Design and control of nitrogen trifluoride distillation separation process

doi:10.11949/0438-1157.20240738

Abstract

Abstract:

Nitrogen trifluoride plays a critical role in the etching and cleaning processes in integrated circuit fabrication.Its product purity and purity stability are high, and the energy consumption is high. Focusing on the energy efficiency and controllability of the nitrogen trifluoride distillation process, the separation sequences, thermal integration, and dynamic control of the process were systematically studied. Based on the existing industrial direct separation sequence process, the indirect separation sequence process, the heat-integrated direct separation sequence process, and the heat-integrated indirect separation sequence process were proposed. Simulation results indicate that the heat-integrated indirect separation sequence process is optimal, reducing the total annual cost by 96.4×10⁴ CNY compared to the direct separation sequence process with an annual capacity of 120000 kmol. A dynamic control structure study for the direct separation sequence process and the heat-integrated indirect separation sequence process was conducted. The results show that the proposed control structures exhibit excellent control performance for disturbances in feed flow and composition. The findings provide reference on energy-saving and control strategies for the industrial nitrogen trifluoride distillation process.

Key words: distillation, purification, separation, dynamic simulation

摘要：

三氟化氮在集成电路制造的刻蚀和清洗工艺中起到关键作用，其产品纯度和纯度稳定性要求高，精馏过程能耗大。以三氟化氮精馏过程的节能和可控性为研究对象系统研究了三氟化氮精馏过程的分离序列、热集成和过程控制：在工业现有的顺式分离序列流程基础上提出反式分离序列流程、热集成顺式分离序列流程和热集成反式分离序列流程，模拟计算结果表明热集成反式分离序列流程为较优流程，在年处理量为120000 kmol的情况下与顺式分离序列流程相比年度总成本降低了96.4万元；对顺式分离序列流程和热集成反式分离序列流程进行了动态控制结构研究，结果表明提出的控制结构对进料流量和组成的干扰具有良好的控制性能。研究结果可为工业化的三氟化氮精馏过程的节能和控制提供参考。

关键词: 精馏, 纯化, 分离, 动态模拟

CLC Number:

TQ 117

Xiangjun MENG, Linrui YANG, Lipei PENG, Xiankui YANG, Yingxi HUA, Renren ZHANG, Kaitian ZHENG, Chunjian XU. Design and control of nitrogen trifluoride distillation separation process[J]. CIESC Journal, 2025, 76(2): 707-717.

孟祥军, 杨林睿, 彭立培, 杨献奎, 花莹曦, 张人仁, 郑凯天, 许春建. 三氟化氮精馏分离流程的设计与控制[J]. 化工学报, 2025, 76(2): 707-717.

