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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 張慶源 | |
dc.contributor.author | Yuan-Ho Chen | en |
dc.contributor.author | 陳原禾 | zh_TW |
dc.date.accessioned | 2021-06-13T04:36:51Z | - |
dc.date.available | 2011-07-25 | |
dc.date.copyright | 2006-07-25 | |
dc.date.issued | 2006 | |
dc.date.submitted | 2006-07-18 | |
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Electroanal. Chem., 519, 93-100. 36. Yoneyama, H. (1997) “Photoreduction of carbon dioxide on quantized semiconductor nanoparticles in solution,” Catal. Today, 39, 169-175. 37. 中國四川省科技促進發展研究中心 (2003) (China Szu-Tsuan Research Center of Science and Technology Promotion and Development, CSRCOST, China)。 38. 中國石油公司 (2004) (China Petroleum Corporation, CPC, Taiwan)。 39. 中國科學技術研究所 (2005) (China Institute of Science and Technology, CIST, China)。 40. 行政院環境保護署(2005年01月),「淺談我國推動風力發電之二氧化碳減量效益」,雙 月刊,第76期。 41. 行政院環境保署網站,February (2005)。 42. 周欣穎 (2002),「奈米Ag/TiO2觸媒進行二氧化碳光催化還原反應」,碩士論文,國立台灣大學化學工程學研究所。 43. 陳郁文 (2005),Personal Communication,國立中央大學化學工程研究所。 44. 曾怡享 (2003),「奈米金屬氧化鈦觸媒光催化還原二氧化碳」,博士論文,國立台灣大學化學工程學研究所。 | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/33368 | - |
dc.description.abstract | 近百年來由於工業革命促成石化材料的大量使用,人類對於物質生活越來越講究,使得石化產品急劇的產生,並伴隨著污染物迅速的生成,包含大量CO2的排放。日前京都議定書已通過,使得CO2減量議題成為目前全世界所關注的焦點之一。本研究利用金屬光觸媒還原CO2以生成乙烯,提供作為工業上之原料。一方面可以降低溫室效應氣體排放,另一方面可以增加石化資源的產生來源。
本研究利用光觸媒(Cu/TiO2及Ag/TiO2),經由波長254 nm的UV燈照光產生電子與電洞對,並結合電解程序將CO2還原成石化資源之乙烯。本研究共使用四種不同還原程序,方法與結果分別敘述如下 : 1) Ag/TiO2光催化還原氣相CO2程序:產物主要為甲醇。反應24小時後,最大甲醇產量達到48.3 μg ; 2) Ag/TiO2和Cu/TiO2光催化還原液相CO2程序:反應產物以液相甲醇為主。在溶液初始濃度為5 g L-1 NaOH、飽和CO2、觸媒量為1 g、及反應28小時,結果顯示Ag/TiO2之催化效果較Cu/TiO2為佳。其甲醇產量分別為124.46 及53.93 μg ; 3) 三相(氣(CO2)/液(Na2CO3/CuCl2)/固(Cu/TiO2))光催化還原CO2程序:產物主要為甲烷。當觸媒量為0.5 g,在溶液初始濃度含0.1 M Na2CO3和1 M CuCl2,反應28小時後系統之甲烷產量可達62.5 μg ; 4) 三相(氣(CO2)/液(Na2CO3/CuCl2)/固(Cu/CuCl) )使用紅銅電極電解法還原CO2之程序:此程序反應3小時但無Cu/TiO2觸媒下,最適操作條件為前處理曝CO2一小時下,0.2 M Na2CO3、0.1 M CuCl2濃度、電流為1安培(A)、相對電壓為12伏特(V)時,氣態CO2降解率達88%。乙烯及甲烷產量分別為53,211及3,433 μg,乙烯產量佔氣相有機物達到93.9%。乙烯產量佔氣液相有機物產量總合的73.42%。合成氣 (CO + H2)產量更佔整體氣體產量的49.6%。其他氣體CO、H2、及O2則分別為74,788、80,791、及101,642 μg ; 最後液相甲酸產量為15,832 μg ; 5)三相(氣(CO2)/液(Na2CO3/CuCl2)/固(Cu/TiO2))之光催化結合紅銅電極電解法還原CO2之程序: 在0.2 M Na2CO3,添加0.5 g Cu/TiO2條件下,其甲烷、乙烯、CO、甲酸、H2、及O2之總生成量分別為942、13,160、46,096、4,907、87,975、及100,926 μg。