甘油與甲醇甲基化反應生產新的柴油含氧添加劑

Methylation of Glycerol with Methanol to Produce a New Oxygenate Additive for Diesels

李昱達(Yu-da Lee)

指導教授 ： 張志雄

大同大學/工程學院/化學工程學系所/碩士(2011年)

摘要

以甘油、氫氧化鈉與硫酸二甲酯(DMS)為原料製備出新的柴油含氧添加劑。將DMS添加至含有甘油鈉的反應器中，可以提升甘油在批式反應中甲基化的效率。利用甲基化反應過程為常壓操作下之優點，可用於傳統攪拌槽反應器製備大量含氧添加劑。當DMS對甘油的莫耳比為3 : 2、氫氧化鈉對甘油的莫耳比為3 : 1、反應時間24小時、溫度70℃、H2O/NaOH莫耳比為0.43及DMS添加時間為12小時，在一次的操作下甘油轉化率為93.48%而GDMEs+GTME的產率為71.2%。最後成品為混合的GDMEs (20 wt%)+GTME (80 wt%)其產率為34.48%，可成為新的柴油含氧添加劑。

關鍵字

含氧燃料 ； 甲基化試劑 ； 甲基化反應 ； 甘油

並列摘要

A new oxygenate additive for diesels (bio or petroleum) was manufactured using glycerol, dimethyl sulfate (DMS), and sodium hydroxide pellets as raw materials. By feeding the dimethyl sulfate into the batch reactor containing the sodium glycerate, a semibatch mode operation enhanced the effective methylation of glycerol. A conventional stirred tank reactor that can produce large quantities of oxygenate additives under a normal atmospheric pressure operation became the main feature of the methylation process. With a 3:2 molar ratio of DMS to glycerol, a 3:1 molar ratio of sodium hydroxide to glycerol, and a temperature of 343 K at the reaction time of 24 hours with the feeding time of DMS under 12 hours, The conversion of glycerol (93.5%) and a combined yield of GDMEs and GTME of 71.2% were achieved for a once-through operation. The finished product mixture of GDMEs (20 wt%) and GTME (80 wt%) with 34.5 % yield served as a new oxygenate additive for diesels (bio or petroleum).

並列關鍵字

fuel oxygenates. ； methylation reagents ； methylation reaction ； glycerol

參考文獻

[1] Garcia, J. I.; García-Marín, H.; Mayoral, J. A.; Perez, P. Green Solvents from Glycerol. Synthesis and Physico-Chemical Properties of Alkyl Glycerol Ethers. Green Chem. 2010, 12, 426.

[2] Ott, L.; Bicker, M.; Vogel, H. Catalytic dehydration of glycerol in sub- and supercritical water: a new chemical process for acrolein production. Green Chem. 2006, 8, 214.

[3] Behr, A.; Eilting, J.; Irawadi, K.; Leschinski, J.; Lindner, F. Improved utilisation of renewable resources: New important derivatives of glycerol. Green Chem. 2008, 10, 13.

[4] Arteconi, A.; Mazzarini, A.; Nicola, G. Emissions from Ethers and Organic Carbonate Fuel Additives: A Review. Water, Air, Soil Pollut. 2011.

[5] Sezer, I.; Bilgin, A. Effects of Methyl Tert-butyl Ether Addition to Base Gasoline on the Performance and CO Emissions of A Spark Ignition Engine. Energy Fuels 2008, 22, 1341.