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系統編號:

098STUT8795010

出版年:

研究生:

柳崇仁

研究生(英文姓名):

Chong-Ren Liu

論文名稱:

以奈米硫酸化氧化鋯降低油品酸價之研究

英文論文名稱:

Nano sized sulfated zirconia reduces the acid value of oil

指導教授:

林春榮

指導教授(英文姓名):

Chun-Rong Lin

學位類別:

碩士

校院名稱:

南台科技大學　

系所名稱:

奈米科技研究所

學號:

M97R0209

學年度:

語文別:

中文

論文頁數:

關鍵詞:

固體超酸 ; 酯化反應 ; 棕櫚油泥漿

英文關鍵詞:

Solid Superacid ; Esterification Reaction ;
Palm Oil Sludge

[ 摘要 ]

利用酸觸媒催化酯化反應一般皆採用均相反應法，此方法雖然反應時間較短，但後續的產物分離相當麻烦且會產生大量廢液，導致環境污染。若能以固體超酸做為催化劑，即能減小產物分離的困難度和避免環境污染，並且具有選擇性高、耐高温、不怕水、不怕酸、易活化再生、工藝流程簡單、便於連續操作的優點。氧化鋯具有高硬度、高强度、高韌性、高耐磨性與高的比表面積，因此非常適合作為觸媒。本研究主要是以不同的熱處理溫度(500、700、900℃)及時間(5、24 hr)製備不同結晶顆粒之奈米氧化鋯，並以不同的硫酸濃度利用浸泡法製備奈米氧化鋯固體超酸催化劑。樣品之特性分析包括X.R.D.、B.E.T.表面積測試及氨-程式升溫脫附，並以製得的樣品作為棕櫚酸油泥漿與甲醇進行酯化反應之觸媒，結果發現熱處理條件越嚴苛，會造成氧化鋯結晶顆粒越大，使得樣品表面積及酸性越低，並導致酯化反應的活性越差。另一方面，在1.0 ~ 6.0 M的硫酸濃度範圍內製備奈米氧化鋯固體超酸，硫酸濃度越高會使得觸媒的酸性越強，因此會有最佳的酯化反應活性。

關鍵字: 固體超酸，酯化反應，奈米氧化鋯，棕櫚油泥漿

[ 英文摘要 ]

In general, the esterification reaction is carried out by the homogeneous acid catalyst. The whole procedure procecture takes shorter time, but the subsequent phase separation for product can be very troublesome and results in plenty of waste water leading to environmental pollutions. Using solid superacid as a catalyst can reduce time for product separation and avoid environmental pollutions. On the other hand, it has the resistance high selectivity, high advantages of workability at temperature, water proof acid, quick regeneration, and long-lasting operation cycles. Due to its optimal characteristics in hardness, strength, toughness, wearresistance and large specific surface area, Zirconia is very suitable for the use of catalyst. In this study various heating temperatures (500,700,900℃) and heating time points (5,24hr) were taken to prepare zirconia particles in different nano crystalline sizes. The nano-sized zirconia solid superacid was then prepared by the soaking method with sulfurice acid. The characteristics of samples were examined by XRD, BET surface area and ammonia-TPD experiments. The nano-zirconia solid superacid was used as the catalyst for esterification reaction of palm acid oil. The result shows that the more severe treatment conditions would make zirconia crystal particles larger in size, and BET surface area lower in acidity. It results in the lower acidity of samples and then lower esterification reaction activity. In the range of 1.0 to 6.0M of sulfuric acid soaking concentration, higher soaking concentrations would make samples higher in acidity, and exhibits higher esterification reaction activity.
Keywords: Solid Superacid, Esterification Reaction, Palm Oil Sludge, Nano Zirconium Oxide

[ 論文目次 ]

中文摘要…………………………………………………………………I
英文摘要…………………………………………………………………II
誌謝………………………………………………………………………III
目錄………………………………………………………………………IV
表目錄……………………………………………………………………VII
圖目錄……………………………………………………………………VIII

第一章緒論…………………………………………………………….1
1.1 前言…………………………………………………………………1
1.2 生質能簡介…………………………………………………………3
1.3 生質燃料「生質柴油」……………………………………………4
1.4 國內生質柴油發展趨勢與現況……………………………………5

第二章相關理論……………………………………………………….7
2.1 生質柴油的介紹……………………………………………………7
2.1.1 歷史介紹…………………………………………………………7
2.1.2 生質柴油對環境之貢獻…………………………………………11
2.1.3 生質柴油的特性…………………………………………………14
2.1.4 生質柴油的經濟效應……………………………………………15
2.2 生質柴油製造技術…………………………………………………16
2.2.1 油脂原料之前處理………………………………………………16
2.2.2 醇與催化劑之混合………………………………………………17
2.2.3 轉酯化反應………………………………………………………18
2.2.3.1 酸催化反應……………………………………………………19
2.2.3.2 鹼催化反應……………………………………………………22
2.2.3.3 兩階段催化轉酯………………………………………………24
2.2.4 靜置分離…………………………………………………………25
2.2.5 水洗步驟…………………………………………………………25
2.2.6 醇的移除與回收…………………………………………………26
2.2.7 甘油的純化………………………………………………………26
2.3 生質柴油催化劑……………………………………………………27
2.3.1 液體鹼催化………………………………………………………27
2.3.2 固體鹼催化………………………………………………………28
2.3.3 液體酸催化………………………………………………………28
2.3.4 固體酸催化………………………………………………………29
2.3.5 酶催化製程………………………………………………………29
2.3.6 超臨界製程………………………………………………………30

第三章實驗與方法……………………………………………………31
3.1 研究動機……………………………………………………………31
3.2 氧化鋯的製備及應用………………………………………………32
3.2.1 物理與化學性質…………………………………………………32
3.2.2 製備方法…………………………………………………………33
3.2.2.1固相法…………………………………………………………34
3.2.2.2化學氣相法……………………………………………………34
3.2.2.3沉澱法…………………………………………………………34
3.2.2.4金屬醇鹽法……………………………………………………35
3.2.2.5溶膠-凝膠法……………………………………………………35
3.2.2.6水熱法…………………………………………………………36
3.2.2.7微乳液法………………………………………………………36
3.2.2.8超臨界乾燥法…………………………………………………36
3.3.3 氧化鋯的催化劑及載體應用……………………………………37
3.3 實驗藥品……………………………………………………………38
3.4 實驗步驟……………………………………………………………39
3.4.1 固體超酸觸媒之製備……………………………………………39
3.4.2 生質柴油製備……………………………………………………39
3.4.3 樣品特性分析儀器………………………………………………43

第四章結果與討論………………………………………………………46
4.1 原油的介紹…………………………………………………………46
4.2奈米超酸ZrO2的表徵與測試………………………………………47
4.2.1 比表面積分析……………………………………………………47
4.2.2 X-光繞射(X-ray diffraction, XRD)分析…………………………49
4.2.3 氨-程式升溫脫附分析……………………………………………53
4.3 生質柴油製備之研究………………………………………………54
4.3.1 酸價的滴定………………………………………………………54
4.3.2 熱處理對於酸催化反應的影響…………………………………55
4.3.3 酸催化觸媒量之影響……………………………………………56
4.3.4 酸催化甲醇量之影響……………………………………………57
4.3.5 酸催化溫度之影響………………………………………………58
4.3.6 酸催化吸水材料之影響…………………………………………59

第五章結論………………………………………………………………60

參考文獻…………………………………………………………………62

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