Research progress of reactors for liquid-liquid heterogeneous system

doi:10.11949/0438-1157.20240025

Abstract

Abstract:

There are many liquid-liquid heterogeneous reaction systems involved in the chemical industry production process. Since the reaction process occurs at the two-phase interface, the reaction effect usually depends on the mass transfer efficiency between phases and the degree of mixing. Due to the complexity of most liquid-liquid heterogeneous reaction system, the mass transfer and mixing performance of the used reactors has great effects on the reaction processes. Recently, the research and development of reactors for liquid-liquid heterogeneous system has attracted much attention in order to intensify the liquid-liquid heterogeneous reaction and improve the product quality. In this paper, the research progress of traditional reactors and process-intensified reactors for liquid-liquid heterogeneous reaction systems is reviewed. By comparing the characteristics of traditional reactors and process-intensified reactors, the application scope and optimization strategy are summarized towards reactors for liquid-liquid heterogeneous system. A practicable route is proposed to improve the safety of liquid-liquid heterogeneous reaction systems, which should combine process intensification technology with traditional reactors.

Key words: liquid-liquid heterogeneous reaction, reactor, process intensification

摘要：

化学工业生产过程中涉及众多液-液非均相反应体系，因其反应过程发生于两相界面，反应效果通常取决于相间传质效率及混合程度。由于大多数液-液非均相反应过程复杂，所用反应器的传质和混合性能对反应过程有很大影响。近年来，可通过强化液-液非均相反应进而提升产品质量，液-液非均相反应器的研发备受关注。综述了用于液-液非均相反应体系的传统反应器及过程强化反应器的研究进展，通过对比传统反应器及过程强化反应器的特性，总结了各类反应器的适用范围和优化策略，提出了采用过程强化技术助力液-液非均相反应安全性提升的可行途径。

关键词: 液-液非均相反应, 反应器, 过程强化

CLC Number:

TQ 051

Shaoyang MA, Hanzhuo XU, Liangliang ZHANG, Baochang SUN, Haikui ZOU, Yong LUO, Guangwen CHU. Research progress of reactors for liquid-liquid heterogeneous system[J]. CIESC Journal, 2024, 75(3): 727-742.

马韶阳, 徐涵卓, 张亮亮, 孙宝昌, 邹海魁, 罗勇, 初广文. 液-液非均相反应器研究进展[J]. 化工学报, 2024, 75(3): 727-742.

Figures/Tables 11

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反应器类型	d₃₂/μm	k_La/s^-1	k_L/(m/s)	文献
釜式反应器	100~2000	10^-3~10^-1	10^-7~10^-6	[115]
超声强化釜式反应器	—	10^-2~1	—	[116]
定-转子旋转圆盘反应器	5~130	10^-4~10	10^-9~10^-5	[117]
气体搅拌微通道反应器	10~20	1~10	10^-6~10^-5	[73]
方形微通道反应器	200~600	10^-2~10^-1	10^-6~10^-5	[118]
旋转填充床	10~150	1~10²	10^-5~10^-4	[114]

反应器类型	d₃₂/μm	k_La/s^-1	k_L/(m/s)	文献
釜式反应器	100~2000	10^-3~10^-1	10^-7~10^-6	[115]
超声强化釜式反应器	—	10^-2~1	—	[116]
定-转子旋转圆盘反应器	5~130	10^-4~10	10^-9~10^-5	[117]
气体搅拌微通道反应器	10~20	1~10	10^-6~10^-5	[73]
方形微通道反应器	200~600	10^-2~10^-1	10^-6~10^-5	[118]
旋转填充床	10~150	1~10²	10^-5~10^-4	[114]

