氯化钛白氧化反应器结疤问题分析及数值模拟

doi:10.11949/0438-1157.20221332

摘要/Abstract

摘要：

氯化钛白生产工艺的核心是TiCl₄氧化反应器，而内部关键部位的结疤问题显著影响其长周期稳定生产。通过对工业氯化钛白氧化反应器疤料的分析与表征，探究了氧化反应器关键位置的结疤原因，进而使用ANSYS-Fluent软件对实际运行工况条件下的氧化反应器内部流场和壁面温度进行了计算流体力学(CFD)模拟。模拟结果表明，反应器壁面温度、内部流场等因素对反应器的结疤具有十分重要的影响。提高反应器关键位置壁面温度，能够显著改善结疤现象，为防止KCl和AlCl₃添加剂的沉积，反应器热氧区和TiCl₄进料环的壁面温度应分别高于770和178℃；而为避免新生成的TiO₂在反应器内表面的聚集，应减小或消除回流区，使得新生成的TiO₂尽快通过反应区。

关键词: 数值模拟, 计算流体力学, 氯化钛白, 氧化, 防结疤技术

Abstract:

TiCl₄ oxidation reactor is the key equipment in the chloride process of TiO₂, while the scarring inside the reactor significantly affects its long-period and consistent operation. In this study, the scarring reason in the industrial reactor was firstly investigated by composition analysis, and then, by the CFD simulation of the internal flow and wall temperature distribution, which is employed in the ANSYS-Fluent software package under the circumstance of actual operating conditions. The simulation results show that the reactor wall temperature, internal flow field and other factors have a very important influence on the scarring of the reactor. The wall temperature in the hot-oxygen zone should be higher than 770℃ and that in the TiCl₄ feeding ring should be higher than 178℃, respectively, for preventing the additives of KCl and AlCl₃ depositing on the inner wall of the reactor. In order to avoid the newly generated TiO₂to aggregate on the inner wall of the reaction zone, vortexes should be eliminated or reduced for the newly generated TiO₂with high-activity to timely pass through the reaction zone.

Key words: numerical simulation, CFD, chloride process of titanium dioxide, oxidation, anti-scarring technology

中图分类号:

TF 823

周艾然, 陆平, 夏建辉, 李冬勤, 郭杰, 杜明, 董立春. 氯化钛白氧化反应器结疤问题分析及数值模拟[J]. 化工学报, 2023, 74(4): 1499-1508.

Airan ZHOU, Ping LU, Jianhui XIA, Dongqin LI, Jie GUO, Ming DU, Lichun DONG. Scarring analysis and numerical simulation of TiCl₄ oxidation reactor in chloride process of titanium dioxide[J]. CIESC Journal, 2023, 74(4): 1499-1508.

图/表 14

图1 氧化反应器的三维模型

Fig.1 Three-dimensional schematic of the TiCl4 oxidation reactor

表1 氧化反应器模拟的边界条件

Table 1 Boundary conditions for CFD of the oxidation reactor

项目	温度/℃	流量/(kg/h)	压力/kPa
O₂气体	1600	1200	430
TiCl₄气体	450	5200	435
环前冷却水	25	550	230
反应器壁面初始温度	25	—	—

图2 结疤实物图

Fig.2 Scar samples at different scarring zones

图3 环前疤料的SEM图像

Fig.3 SEM images of the scar samples from the pre-ring zone

表2 环前疤料的EDX能谱结果

Table 2 EDX results of the scar samples from the pre-ring zone

样品位置	成分/%(质量分数)
样品位置	Si	Cl	K	Ti	Al
底层	0.81	36.63	50.46	5.42	0.51
中层	0.59	29.13	41.15	29.13	—
表层	0.54	0.34	0.38	98.74	—

图4 进料环内和进料环后疤料样品的SEM图像

Fig.4 SEM images of scar samples in the feed ring and from the post-ring zone

表3 环内和环后疤料样品的EDX结果

Table 3 EDX results of scar samples in the feed ring and from the post-ring zone

疤料位置	成分/%(质量分数)
疤料位置	O	Al	Si	Cl	Ni	K	Ti
进料环内	—	42.46	0.00	55.58	1.96	—	—
进料环后	0.59	29.13	0.54	0.33	—	0.38	98.74

图5 氧化反应器的壁面温度以及内部TiO2含量分布模拟图

Fig.5 Contour of the wall temperature and TiO2 distribution in the oxidation reactor

