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Al(CF_3SO_3)_3催化选择性氧化甘油转化为甲酸(英文) 被引量:1
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作者 孔康 李迪帆 +3 位作者 马文保 周青青 唐国平 侯震山 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 北大核心 2019年第4期534-542,M0003,共10页
化石能源的日渐紧缺以及在使用过程中带来的环境污染引起了世界范围内学术界和工业界的密切关注,而生物柴油作为一种环境友好的可再生资源,可以替代化石能源,具有非常好的发展前景.虽然生物柴油生产过程中会产生大量甘油副产物,但是甘... 化石能源的日渐紧缺以及在使用过程中带来的环境污染引起了世界范围内学术界和工业界的密切关注,而生物柴油作为一种环境友好的可再生资源,可以替代化石能源,具有非常好的发展前景.虽然生物柴油生产过程中会产生大量甘油副产物,但是甘油也是一种重要的生物质平台分子,可用于生产多种高附加值的化学品.为了提高甘油的利用价值,同时探索一条高产率制备甲酸的可替代路径,本文研究了一个在较温和条件下,以三氟甲磺酸盐为催化剂,过氧化氢为氧化剂,将甘油选择性氧化为甲酸和乙醇酸的催化体系.结果表明,金属阳离子的催化活性与它们的水解常数(Kh)和内含水配体取代的交换速率常数(水交换速率常数, WERC)之间存在密切的相关性,适当的水解常数和较高的水交换速率常数有利于甘油氧化反应.在考察的多种金属三氟甲磺酸盐中,三氟甲磺酸铝(Ⅲ)是甘油选择性氧化为甲酸最有效的催化剂.在温度为70°C,反应12 h的条件下,甲酸收率可达72%.另外,反应体系中甘油、催化剂和H_2O_2的比例对甘油氧化产物分布有一定影响.一系列实验研究表明,催化体系中产生的Lewis酸和Br?nsted酸存在协同作用,具有适当Lewis酸和Br?nsted酸比例的金属盐呈现出良好的催化性能,催化剂过度水解可降低其催化活性.Al(OTf)_3原位水解过程中产生的Lewis酸性物种[Al(OH)_x]^(n+)和Br?nsted酸物种CF_3SO_3H是催化甘油转化的活性中心,另外在H_2O_2存在下产生的Al过氧物种可能是甘油氧化的活性中心.反应动力学和~1H NMR研究表明,在甘油转化为甲酸的过程中,甘油酸、乙醇酸和乙酸可能是反应的中间产物,可以继续氧化转化为甲酸.该催化剂体系同样适用于其他生物平台分子选择性氧化转化为有机羧酸,并且能够在甘油氧化反应中多次循环使用.Al(OTf)_3作为简单易得的催化剂具有高效的催化性能和优异的循环使用性能,这将为甘油选择性氧化转化为高附加值产品开辟一种新的方法. 展开更多
关键词 Al(OTf)3 甘油 过氧化氢 选择性氧化 甲酸
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Modifed Pre-stretching Assembly Method for Cable-Driven Systems 被引量:2
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作者 Guokai Zhang Xuyang Ren +3 位作者 Jinhua Li kang kong Shuxin Wang Jingchao Shen 《Chinese Journal of Mechanical Engineering》 SCIE EI CAS CSCD 2019年第3期17-32,共16页
Soft cable-driven systems have been employed in many assembled mechanisms, such as industrial robots, parallel kinematic mechanism machines, medical devices, and humaniform hands. A pre-stretching process is necessary... Soft cable-driven systems have been employed in many assembled mechanisms, such as industrial robots, parallel kinematic mechanism machines, medical devices, and humaniform hands. A pre-stretching process is necessary to guarantee the quality of cable-driven systems during the assembly process. However, the stress relaxation of cables becomes a critical concern during long-term operation. This study investigates the effects of non-uniform deformation and long-term stress relaxation of the driven cables owing to moving parts in the system. A simple closed-loop cable-driven system is built and an alternating load is applied to it to replicate the operation of transmission cables. Under different experimental conditions, the cable tension is recorded and the boundary data are selected to be curve-fitted. Based on the fitted results, a formula is presented to estimate the stress relaxation of cables to evaluate the assembly performance. Further experimental results show that the stress relaxation is mainly caused by cable creep and the assembly procedure. To remove the influence of the assembly procedure, a modified pre-stretching assembly method based on the stress relaxation theory is proposed and verification experiments are performed. Finally, the assembly performance is optimized using a cable-driven surgical robot as an example. This paper proposes a dual stretching method instead of the pre-stretching method to assemble the cable-driven system to improve its performance and prolong its service life. 展开更多
关键词 PERFORMANCE CABLE-DRIVEN system PRE-STRETCHING ASSEMBLY
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