反应器类型	结构特征	应用于液-液非均相反应体系待优化方向	适用范围		优化策略
反应器类型	结构特征	应用于液-液非均相反应体系待优化方向	反应类型	体系物性	优化策略
釜式反应器	通常为在中心轴安装有一个或多个搅拌叶轮的釜式结构	1.液体在叶轮附近受到剪切作用最为强烈，但在挡板附近却会存在死区，因此叶轮常受到侵蚀损伤，挡板附近需定期清除沉积物 2.常存在传质速率无法与快速/瞬时液-液非均相反应的反应速率相匹配的问题，很难快速实现分子级别的均匀混合	热效应较小的中、慢速液-液非均相体系	适用于高密度差，高黏度体系和反应结晶体系	新型叶轮结构，新型挡板结构及安装位置，增加叶轮级数，改变叶片位置及材质
管式反应器（不含静态混合内构件）	具有较大长径比的管状结构连续操作反应器	1.液体主要依靠自身经泵送所获得能量经过管路折流、收缩扩张、扰动等作用实现液-液非均相的混合，对于慢速反应需要较长的反应管道 2.缺少主动混合方式，传质与混合效果受限，在长停留时间下，易发生分层	热效应大的慢速反应	适用于低密度差、低黏度体系和固体生成反应体系	增加螺纹或收缩扩张等结构，改变管形与排布方式
静态混合器	在管路内部添加混合单元或管壁安装不同结构的叶片	1.复杂结构混合单元虽能提供较好的混合程度，但增大流体阻力与静态混合器的生产成本 2.径向混合较多，轴向混合较少 3.连接结构较多，对于一些强放热或危险化学反应需要考虑及时撤热、防泄漏，防腐蚀等问题	处理量较大的吸放热反应	适用于低密度差，中高黏度体系，对于高密度差体系容易分层，不易实现均匀混合	设计新型混合器件结构或者管壁安装不同形状叶片结构
微反应器	利用不同方式的预混形式和不同几何结构的微通道实现混合	1.工业放大只能通过“数量放大”，不适用于较高产量需求的化学品工业生产 2.微通道尺寸狭小，目前增强微通道内部液体混合只能通过改变入口直径和方式、挡板数量和挡板之间的间隔距离等，这会导致微通道结构过于复杂，难以批量生产，实用性下降 3.微反应器内流体流动具有Reynolds数低和高表面张力的特点，对流扩散通常较弱，存在堵塞敏感性高的问题，特别是对于生产工艺中有固体反应物以及反应结晶体系^[126]	强吸放热快速反应	适用于低密度差，低黏度体系，对于有固体生成或高黏度体系易出现堵塞问题	优化微通道几何结构构型，优化两相流体接触方式
旋转填充床	利用高速旋转的填料将经过液体分布器的液体进行破碎分散	1.相对于径向运动，液体在填料中的横向漂移能力有限，导致液体在填料中的分布不均匀 2.旋转部件包括转子、轴承等需要保证密封，尤其是对于一些腐蚀性或危险化学反应，需要保证长期的可靠性^[127]	快速复杂反应	适用于高密度差体系和高黏度体系，对于有固体生成体系易出现堵塞问题	优化转子结构，优化预混合及液体分布器结构

反应器类型	结构特征	应用于液-液非均相反应体系待优化方向	适用范围		优化策略
反应器类型	结构特征	应用于液-液非均相反应体系待优化方向	反应类型	体系物性	优化策略
釜式反应器	通常为在中心轴安装有一个或多个搅拌叶轮的釜式结构	1.液体在叶轮附近受到剪切作用最为强烈，但在挡板附近却会存在死区，因此叶轮常受到侵蚀损伤，挡板附近需定期清除沉积物 2.常存在传质速率无法与快速/瞬时液-液非均相反应的反应速率相匹配的问题，很难快速实现分子级别的均匀混合	热效应较小的中、慢速液-液非均相体系	适用于高密度差，高黏度体系和反应结晶体系	新型叶轮结构，新型挡板结构及安装位置，增加叶轮级数，改变叶片位置及材质
管式反应器（不含静态混合内构件）	具有较大长径比的管状结构连续操作反应器	1.液体主要依靠自身经泵送所获得能量经过管路折流、收缩扩张、扰动等作用实现液-液非均相的混合，对于慢速反应需要较长的反应管道 2.缺少主动混合方式，传质与混合效果受限，在长停留时间下，易发生分层	热效应大的慢速反应	适用于低密度差、低黏度体系和固体生成反应体系	增加螺纹或收缩扩张等结构，改变管形与排布方式
静态混合器	在管路内部添加混合单元或管壁安装不同结构的叶片	1.复杂结构混合单元虽能提供较好的混合程度，但增大流体阻力与静态混合器的生产成本 2.径向混合较多，轴向混合较少 3.连接结构较多，对于一些强放热或危险化学反应需要考虑及时撤热、防泄漏，防腐蚀等问题	处理量较大的吸放热反应	适用于低密度差，中高黏度体系，对于高密度差体系容易分层，不易实现均匀混合	设计新型混合器件结构或者管壁安装不同形状叶片结构
微反应器	利用不同方式的预混形式和不同几何结构的微通道实现混合	1.工业放大只能通过“数量放大”，不适用于较高产量需求的化学品工业生产 2.微通道尺寸狭小，目前增强微通道内部液体混合只能通过改变入口直径和方式、挡板数量和挡板之间的间隔距离等，这会导致微通道结构过于复杂，难以批量生产，实用性下降 3.微反应器内流体流动具有Reynolds数低和高表面张力的特点，对流扩散通常较弱，存在堵塞敏感性高的问题，特别是对于生产工艺中有固体反应物以及反应结晶体系^[126]	强吸放热快速反应	适用于低密度差，低黏度体系，对于有固体生成或高黏度体系易出现堵塞问题	优化微通道几何结构构型，优化两相流体接触方式
旋转填充床	利用高速旋转的填料将经过液体分布器的液体进行破碎分散	1.相对于径向运动，液体在填料中的横向漂移能力有限，导致液体在填料中的分布不均匀 2.旋转部件包括转子、轴承等需要保证密封，尤其是对于一些腐蚀性或危险化学反应，需要保证长期的可靠性^[127]	快速复杂反应	适用于高密度差体系和高黏度体系，对于有固体生成体系易出现堵塞问题	优化转子结构，优化预混合及液体分布器结构

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