氯化法钛白氧化反应器内颗粒碰撞行为及生成演化过程理论分析

doi:10.11949/0438-1157.20241476

化工学报 ›› 2025, Vol. 76 ›› Issue (7): 3316-3324.DOI: 10.11949/0438-1157.20241476

• 催化、动力学与反应器 • 上一篇下一篇

氯化法钛白氧化反应器内颗粒碰撞行为及生成演化过程理论分析

马谌睿¹^,²(), 王翔¹(), 宋民航¹^,³, 敬军⁴, 吴琼⁴, 黄云¹^,²()

^1.中国科学院过程工程研究所介科学与工程全国重点实验室，北京 100190
^2.中国科学院大学化学工程学院，北京 100049
^3.华北科技学院安全工程学院，河北廊坊 065201
^4.中信钛业股份有限公司，辽宁锦州 121005

收稿日期:2024-12-19 修回日期:2025-04-14 出版日期:2025-07-25 发布日期:2025-08-13
通讯作者: 王翔,黄云
作者简介:马谌睿（2001—），男，硕士研究生，machenrui23@ipe.ac.cn
基金资助:
中信集团重大科技创新项目(2022ZXKYA06100);国家自然科学基金项目(52130606)

Theoretical research on collision behavior and production evolution of titania particles in an industrial oxidation reactor of chlorination process

Chenrui MA¹^,²(), Xiang WANG¹(), Minhang SONG¹^,³, Jun JING⁴, Qiong WU⁴, Yun HUANG¹^,²()

^1.State Key Laboratory of Mesoscience and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^2.School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
^3.School of Safety Engineering, North China Institute of Science and Technology, Langfang 065201, Hebei, China
^4.CITIC Titanium Co. , Ltd. , Jinzhou 121005, Liaoning, China

Received:2024-12-19 Revised:2025-04-14 Online:2025-07-25 Published:2025-08-13
Contact: Xiang WANG, Yun HUANG

摘要/Abstract

摘要：

氯化法作为合成钛白粉（TiO₂）的主要工艺之一，具有产量大、自动化程度高和质量好的优势。以工业级氯化法钛白合成氧化反应器结构尺度及运行参数为基础，对氧化反应器内TiO₂颗粒的氧化、核化和碰撞等动力学事件以及TiO₂颗粒碰撞后的烧结过程进行了研究。结果表明，TiCl₄气相氧化是氧化反应器内的主要反应过程，氧化后生成的TiO₂分子瞬间（核化特征时间约为4.44×10^-13 s）成为凝结核；布朗运动是粒径≤600 nm TiO₂颗粒碰撞的主要机制，湍流作用是粒径>600 nm TiO₂颗粒碰撞的主要机制；碰撞后形成团聚体中初始粒径为50~100 nm。研究结果可为工业级真实反应器内颗粒群平衡模型的建立提供理论支撑。

关键词: 钛白粉, 碰撞, 团聚, 成核, 烧结

Abstract:

As one of the main processes for synthesizing titanium dioxide (TiO₂), the chloride process has the advantages of large output, high degree of automation and good quality. Based on operating parameters and structural dimensions of industrial titanium oxidation reactor in chlorination process, the TiO₂ particles evolutions, including oxidation, nucleation, collision and the sintering, were studied in this paper. The results indicate that the vapor-phase oxidation reaction of TiCl₄ is the dominant mechanism in the oxidation reactor. Following the oxidation reaction, TiO₂ molecules act as precursors for nucleation, with a characteristic nucleation time of approximately 4.44×10^-¹³ s. For TiO₂ particles smaller than 600 nm, Brownian motion is the primary mechanism driving particle collisions, while for particles larger than 600 nm, turbulence becomes the dominant mechanism. The initial particle size within collision-induced agglomerates is approximately 50—100 nm. These results will provide a theoretical support for the establishment of particles balance model in the industrial titanium oxidation reactor.

Key words: titanium dioxide, collision, agglomeration, nucleation, sintering

中图分类号:

TF 823

马谌睿, 王翔, 宋民航, 敬军, 吴琼, 黄云. 氯化法钛白氧化反应器内颗粒碰撞行为及生成演化过程理论分析[J]. 化工学报, 2025, 76(7): 3316-3324.

Chenrui MA, Xiang WANG, Minhang SONG, Jun JING, Qiong WU, Yun HUANG. Theoretical research on collision behavior and production evolution of titania particles in an industrial oxidation reactor of chlorination process[J]. CIESC Journal, 2025, 76(7): 3316-3324.

图/表 11

图1 氯化法钛白氧化反应器结构示意图

Fig.1 Configuration of the chlorination process titania reactor

图2 氧化反应器内颗粒转化过程

Fig.2 Particle formation and growth processes in the reactor

图3 氧化反应的反应速率常数

Fig.3 Reaction rate constants of oxidation reaction

图4 氧化反应特征时间

Fig.4 Characteristic time of oxidation reaction

图5 TiO2晶核的临界成核半径

Fig.5 Critical radius of nucleation of TiO2

图6 TiO2核化速率和核化特征时间

Fig.6 Nucleation rate and characteristic nucleation time of TiO2

图7 Kn随TiO2粒径的变化规律

Fig.7 Variation of Knudsen number with particle size of TiO2

图8 St随TiO2粒径的变化规律

Fig.8 Variation of Stokes number with particle size of TiO2

图9 碰撞核函数随TiO2粒径的变化规律

Fig.9 Variation of coagulation kernel with particle size of TiO2

图10 TiO2颗粒碰撞形成团聚体

Fig.10 Agglomeration formed by collision of TiO2 particles

图11 TiO2颗粒碰撞过程中特征时间分析

Fig.11 Characteristic collision time of TiO2 particles

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氯化法钛白氧化反应器内颗粒碰撞行为及生成演化过程理论分析

Theoretical research on collision behavior and production evolution of titania particles in an industrial oxidation reactor of chlorination process

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