Abstract:

Biomass has been widely applied to the research on synthesizing acrylonitrile due to its characteristics such as abundance in nature, environmentally friendliness and recyclability. In this article, the ongoing research in the process of acrylonitrile synthesis was reviewed, focusing on renewable biomass resource including glycerol, glutamic acid and 3-hydroxypropionic acid. Three processes using different catalysts were introduced and discussed, including two steps (dehydration and ammoxidation) of glycerol, decarboxylation from glutamic acid and nitrilation of 3-hydroxypropionic acid. The yield of acrylonitrile using the first process was around 60%, which was much less than 80%+ of propene ammoxidation process. Besides, catalyst used in the process has a poor stability because of carbonaceous deposits. Therefore, increasing acrylonitrile yield and catalyst stability would be the primary goals in the future research. The advantage of the second process is significant without ammonia feedstock, while the process is more complex and less environmentally friendly. The yield of acrylonitrile was no more than 20%, so further exploration of the optimal process and catalytic performance should be included in future research. As for the third process, the absence of oxygen feedstock from the reaction sharply reduced the production of carbon oxides and side products, especially hydrogen cyanide. The acrylonitrile yield of this process exceeded over 90%, which is far beyond than that of propene ammoxidation process. Thus, nitrilation process of 3-hydroxypropionic acid provides a cost-comparable, sustainable route to acrylonitrile, which makes it possible to produce low-cost PAN carbon fibers in domestic market.

Key words: acrylonitrile, biomass, glycerol, glutamic acid, 3-hydroxypropionic acid, catalyst

摘要：

生物质原料由于具有来源广泛、绿色环保和可再生循环利用等特点，近年来逐渐应用于丙烯腈的合成研究。本文简述了以生物质（甘油、谷氨酸和3-羟基丙酸）为原料合成丙烯腈3种新工艺的研究进展，主要介绍和讨论了甘油两段法、谷氨酸脱羧基法和3-羟基丙酸腈化法的合成工艺及其催化剂的性能。目前甘油两段法丙烯腈总收率在60%左右，远低于丙烯法工业装置高于80%的水平，并且催化剂较易积炭而失活，今后仍需努力提高丙烯腈收率和催化剂的稳定性；谷氨酸脱羧基法的优点是反应过程中不需要引入氨，但是工艺复杂且对环境影响较大，丙烯腈单收只有20%左右，合成工艺仍待进一步优化；而3-羟基丙酸腈化法不需要氧气参与反应，副产物较少，碳氧化物的排放显著降低且不产生氢氰酸，丙烯腈单收大于90%远高于丙烯法，通过该工艺生产的丙烯腈具有一定的成本优势，比较适合应用于国内低成本聚丙烯腈基碳纤维的生产。

关键词: 丙烯腈, 生物质, 甘油, 谷氨酸, 3-羟基丙酸, 催化剂