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Production of glycerol acetonide as a fuel oxygenate through chemical conversion of glycerol with acetone
|Authors: ||Hsiao-Yu Lin|
|Contributors: ||NTOU:Department of Marine Engineering|
glycerol conversion;sulfuric acid-functionalized mesoporous catalyst;glycerol tert-butyl ether;glycerol acetonide;fuel additive
|Issue Date: ||2013-10-07T03:01:24Z
|Abstract: ||為提昇生質柴油副產品甘油之經濟價值，本研究將甘油轉化為具有較高價值之油品添加劑，首先利用酸性合成法製備孔洞觸媒載體，並使用嫁接-萃取法將孔洞觸媒載體反應為磺酸基孔洞觸媒，所製備完成之觸媒分析其結構與元素組成。實驗發現觸媒具孔洞結構，由硫元素覆蓋過鉀、鈉、氯元素，推斷磺酸基確實嫁接至觸媒載體表面上。其後利用所製備磺酸基孔洞觸媒催化甘油與異丁烯，發現在異丁烯/甘油莫耳比為3、觸媒量為甘油重13 wt.%、反應時間6小時、及反應溫度為110℃的條件下，可得到純度為96%的甘油第三丁基醚。之後以超級柴油重量比例2 wt. %及5 wt. %的甘油第三丁基醚加入超級柴油中，發現此添加劑可以提高油品之蒸餾溫度、比重及十六烷指數。本論文第二階段分別利用本實驗所製備的磺酸基孔洞觸媒與對甲苯磺酸觸媒催化甘油與丙酮的縮酮反應，發現使用對甲苯磺酸觸媒時，在丙酮/甘油莫耳比為3、觸媒量為甘油重8 wt. %、反應時間6小時、及反應溫度為56℃的條件下，製備得到的丙酮甘油縮酮產物具有最高的熱值、最低的運動黏度及冷濾點。再將丙酮甘油縮酮與超級柴油混合，發現在丙酮甘油縮酮/超級柴油重量比例為5/95時，具有最低之冷濾點，但當繼續增加丙酮甘油縮酮/超級柴油重量比例時，發現於超級柴油中的丙酮甘油縮酮開始有沉澱現象。|
Glycerol which is a by-product from biodiesel production process was chemically converted to be fuel additives in order to increase its economic value in this study. A silica mesoporous catalyst-carrier was first synthesized in an acidic environment. The catalyst-carrier was then reacted to form a sulfuric acid-functionalized mesoporous catalyst by a grafting-extraction method. The compositions and structure of the prepared catalyst were analyzed afterwards. The experimental results showed that the catalyst bore mesoporous structure and the elemental contents of potassium, sodium, and chlorine were covered with sulfur compound on the catalyst surface. It is inferred that sulfuric acids have been grafted into the carrier surface. The sulfuric acid-functionalized mesoporous catalyst was used for the etherification reaction between glycerol and isobutene. It was found that glycerol tert-butyl ether (GTBE) of 96% purity was produced under the experimental conditions of isobutene / glycerol molar ratio equal to 3, the catalyst / glycerol weight ratio 13 wt.%, the reacting time 6 hrs, and the reacting temperature 110°C. The GTBE product mixture was thereafter mixed with super low sulfur diesel (SLSD) in weight ratios of 2 wt. % and 5 wt. %, respectively. All the distillation temperature, specific gravity and cetane index of the SLSD increased with the addition of the GTBE mixture. At the second stage of this study, the catalyzing effect of the sulfuric acid-functionalized mesoporous catalyst and p-toluene sulfuric acid catalyst for the ketalization reaction between glycerol and acetone were compared. It was observed that the glycerol acetonide product had the highest heating value, and the lowest kinematic viscosity and cold filter filtering point when the p-toluene sulfuric acid catalyst was used under the conditions of acetone / glycerol equal to 3, the catalyst /glycerol weight ratio 8 wt. %, reacting time 6 hrs, and the reacting temperature 56 °C. In addition, the cold filter plugging point of SLSD was found to be decreased the lowest when the glycerol acetonide product at a weight ratio of glycerol acetonide / SLSD equal to 5/95 was added into SLSD. The glycerol acetonide product began to settle and separate from SLSD after further adding glycerol acetonide at a larger weight ratio of glycerol acetonide / SLSD than 5/95.
|Appears in Collections:||[輪機工程學系] 博碩士論文|
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