Research on flow behavior of liquid-phase precipitation reaction in the tubular microchannel reactor

doi:10.11949/0438-1157.20220609

Abstract

Abstract:

With the aqueous-phase synthesis of calcium carbonate (CaCO₃) as the model reaction and based on the magnifying observation of flow-reaction process, the flow behavior characteristics of liquid-phase precipitation reaction in the milli-scale tubular microchannel and the mechanism of channel clogging were analyzed from the rheological properties of the suspension. The results showed that the viscosity of CaCO₃-water suspension increased sharply with the increase of solid content at low shear rate and the nature of clogging could be attributed to the formation of local high viscosity area with high solid content on the wall and in the bulk flow, which made the fluidity seriously deteriorate. Increasing the flow rate of the reaction accelerated the formation of sedimentary layer and precipitation particle aggregates, thus the clogging was accelerated. The formation of aggregates was much faster than the accumulation of sedimentary layer, making“bridging”of aggregates the main factor of channel clogging. Based on the local high-viscosity region that destroys the flow wall and main body, two new microchannel reactor models are designed, which may provide new ideas for solving the problem of clogging of the reaction channel.

Key words: precipitation, reactors, flow, clogging mechanism, viscosity, rheology, suspensions, agglomeration

摘要：

以碳酸钙水相合成为模型反应，借助对流动反应过程的放大观测，从沉淀悬浮液的流变特性分析了液相沉淀反应在毫米级管式微通道中的流动行为特征以及通道堵塞的过程机理。结果表明，碳酸钙-水悬浮体系的黏度在低剪切速率下随固含率的增加而飙升，而反应通道堵塞的本质可归因于在壁面和流动主体区形成了固含率较高的局部高黏区，使流动性严重恶化。提高反应的流速加快了壁面沉积层和沉淀颗粒团聚体的形成，反而加快了堵塞；其中团聚体的形成远快于沉积层的积累，使团聚体的“架桥”虽晚于沉积层出现，却成为管路堵塞的主要因素。基于破坏流动壁面和主体的局部高黏区，设计了两种新型的微通道反应器模型，有可能为解决反应通道堵塞这一难题提供新的思路。

关键词: 沉淀, 反应器, 流动, 堵塞机理, 黏度, 流变学, 悬浮系, 团聚

CLC Number:

TQ 021.1

Hanlin YAO, Zhong XIN. Research on flow behavior of liquid-phase precipitation reaction in the tubular microchannel reactor[J]. CIESC Journal, 2022, 73(8): 3518-3528.

姚翰林, 辛忠. 液相沉淀反应在管式微通道反应器中的流动行为研究[J]. 化工学报, 2022, 73(8): 3518-3528.

Figures/Tables 17

Fig. 1 Schematic diagram of visual observation process for CaCO3 aqueous-phase continuous flow synthesis

Fig. 2 Rotational rheometer and coaxial cylinder module

Fig.3 Change of suspension viscosity over solid content and a possible “sedimentation-clogging” mechanism

Fig.4 Changes of CaCO3 aqueous-phase flow-synthesis process over reaction time at different flow rates

Fig.5 Change of CaCO3 aqueous-phase flow-synthesis process over reaction time when the tube diameter was 1 mm

Fig.6 Change of CaCO3 aqueous-phase flow-synthesis process over reaction time when adding surfactants

Fig.7 Particle size distribution of CaCO3 precipitation at different flow rates

Fig.8 Changes of CaCO3-water suspension viscosity over shear rate at different solid contents

Fig.9 Effect of solid content on the suspension sample state

Fig.10 Changes of CaCO3-water suspension viscosity over shear rate at different particle sizes

Fig.11 Extrusion of liquid phase in interspace by inertial motion of precipitation particles and formation of local high viscosity area

Fig.12 Effects of sedimentation and bridging on the tube pressure drop

Fig.13 Flow of precipitation particle aggregates when liquid layers exist near the wall surface (tube inner diameter: 4 mm; flow: 50.000 ml/min)

Fig.14 Microchannel reactor with outer-ring liquid layer (plan)

Fig.15 Graphical integration of tube reactors

Fig.16 Tube-in-tube microchannel reactor (plan)

Table 1 Analysis of potential superiorities and flaws of two novel static mixing microchannel reactor models

1. 对反应沉淀和流动壁面的阻隔作用更加明显

2. 可保持反应物浓度和反应速率不被降低

1. 可保持反应器本身的传热性能

2. 不存在液液两相的分离问题

1. 射流速度高，可有效破坏沉积层和团聚体

2. 混合效果好

劣势

1. 增加了对反应物料的传热阻力

2. 增加了反应容积（管长）

3. 增加了分离难度和原料成本

1. 降低了反应物浓度和反应速率，增加了反应容积（管长）

2. 均匀混合后反应沉淀仍可能在壁面沉积

1. 内管压力大

2. 微孔加工精度要求高

3. 反应物的物质的量比可能失准，需要通过实验验证

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