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在水性碱存在下甘油催化转化为乳酸的综述。

A review of the catalytic conversion of glycerol to lactic acid in the presence of aqueous base.

作者信息

Akbulut Doğan, Özkar Saim

机构信息

Department of Chemistry, Middle East Technical University Ankara Turkey

出版信息

RSC Adv. 2022 Jun 29;12(29):18864-18883. doi: 10.1039/d2ra03085c. eCollection 2022 Jun 22.

Abstract

Lactic acid is a high-value-added chemical with large production, which is used in many industries including the production of pyruvic and acrylic acids. Lactic acid is largely obtained from the oxidation of glycerol, which is a prevalent by-product of biodiesel production. However, the oxidation of glycerol to lactic acid requires harsh reaction conditions such as high temperature and pressure as well as the use of a hefty strong base. In the presence of suitable catalysts, the production of lactic acid from glycerol can be achieved under mild conditions with 1 equivalent base per mole of glycerol. Herein, we review the reports of the catalytic conversion of glycerol to lactic acid in an aqueous alkaline medium considering the reaction conditions, catalytic activity for glycerol conversion and selectivity for lactic acid. We start first with the reports on the use of homogeneous catalysts that have high catalytic activity but miserable recovery. Next, we discuss the employment of colloidal metal(0) nanoparticles as catalysts in glycerol oxidation. The papers on the use of supported metal(0) nanoparticles are reviewed according to the type of support. We then review the polymetallic and metal/metal oxide nanocatalysts used for the conversion of glycerol to lactic acid in an alkaline medium. The catalysts tested for glycerol conversion to lactic acid without any additional bases are also discussed to emphasize the importance of a strong base for catalytic performance. The proposed mechanisms of glycerol oxidation to lactic acid in the presence or absence of catalysts as well as for the formation of side products are discussed. The available experimental kinetics data are shown to fit the mechanism with the formation of glyceraldehyde from glycerol alkoxide as the rate-determining step.

摘要

乳酸是一种产量大的高附加值化学品,用于包括丙酮酸和丙烯酸生产在内的许多行业。乳酸主要从甘油的氧化中获得,甘油是生物柴油生产中普遍存在的副产物。然而,将甘油氧化为乳酸需要苛刻的反应条件,如高温高压以及使用大量强碱。在合适的催化剂存在下,每摩尔甘油使用1当量碱,可在温和条件下由甘油生产乳酸。在此,我们考虑反应条件、甘油转化的催化活性和乳酸的选择性,综述了在碱性水介质中将甘油催化转化为乳酸的相关报道。我们首先从使用均相催化剂的报道开始,这些催化剂具有高催化活性但回收困难。接下来,我们讨论将胶体金属(0)纳米颗粒用作甘油氧化催化剂的情况。根据载体类型综述了关于使用负载型金属(0)纳米颗粒的论文。然后,我们综述了用于在碱性介质中将甘油转化为乳酸的多金属和金属/金属氧化物纳米催化剂。还讨论了在不使用任何额外碱的情况下测试甘油转化为乳酸的催化剂,以强调强碱对催化性能的重要性。讨论了在有或没有催化剂的情况下甘油氧化为乳酸以及副产物形成的推测机理。现有的实验动力学数据表明,该机理符合以甘油醇盐生成甘油醛为速率决定步骤的情况。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6b5c/9240816/2ccaf55939d9/d2ra03085c-f1.jpg

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