图6 氧化反应器内部的速度矢量分布

Fig.6 Velocity vector distribution in the oxidation reactor

表 4 动量比与环缝宽度对应关系

Table 4 Correlation of momentum ratio and feeding gap width

环缝宽度/mm	TiCl₄/O₂动量比
14	3.50
23	2.04
32	1.47
41	1.15

图7 不同环缝宽度对氧化反应器反应区流场的影响

Fig.7 Effect of feeding ring gap width on flow field inside the reaction zone of oxidation reactor

图8 不同环缝宽度对氧化反应器内二氧化钛物质分布的影响

Fig.8 Effect of feeding gap width on TiO2 distribution inside reaction reactor

图9 不同气体流量条件下氧化反应器内壁温度分布

Fig.9 Wall temperature distribution of oxidation reactor under different gas flow rates

表5 不同气体流量条件下壁面温度分布模拟结果

Table 5 Simulation results of wall temperature distribution under different gas flow rates

常温O₂流量/(kg/h)	进料环内壁面温度/℃		热氧区内壁面温度/℃
常温O₂流量/(kg/h)	最高	最低	最高	最低
240	440	242	650	248
120	443	295	720	347
60	445	355	825	475

参考文献 38

1	唐振宁. 钛白粉的生产与环境治理[M]. 北京: 化学工业出版社, 2000.
	Tang Z N. Production and Environmental Treatment of Titanium Dioxide[M]. Beijing: Chemical Industry Press, 2000.
2	唐文骞, 张锦宝. 硫酸法和氯化法钛白能耗分析与评述[J]. 无机盐工业, 2011, 43(6): 7-9.
	Tang W Q, Zhang J B. Energy consumption analysis and comments of manufacturing titanium dioxide by sulfuric acid process and chloride process[J]. Inorganic Chemicals Industry, 2011, 43(6): 7-9.
3	江书安, 刘建良, 李雪刚. 中国氯化钛白现状及发展趋势[J]. 有色金属设计, 2016, 43(3): 60-64.
	Jiang S A, Liu J L, Li X G. Current situations and development tendencies of titanium dioxide with chloride process of China[J]. Nonferrous Metals Design, 2016, 43(3): 60-64.
4	程易, 刘喆, 骆培成, 等. 氯化法钛白氧化反应器气体错流混合[J]. 化工学报, 2006, 57(12): 2840-2846.
	Cheng Y, Liu Z, Luo P C, et al. Gas cross-flow mixing in TiO₂ oxidation reactor of chloride process[J]. Journal of Chemical Industry and Engineering (China), 2006, 57(12): 2840-2846.
5	刘飞生, 谢刚, 于站良, 等. 氯化法生产钛白工艺的研究进展[J]. 材料导报, 2014, 28(15): 113-118.
	Liu F S, Xie G, Yu Z L, et al. Research and development of titania powders by chlorination technology[J]. Materials Review, 2014, 28(15): 113-118.
6	周峨, 郑少华, 袁章福, 等. 氯化法钛白氧化反应器结构分析与模拟[J]. 钛工业进展, 2004, 21(6): 35-39.
	Zhou E, Zheng S H, Yuan Z F, et al. Structure analysis and modeling on the oxidation reactor in the titanium white synthesis with chloride process[J]. Titanium Industry Progress, 2004, 21(6): 35-39.
7	Jr D W W, Stoddard C K, Rodman H G. Vapor phase production of titanium dioxide pigments: US3560152[P]. 1971-02-02.
8	Davis B R, Rahm J A. Process for manufacturing titanium dioxide: US4288418[P]. 1981-09-08.
9	Ackim K, Hans S, Hermann T. Means for production titanium dioxide pigment: US3540853[P]. 1970-11-17.
10	Portes P J, Mas R J, Richerd J H. Process for producing titanium dioxide by the vapor phase oxidation of titanium tetrachloride: US3499730[P]. 1970-03-10.
11	赵维安. 气相氧化法钛白反应器中物料混合试验[J]. 钢铁钒钛, 1987, 8(4): 25-30.
	Zhao W A. Material mixing test in titanium dioxide reactor by gas phase oxidation[J]. Iron Steel Vanadium Titanium, 1987, 8(4): 25-30.
12	赵维安. 管式反应器气相初始混合最佳条件的实验研究[J]. 化学工程, 1991, 19(4): 31-36, 3.
	Zhao W A. Experimental study on optimum condition of initial gases mixing in a tubular reactor[J]. Chemical Engineering (China), 1991, 19(4): 31-36, 3.
