乙醛低温绿色合成:焦磷酸锆催化乳酸脱羰反应
Green Synthesis of Acetaldehyde at Low Temperature: Decarbonylation of Lactic Acid Catalyzed by Zirconium Pyrophosphate
作者单位E-mail
唐聪明 重庆理工大学化学化工学院, 重庆 400054 tcmtang2001@163.com 
张瑜 重庆理工大学化学化工学院, 重庆 400054  
李新利 重庆理工大学化学化工学院, 重庆 400054  
谭平华 重庆理工大学化学化工学院, 重庆 400054  
邹伟欣 南京大学分析测试中心, 江苏省机动车尾气污染控制重点实验室, 南京 210093  
董林 南京大学分析测试中心, 江苏省机动车尾气污染控制重点实验室, 南京 210093  
庞均 重庆理工大学化学化工学院, 重庆 400054
西华师范大学化学合成与污染控制省级重点实验室, 南充 637002 
 
张菊 重庆理工大学化学化工学院, 重庆 400054
西华师范大学化学合成与污染控制省级重点实验室, 南充 637002 
 
摘要: 以生物基乳酸为原料,焦磷酸锆为催化剂,通过脱羰反应制备乙醛。探讨了模板剂、焙烧温度对催化剂的织构、表面酸碱性以及催化活性的影响规律。以此为基础,进一步揭示了催化剂的表面性质与脱羰反应活性之间的构效关系,发现乳酸脱羰反应由催化剂表面的酸碱位协同催化。和文献报道的相关催化剂比较,该催化剂拥有良好的低温催化活性。此外,在较高液空速、低催化剂用量以及控制低乳酸转化率(<40%)下,催化剂连续运行50 h左右后,乳酸转化率及乙醛选择性没有明显变化,表明该催化剂拥有良好的稳定性能。通过反应尾气分析,证实了乙醛的合成主要是通过乳酸脱羰反应途径实现。
关键词: 焦磷酸锆  脱羰  乳酸  乙醛  生物质
基金项目: 重庆市教委青年项目(No.KJQN201801109)和江苏省机动车尾气污染控制重点实验室开放课题基金(No.OVEC032)资助
Abstract: Acetaldehyde was prepared via decarbonylation of lactic acid using zirconium pyrophosphate catalyst. The zirconium pyrophosphate was prepared through reaction of zirconyl nitrate with pyrophosphatic acid in ethanol-water-dispersant mixed solution at ambient temperature. Effect of catalyst preparation conditions such as template agent and calcined temperature on decarbonylation of lactic acid to acetaldehyde was investigated. Several measurements such as wide X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), nitrogen physisorption, NH3-temperature programmed desorption (NH3-TPD), and CO2-temperature programmed desorption (CO2-TPD) were performed to disclose the structure and surface properties of catalysts. Furthermore, the relationship between template agent and calcined temperature, and texture, acid-base properties, and activity was discussed. Based on this discussion, we reveal that the decarbonylation of lactic acid to acetaldehyde is synergistically catalyzed by acidic sites and basic sites. Besides, the reaction conditions such as reaction temperature and lactic acid feed flow rate were also investigated. Compared with other related catalysts, this catalyst has better low temperature activity. Acetaldehyde selectivity almost remained unchanged although lactic acid conversion varied with lactic acid feed flow rates. The stability of catalyst was evaluated at high lactic acid liquid hourly space velocity (LHSV), less amount of catalyst, and low lactic acid conversion (<40%). As a result, lactic acid conversion and acetaldehyde selectivity were almost unchanged in 50 h on stream, suggesting an excellent stability in this catalyst. In addition, over the zirconium pyrophosphate catalyst, the possible catalytic reaction mechanism on decarbonylation of lactic acid to acetaldehyde was proposed. Tail gas detection demonstrates that the formation of acetaldehyde from lactic acid ascribes the decarbonylation reaction as the main path.
Keywords: zirconium pyrophosphate  decarbonylation  lactic acid  acetaldehyde  biomass
投稿时间:2018-11-07 修订日期:2019-03-19
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唐聪明,张瑜,李新利,谭平华,邹伟欣,董林,庞均,张菊.乙醛低温绿色合成:焦磷酸锆催化乳酸脱羰反应[J].无机化学学报,2019,35(5):819-827.
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