與程序4相比較,乙烯、甲烷、及甲酸產率下降三分之二,CO產率下降二分之一,O2產率不變,而H2產率稍微上昇。由此可知,於較高Na2CO3濃度( 0.2 M )時添加Cu/TiO2光觸媒進行光電解反應會抑制甲烷、乙烯、CO、及甲酸之生成,但會稍微增加氫氣的產生。顯示出電解與光觸媒兩系統結合將CO2還原,其效能有降低之效果。 以上各程序所使用之觸媒量中,程序(1)為Ag/TiO2觸媒0.85 g,程序(2)為Ag/TiO2及Cu/TiO2觸媒1 g,程序(3)及(4)皆為Cu/TiO2觸媒0.5 g,Ag/ TiO2和Cu/TiO2之Ag和Cu為2 wt.%;程序(1)之氣體體積為1060 mL,而程序(2)之液相體積1000 mL,程序(3)及(4)之液相體積皆為500 mL。未來後續研究仍需針對乙烯產率及選擇性做更進一步之提升。 | zh_TW |
dc.description.abstract | This study investigated the application of the ultra violet (UV) with reduction photocatalyst to convert the green-house air pollutants to the useful chemicals. The method is denoted as UV/photocatalyst process. Carbon dioxide, which has a highest concentration among green-house air pollutants was taken as a model compound. The emission of CO2 to the atmosphere was substantially found in the industrial waste gaseous streams. The operation parameters and influential factors such as the type, amount, and coating of photocatalysts, treatment temperature, initial concentration of CO2, intensity and wave length of UV radiation, type of solutions, and hydrogen sources, etc. were examined in order to find the proper conditions for the effective reduction of CO2 to useful chemicals. The photocatalyts used in this study were Ag/TiO2 and Cu/TiO2 made by the impregnation method. The wavelength of UV irradiation was 254 nm. The photocatalytic reductions of CO2 were performed via three different methods. In method 1, only gases CO2 was presented in the reactor to process the phtocatalytic reaction with catalyst on glass plates. As for method 2, sources of CO2 were from the liquid solution of Na2CO3 and gaseous CO2 above the liquid solution containing suspended particles of catalyst. Method 3 was similar to method 2 with addition of CuCl2 in the liquid solution of Na2CO3. The major product via methods 1 and 2 was methanol. An addition of CuCl2 to the solution containing suspended Cu/TiO2 catalyst can form CuCl/Cu/TiO2 which further catalytically enhanced the reduction of CO2 and CH3OH, producing CH4 and increasing its yield. The determining step for the production of methane is the additions of Na2CO3 and CuCl2 in the aqueous solution. The orders of concentrations of Na2CO3 enhancing the methane yields were 0.1 > 0.2 > 0.3 > 0.05 M Na2CO3 at 0.1 M CuCl2, while those of CuCl2 were 1 > 2 > 0.1 > 0 > 4 M CuCl2 at 0.1 