13	朱以华, 陈爱平, 李春忠, 等. 化学气相合成TiO₂过程中的冷壁凝结机理[J]. 华东理工大学学报, 1999, 25(4): 382-385.
	Zhu Y H, Chen A P, Li C Z, et al. Mechanism of powder deposition on cool wall during the process of chemical synthesis of TiO₂ in vapor phase[J]. Journal of East China University of Science and Technology, 1999, 25(4): 382-385.
14	施利毅, 李春忠, 房鼎业. 气相氧化法制备超细TiO₂粒子的研究进展[J]. 材料导报, 1998, 12(6): 23-26.
	Shi L Y, Li C Z, Fang D Y. Research advance in vapor-phase synthesis of ultrafine titania particles[J]. Materials Review, 1998, 12(6): 23-26.
15	Anderson J D, Wu S P, Liu Z M. Computational Fluid Dynamics[M]. Beijing: China Machine Press, 2007.
16	张兵兵, 李俊峰, 柳少军, 等. 氯化法钛白粉氧化反应器降低结疤因素研究[J]. 河南化工, 2014, 31(2): 54-55.
	Zhang B B, Li J F, Liu S J, et al. Study on factors of reducing scar in titanium dioxide oxidation reactor by chlorination method[J]. Henan Chemical Industry, 2014, 31(2): 54-55.
17	吕滨, 臧颖波, 张树峰, 等. TiCl₄气相氧化法制备金红石型TiO₂的工艺[J]. 应用化工, 2011, 40(8): 1326-1328.
	Lv B, Zang Y B, Zhang S F, et al. Producing rutile titanium dioxide via titanium tetrachloride vapor phase oxidation approach[J]. Applied Chemical Industry, 2011, 40(8): 1326-1328.
18	姜海波, 李春忠, 吕志敏, 等. 氯化钛白氧化反应器壁结疤机理[J]. 华东理工大学学报, 2001, 27(2): 152-156.
	Jiang H B, Li C Z, Lv Z M, et al. Sacling mechanism on the oxidation reactor wall in TiO₂ synthesis with chloride process[J]. Journal of East China University of Science and Technology, 2001, 27(2): 152-156.
19	刘强. 氯化法钛白技术氧化反应器内流场的数值研究[D]. 沈阳: 东北大学, 2017.
	Liu Q. Numerical study on flow field in oxidation reactor with chlorination titanium dioxide[D]. Shenyang: Northeastern University, 2017.
20	李亚东. 氯化法生产钛白中氧化反应器内流体动力学的研究及建模[D]. 昆明: 昆明理工大学, 2016.
	Li Y D. Study and modeling of fluid dynamics in oxidation reactor in titanium dioxide production by chlorination method[D]. Kunming: Kunming University of Science and Technology, 2016.
21	周艾然. 氯化法钛白氧化反应器结疤机理和除疤方法研究[J]. 钢铁钒钛, 2019, 40(2): 25-30.
	Zhou A R. Study on scar-formation mechanism and scar removal for oxidation reactor of TiO₂ by chlorination process[J]. Iron Steel Vanadium Titanium, 2019, 40(2): 25-30.
22	李春忠, 丛德滋, 吕志敏, 等. 氯化钛白氧化反应器: 00116465.1[P]. 2000-12-27.
	Li C Z, Cong D Z, Lv Z M, et al. Oxidation reactor of TiO2 by chlorination process: 00116465.1[P]. 2000-12-27.
23	Morris A J, Coe M D. System for increasing the capacity of a titanium dioxide producing process: US4803056[P]. 1989-02-07.
24	高殿荣, 王益群, 申功炘. DPIV技术及其在流场测量中的应用[J]. 液压气动与密封, 2001, 21(5): 30-33.
	Gao D R, Wang Y Q, Shen G X. DPIV technique and its application in flow field measurement[J]. Hydraulics Pnenmatics & Seals, 2001, 21(5): 30-33.
25	王汉封, 柳朝晖, 郭福水, 等. 用PIV数据估算槽道内湍流动能耗散率[J]. 化工学报, 2004, 55(7): 1066-1071.
	Wang H F, Liu Z H, Guo F S, et al. Estimation of turbulent kinetic energy dissipation rate in channel flow by PIV[J]. Journal of Chemical Industry and Engineering (China), 2004, 55(7):1066-1071.
26	马青山, 聂毅强, 包雨云, 等. 搅拌槽内三维流场的数值模拟[J]. 化工学报, 2003, 54(5): 612-618.
