Construction of a Concept on Instabilities and Fluctuations of Complex Systems of Chemical Processes

本研究的目的是建立一种新的涌现合成概念，并将其引入到复杂化工过程系统的设计方法学中。在连续搅拌釜式反应器（CSTR）和泰勒涡流反应器（TVFR）中进行了Belousov-Zhabotinskii反应和醋酸乙烯酯乳液聚合。(1)在CSTRs中进行的BZ反应中，证实了一种特殊的化学振荡分岔现象，即在单周期振荡和混沌振荡之间存在一个混沌不连续窗口。(2)在TVFR中的BZ反应中成功地观察到了化学振荡的流向传播特性，发现由于TVFR固有振荡与作为预反应器的CSTR提供的强迫振荡输入之间的非线性耦合，在入口区域出现了一些不规则或准周期性。在下游区域，不稳定的化学振荡被衰减为规则的单周期振荡。(3)醋酸乙烯酯连续乳液聚合在低浓度乳化剂（低于CMC）的水相中存在化学振荡现象。一次粒子的均匀成核长大过程与一次粒子的团聚过程交替发生。这表明有可能控制粒度分布。

This research has been made in order to construct a new concept of emergent synthesis and introduce it into the methodology for designing complex systems of chemical processes. Belousov-Zhabotinskii reaction and emulsion polymerization of vinyl acetate were conducted in two kinds of continuous flow reactor : continuous stirred tank reactor (CSTR) and Taylor vortex flow reactor (TVFR).(1) A peculiar bifurcation scenario of chemical oscillations which has a window of chaotic intermittency between the singly-periodic and the chaotic oscillations has been confirmed in the BZ reaction conducted in CSTRs.(2) The characteristics of streamwise propagation of chemical oscillations were successfully observed in the BZ reaction in a TVFR.It has been found that some irregularity or quasi-periodicity appears at the entrance region owing to nonlinear coupling between the inherent oscillation of the TVFR and the input of forced oscillation supplied from the CSTR used as a pre-reactor. In the downstream region, the unstable chemical oscillations are attenuated to become regular singly-periodic oscillation.(3) The continuous emulsion polymerization of vinyl acetate showed chemical oscillations under the feed condition of emulsifier giving low concentration below CMC in the aqueous phase. The process of homogeneous nucleation and growth of primary particles and the process of agglomeration of primary particles occurred alternately. This suggests a possibility of controlling the size distribution.