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紧急合成概念，并将其引入复杂化学过程系统的设计方法中。在连续搅拌槽反应器（CSTR）和泰勒涡流反应器（TVFR）两种连续流反应器中进行了醋酸乙烯酯的Belousov-Zhabotinskii反应和乳液聚合。(1)在cstr中进行的BZ反应中证实了一种特殊的化学振荡分岔情景，即在单周期振荡和混沌振荡之间存在一个混沌间歇窗口。(2)成功地观察了化学振荡在TVFR中BZ反应的顺流传播特征。研究发现，由于tfr的固有振荡与用作预反应器的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)醋酸乙烯酯的连续乳液聚合在乳化剂进料条件下出现化学振荡，使水相乳化剂浓度低于CMC。初生颗粒均形核长大过程与初生颗粒团聚过程交替发生。这表明有可能控制大小分布。

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.