	Ma Q S, Nie Y Q, Bao Y Y, et al. Numerical simulation of hydrodynamics in stirred tank[J]. Journal of Chemical Industry and Engineering (China), 2003, 54(5): 612-618.
27	孙元智, 张清. 我国氯化法钛白生产技术的进展和今后的工作[J]. 钛工业进展, 2001, 18(3): 6-10.
	Sun Y Z, Zhang Q. Progress and future work of titanium dioxide production technology by chlorination in China[J]. Titanium Industry Progress, 2001, 18(3): 6-10.
28	高佳明, 王明, 马晓华, 等. 烧结温度对TiO₂/不锈钢中空纤维复合膜结构和性能的影响[J]. 化工学报, 2018, 69(11): 4879-4886.
	Gao J M, Wang M, Ma X H, et al. Effect of sintering temperature on structures and properties of TiO₂/stainless steel hollow fiber composite membrane[J]. CIESC Journal, 2018, 69(11): 4879-4886.
29	Zheng Y, Zhu J X, Wen J Z, et al. The axial hydrodynamic behavior in a liquid-solid circulating fluidized bed[J]. The Canadian Journal of Chemical Engineering, 1999, 77(2): 284-290.
30	金涌. 流态化工程原理[M]. 北京: 清华大学出版社, 2001.
	Jin Y. Fluidization Engineering Principles[M]. Beijing: Tsinghua University Press, 2001.
31	张霞, 胡芸, 龚倩, 等. 锰掺杂纳米二氧化钛的制备及其可见光催化性能[J]. 化工进展, 2010, 29(6): 1071-1074, 1079.
	Zhang X, Hu Y, Gong Q, et al. Mn-doped nano-TiO₂, preparation and photocatalytic reactivity under visible light irradiation[J]. Chemical Industry and Engineering Progress, 2010, 29(6): 1071-1074, 1079.
32	任盼锋, 海润泽, 李奇, 等. 流化床液固两相传质过程的模拟研究进展[J]. 化工学报, 2022, 73(1): 1-17.
	Ren P F, Hai R Z, Li Q, et al. Review of numerical study on liquid-solids two-phase mass transfer process in fluidized bed[J]. CIESC Journal, 2022, 73(1): 1-17.
33	朱凌云, 郎红方, 周帼彦, 等. 三叶孔板换热器壳程流动及传热数值模拟[J]. 化工学报, 2014, 65(3): 829-835.
	Zhu L Y, Lang H F, Zhou G Y, et al. Numerical simulation on shell side fluid flow and heat transfer in heat exchanger with trefoil-baffles[J]. CIESC Journal, 2014, 65(3): 829-835.
34	黄陆月, 刘畅, 许勇毅, 等. CDI二维浓度传质模型的建立以及实验验证[J]. 化工学报, 2022, 73(7): 2933-2943.
	Huang L Y, Liu C, Xu Y Y, et al. Development of CDI two-dimensional concentration mass transfer model and experimental validation[J]. CIESC Journal, 2022, 73(7): 2933-2943.
35	周少伟, 姜任秋, 宋福元, 等. 涡流管内流动与传热数值模拟[J]. 化工学报, 2006, 57(7): 1548-1552.
	Zhou S W, Jiang R Q, Song F Y, et al. Numerical simulation of flow field and heat transfer within a vortex tube[J]. Journal of Chemical Industry and Engineering (China), 2006, 57(7): 1548-1552.
36	闫云飞, 刘科, 张力. 强化换热凹槽管内流动与传热数值模拟[J]. 化工进展, 2010, 29(12): 2250-2253.
	Yan Y F, Liu K, Zhang L. Numerical investigation on flow and heat transfer in heat transfer enhancement fluted tube[J]. Chemical Industry and Engineering Progress, 2010, 29(12): 2250-2253.
37	胡宇鹏, 莫东鸣, 李友荣. 复杂几何结构腔体内冷水自然对流传热数值模拟[J]. 化工学报, 2014, 65(S1): 66-72.
	Hu Y P, Mo D M, Li Y R. Natural convection of water near its density maximum in cavity with complex geometry structure[J]. CIESC Journal, 2014, 65(S1): 66-72.
38	田增冬. 基于涡耗散模型的HIFiRE-2超燃冲压发动机仿真[J]. 电子测试, 2020(7): 60-61, 108.
	Tian Z D. Simulation of HIFiRE-2 Scramjet based on eddy dissipation model[J]. Electronic Test, 2020(7): 60-61, 108.

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