M Na2CO3. The results obtained from this study are useful for better understanding the UV/photocatlyst process for the reuse of CO2. Method 4 was electrolysis using red copper electrode with power supply standards of 12 relative volts and 1 amp. The orders of concentrations of Na2CO3 enhancing the ethylene yields were 0.2 > 0.1 > 0.3 > 0.4 M Na2CO3 at 0.1 M CuCl2. As for the enhancing effects of concentrations of CuCl2 on the methane yields, the orders were 0.1 > 0.05 > 0 > 0.2 M CuCl2 at 0.2 M Na2CO3. The degradation efficiencies of gaseous CO2 was 88% and the products yielded of C2H4, CO, CH4, HCOOH, H2, and O2 were 53211, 74788, 3433, 15832, 80791 and 101642 μg at 0.2 M Na2CO3 and 0.1 M CuCl2. Method 5 was combining photocatalyst and electrolysis processes for the reduction of CO2. The yields of products of method 5 relative to those of method 4 decreased two-thirds for C2H4, CH4 and HCOOH, and half for CO. As for O2, the yields of method 5 and 4 were about the same. However, the yield of H2 of method 5 increased slightly as compared to that of method 4 with the addition of 0.5 g Cu/TiO2 catalyst at 0.2 M Na2CO3 and 0.1 M CuCl2. The result indicated that combining photocatalyst and electrolysis processes would restrain the reduction efficiency of CO2. The technology for the reduction of CO2 to useful chemicals elucidated by this study is environmentally favorable. | en |
dc.description.provenance | Made available in DSpace on 2021-06-13T04:36:51Z (GMT). No. of bitstreams: 1 ntu-95-R93541120-1.pdf: 5521337 bytes, checksum: 7ab7576c17646b9e9c49df68d7289eb7 (MD5) Previous issue date: 2006 | en |
dc.description.tableofcontents | 誌謝 i
中文摘要 ii 英文摘要 iv 目錄 vi 圖目錄 x 表目錄 xix 符號說明 xx 第一章 研究緣起與目的 1 1.1 前言 1 1.2 研究目的 1 第二章 文獻探討 3 2.1 二氧化碳排放現況 3 2.2 二氧化碳固定法 3 2.3 光觸媒氧化還原理論 5 2.4 光觸媒還原溫室氣體以合成低碳數原料 6 2.5 還原性光觸媒還原二氧化碳以生成乙烯 7 2.6 電解二氧化碳以生成乙烯 8 第三章 研究方法 15 3.1 實驗藥品與器材 15 3.1-1 實驗藥品 15 3.1-2 實驗器材 15 3.2 實驗流程 16 3.2-1 實驗架構 16 3.2-2 Ag/TiO2觸媒製作流程 17 3.2-3 Cu/TiO2觸媒製作流程 18 3.2-4 Ag/TiO2觸媒披覆流程 18 3.3 反應器 19 3.3-1 反應器設計 19 3.3-2 實驗前反應器前置處理 19 3.4 實驗步驟 20 3.4-1 方法一:氣相CO2之氣/固光催化還原反應 20 3.4-2 方法二:液相CO2之液/固光催化還原反應 21 3.4-3 方法三:三相(氣(CO2)/液(Na2CO3/CuCl2)/固(Cu/TiO2))光催化還原反應 21 3.4-4 方法四:三相(氣(CO2)/液相(Na2CO3/CuCl2)/固(Cu/TiO2))光催化結合 電解反應 22 3.4-5 方法五:三相(氣(CO2)/液相(Na2CO3/CuCl2)/固(Cu/TiO2))光催化 結合電解反應 23 3.5 反應物與產物分析 24 