甘油再利用產製三醋酸甘油酯或1,2-丙二醇之程序設計

由於近年來生質柴油大量生產，使得發展其副產物甘油的再利用製程越來越受到重視，而本研究探討其中二種甘油應用並使用Aspen Plus進行模擬，其一為甘油與醋酸進行酯化反應生成三醋酸甘油酯(Triacetin)，其二為甘油與氫氣進行反應生產1,2-丙二醇(1,2- Propanediol)。三醋酸甘油酯能應用於生產塑化劑、高分子塗膠劑、炸藥、菸草、藥物及化妝品之添加劑。本研究以反應蒸餾塔進行模擬，並以最低年度總成本(TAC)為目標完成最適化設計。接著探討加入共沸劑醋酸異丁酯或1,2-二氯乙烷對整體系統的影響，而結果顯示以醋酸異丁酯作為共沸劑的共沸反應蒸餾系統為此製程的最佳設計，並提出以單點溫度控制架構作為干擾排除的控制策略。而另一種甘油的應用則是1,2-丙二醇，主要應用於製造聚酯類樹脂，作為食品的營養添加劑、非離子型去汙劑、液體洗滌劑、防凍劑、除冰劑及化妝品產業當中。本研究以傳統反應器CSTR進行反應，在反應部分以固定進入反應器的甘油進料流量下生成最多1,2-丙二醇產物為最適化設計，後續以蒸餾塔序列進行分離，並以最低年度總成本(TAC)為目標完成最適化設計，最後提出萃取蒸餾的方式增進部分分離製程的經濟效益。

關鍵字

甘油；三醋酸甘油酯； 1,2-丙二醇；程序設計

並列摘要

In recent years, mass production of biodiesel making the development of its byproduct glycerol utilization process more and more attention, and in which two kinds of this study was to investigate and use Aspen Plus to do the simulation work. One for the esterification of glycerol with acetic acid to produce triacetin, the second is glycerol react with hydrogen to produce 1,2-propanediol. Triacetin is used mainly as a plasticizer and a gelatinizing agent in polymers, explosives and as an additive in tobacco, pharmaceutical compounds, and cosmetics. In this study, reactive distillation is used as the main part of this process, and minimize the total annual cost(TAC) as the optimal design. Furthermore, the effect of azeotropic agents, like iso-butyl acetate and 1,2-dichloroethane are also discussed. The results show heterogeneous azeotropic reactive distillation process with usage of iso-butyl acetate as entrainer is the best case. Finally, the single-point temperature control will be used as control strategy. The second study is about the other glycerol utilization to produce 1,2-propanediol, which mainly used in the manufacture of polyester resin, as a nutritional additive, non-ionic detergents, liquid detergents, antifreeze, de-icing agents and application in cosmetic industry. The overall process, CSTR is used to react, and find the optimal case that has most production of 1,2-propanediol with fixed glycerol flow rate into the reactor is the goal in this part. Afterward a series of distillation columns is used to purify the product, and also finish the optimal design of each unit. Due to it is difficult to separate between 1,2-propanediol and ethylene glycol, extractive distillation is introduced to improve the economics of the process.

並列關鍵字

Glycerol ； Triacetin ； 1,2-Propanediol ； Process design

參考文獻

[1] Zhou, C. H.; Beltramini, J. N.; Fan Y. X.; Lu, G. Q. Chemoselective Catalytic Conversion of Glycerol as a Biorenewable Source to Valuable Commodity Chemicals. Chem. Soc. Rev. 2007, 37, 527–549.

[2] Behr, A.; Westfechtel, A.; Gomes, J. P. Catalytic Processes for Technical Use of Natural Fats and Oils. Chem. Eng. Technol. 2008, 31, 700–714.

[5] Gelosa, D.; Ramaioli, M.; Valente, G.; Morbidelli, M. Chromato-graphic reactors: Esterification of glycerol with acetic acid using acidic polymeric resins. Ind. Eng. Chem. Res. 2003, 42, 6536–6544.

[6] Thotla, S.; Srinivas, S.; Mahajani, S. M. Entrainer based reactive distillation of ethylene glycol with acetic acid. Ind. Eng. Chem. Res. 2008, 47, 698–703.

[7] Hasabnis, A. ; Mahajani, S. Entrainer-Based Reactive Distillation for Esterification of Glycerol with Acetic Acid. Ind. Eng. Chem. Res. 2010, 49, 9058–9067.

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甘油再利用產製三醋酸甘油酯或1,2-丙二醇之程序設計

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