 4–9 Evolution of glycerol conversion as a function of time on stream at 290oC for the WO3/ZrO2–450 and NbWOx/ZrO2–450 catalysts with 50 mg catalyst. 73 Fig. 4–10 Evolution of selectivity to acrolein as a function of time on stream at 290oC for the WO3/ZrO2–450 and NbWOx/ZrO2–450 catalysts with 50 mg catalyst. 73 Fig. 4–11 Evolution of glycerol conversion as a function of time on stream at 290oC for the WO3/ZrO2–450 catalyst with different catalyst weight. 74 Fig. 4–12 Evolution of selectivity to acrolein as a function of time on stream at 290oC for the WO3/ZrO2–450 catalyst with different catalyst weight. 74 Fig. 4–13 Thermograimetric analysis of 3–NbWOx/ZrO2–450 under air atmosphere after catalytic reaction. 76 Fig. 4–14 Evolution of glycerol conversion as a function of time on stream at 290oC for 3–NbWOx/ZrO2–450 after regeneration. 0.3 g catalyst, GHSV = 1117 h-1, 60 mL/min N2 flow rate. 76 Fig. 4–15 Evolution of selectivity to acrolein as a function of time on stream at 290oC for 3–NbWOx/ZrO2–450 after regeneration. 0.3 g catalyst, GHSV = 1117 h-1, 60 mL/min N2 flow rate. 77 | |
dc.language.iso | zh-TW | |
dc.title | 鎢鋯金屬氧化物摻混氧化铌用於甘油氣相脫水反應 | zh_TW |
dc.title | Effect of Nb doping in WO3/ZrO2 catalysts for gas phase dehydration of glycerol to form acrolein | en |
dc.type | Thesis | |
dc.date.schoolyear | 101-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 萬本儒(Ben-Zu Wan),簡淑華(Shu-Hua Chien) | |
dc.subject.keyword | 氧化鎢,二氧化鋯,鈮,甘油,丙烯醛, | zh_TW |
dc.subject.keyword | WO3,ZrO2,Nb,Glycerol,Acrolein, | en |
dc.relation.page | 81 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2013-08-16 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
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