3.5-1 儀器與操作條件 24 3.5-2 產物定性與定量 25 3.6 觸媒的鑑定與分析 25 3.6-1 掃描式電子顯微鏡 + 光能譜分析儀 (SEM + EDS) 25 3.6-2 穿透式電子顯微鏡 (TEM) 26 3.6-3 化學分析影像能譜儀 (ESCA) 26 3.6-4 X光繞射儀 (XRD ) 27 3.6-5 比表面積量測儀 (BET) 27 第四章 二氧化碳還原效能之結果與討論 35 4.1 主要工作內容 35 4.2 方法一: 氣相(氣/固)二氧化碳光催化還原反應 35 4.3 方法二: 液相(液/固)二氧化碳光催化還原反應 35 4.4 方法三: 三相(氣(CO2)/液相(Na2CO3/CuCl2)/固(Cu/TiO2))光催化還原反應 36 4.4-1 固定CuCl2濃度,添加不同Na2CO3濃度之影響 36 4.4-2 固定Na2CO3濃度,添加不同CuCl2濃度之影響 37 4.5 方法四: 三相(氣(CO2)/液(Na2CO3/CuCl2)/固(Cu/CuCl))電解反應 38 4.5-1 CO2降解率 38 4.5-2 不同電極材質之影響 39 4.5-3 添加Na2CO3之影響 39 4.5-4 固定CuCl2濃度,添加不同Na2CO3濃度之影響 39 4.5-5 固定Na2CO3濃度,添加不同CuCl2濃度之影響 41 4.6 方法五: 三相(氣(CO2)/液(Na2CO3/CuCl2)/固(Cu/TiO2))光催化結合紅銅 電解反應 43 4.7 不同產物產生量之比較 (方法四) 44 4.8 反應前後電極重量之變化 (方法四及五) 44 4.9 反應機制探討 45 4.10 方法四陰極電極重覆使用之探討 46 4-11 能源效益分析 47 4.11-1 能量轉化率 (Energy Conversion, Ec) 48 4.11-2光能效率 (Photo Energy Efficiency, PEE) 48 4.11-2 視光量子產率 (Apparent Quantum Yield) 49 4.12 二氧化碳轉化率 49 4.13 經濟效益初步評估 50 4.14 乙烯選擇性探討 52 第五章 觸媒及電極特性分析之結果與討論 105 5-1 掃描式電子顯微鏡 + 光能譜分析儀 (SEM + EDS) 105 5-2 穿透式電子顯微鏡 (TEM) 106 5-3 X光繞射儀 (XRD ) 106 5-4 比表面積量測儀 (BET) 106 5-5 化學分析影像能譜儀 (ESCA) 107 5-6 紅銅、黃銅電極成分分析 107 5-7 陰極電極產物分析 107 第六章 結論與建議 127 6.1 結論 127 6.2 建議 130 參考文獻 131 附錄A 檢量線製作 136 附錄B 乙烯方法偵測極限 ( Method Detection Limit, MDL ) 150 附錄C 水中有機物分析方法溫度之決定 152 附錄D 能量轉化率計算 153 附錄E 平均光能效率 (Average Photo Energy Efficiency) 155 附錄F 視光量子效率 (Apparent Quantum Yield, Φapp) 157 附錄G TiO2之XRD標準晶型圖譜 159 附錄H 方法四及五反應前後pH、氧化還原電位(ORP)、及導電度值變化 160 附錄I 投稿文章: the Air & Waste Management Association’s 99th Conference and Exhibition, New Orleans, Louisiana, June 20-23 (2006) 161 | |
dc.language.iso | zh-TW | |
dc.title | 二氧化碳再利用生成乙烯之研究 | zh_TW |
dc.title | Reduction of Carbon Dioxide to Ethylene | en |
dc.type | Thesis | |
dc.date.schoolyear | 94-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 陳郁文,謝哲隆 | |
dc.subject.keyword | 溫室氣體減量,光觸媒還原,CO2,乙烯,電解,Ag/TiO2,Cu/TiO2, | zh_TW |
dc.subject.keyword | Green-house gas reduction,photocatalyst,carbon dioxide,ethylene, electrolysis, | en |
dc.relation.page | 170 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2006-07-19 | |
dc.contributor.author-college | 工學院 | zh_TW |
dc.contributor.author-dept | 環境工程學研究所 | zh_TW |
顯示於系所單位: | 環境工程學研究所 |
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ntu-95-1.pdf 目前未授權公開取用 | 5.39 MB | Adobe PDF |
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