Figures/Tables 18

References 28

7	Tasaka A. Electrochemical synthesis and application of NF₃ [J]. Journal of Fluorine Chemistry, 2007, 38(4): 296-310.
8	周言, 钟强, 刘倩, 等. NF₃与CF₄分离纯化技术路线研究进展[J]. 应用化工, 2023, 52(1): 266-272.
	Zhou Y, Zhong Q, Liu Q, et al. Progress on technology route for separation and purification of NF₃ and CF₄ [J]. Applied Chemical Industry, 2023, 52(1): 266-272.
9	彭立培, 王少波, 李绍波, 等. 三氟化氮纯化方法进展[J]. 化学工业与工程, 2007, 24(1): 86-90, 94.
	Peng L P, Wang S B, Li S B, et al. Review on process for purifying nitrogen trifluoride[J]. Chemical Industry and Engineering, 2007, 24(1): 86-90, 94.
10	杜伟华. 三氟化氮萃取精馏工艺研究[J]. 低温与特气, 2009, 27(2): 14-17.
	Du W H. Study on NF₃ extractive distillation process[J]. Low Temperature and Specialty Gases, 2009, 27(2): 14-17.
11	Hassanalizadeh R, Nelson W M, Naidoo B K, et al. Purification of nitrogen trifluoride by physical separation[J]. Fluid Phase Equilibria, 2022, 560: 113405.
12	Zhang M H, Liu L, Li Q H, et al. Theoretical design of MOFs and PSA process for efficient separation of CF₄/NF₃ [J]. Industrial & Engineering Chemistry Research, 2023, 62(18): 7103-7113.
13	Branken D J, Krieg H M, Le Roux J P, et al. Separation of NF₃ and CF₄ using amorphous glassy perfluoropolymer Teflon AF and Hyflon AD60 membranes[J]. Journal of Membrane Science, 2014, 462: 75-87.
14	Flores O A, Cárdenas J C, Hernández S, et al. Thermodynamic analysis of thermally coupled distillation sequences[J]. Industrial & Engineering Chemistry Research, 2003, 42(23): 5940-5945.
15	Li Q, Finn A J, Doyle S J, et al. Synthesis and optimization of energy integrated advanced distillation sequences[J]. Separation and Purification Technology, 2023, 315: 123717.
16	Yang A, Su Y, Shi T, et al. Energy-efficient recovery of tetrahydrofuran and ethyl acetate by triple-column extractive distillation: entrainer design and process optimization[J]. Frontiers of Chemical Science and Engineering, 2022, 16(2): 303-315.
1	Ramachandran P V, Reddy G V. Preparative-scale one-pot syntheses of hexafluoro-1,3-butadiene[J]. Journal of Fluorine Chemistry, 2008, 129(5): 443-446.
2	Choi R, Onishi K, Kang C S, et al. Effects of deuterium anneal on MOSFETs with HfO₂ gate dielectrics[J]. IEEE Electron Device Letters, 2003, 24(3): 144-146.
3	Miyazaki T, Mori I, Umezaki T, et al. NF₃ synthesis using ClF₃ as a mediator[J]. Journal of Fluorine Chemistry, 2019, 219: 55-61.
4	Yeom H J, Choi D H, Lee Y S, et al. Plasma density measurement and downstream etching of silicon and silicon oxide in Ar/NF₃ mixture remote plasma source[J]. Plasma Science and Technology, 2019, 21(6): 064007.
5	Ianno N J, Greenberg K E, Verdeyen J T, et al. Comparison of the etching and plasma characteristics of discharges in CF₄ and NF₃ [J]. Journal of the Electrochemical Society, 1981, 128(10): 2174-2179.
6	张振, 李梅, 李贤武, 等. 电解法制备NF₃的研究现状[J]. 低温与特气, 2024, 42(2): 1-6.
	Zhang Z, Li M, Li X W, et al. Current status of NF₃preparation by electrolysis[J]. Low Temperature and Specialty Gases, 2024, 42(2): 1-6.
17	Zhai J, Chen X, Sun X Q, et al. Economically and thermodynamically efficient pressure-swing distillation with heat integration and heat pump techniques[J]. Applied Thermal Engineering, 2023, 218: 119389.
18	Mao W X, Cao Y Q, Shen R C, et al. Heat integrated technology assisted pressure-swing distillation for the mixture of ethylene glycol and 1,2-butanediol[J]. Separation and Purification Technology, 2020, 241: 116740.
19	Shi T, Chun W, Yang A, et al. Optimization and control of energy saving side-stream extractive distillation with heat integration for separating ethyl acetate-ethanol azeotrope[J]. Chemical Engineering Science, 2020, 215: 115373.
20	Huang J H, Chen Y X, Zhang Q J, et al. Dynamic control strategy of the ternary azeotrope separation process assisted by reactive-extractive distillation for ethyl acetate/isopropanol/water[J]. Chemical Engineering and Processing-Process Intensification, 2024, 199: 109762.
21	Feng Z M, Wang W H, Xu D, et al. Dynamic controllability of temperature difference control for the operation of double liquid-only side-stream distillation[J]. Computers & Chemical Engineering, 2022, 164: 107870.
22	Yang A, Shen W F, Wei S A, et al. Design and control of pressure-swing distillation for separating ternary systems with three binary minimum azeotropes[J]. AIChE Journal, 2019, 65(4): 1281-1293.
23	Douglas J M. Conceptual Design of Chemical Processes[M]. New York: McGraw-Hill, 1998.
24	Luyben W L. Estimating refrigeration costs at cryogenic temperatures[J]. Computers & Chemical Engineering, 2017, 103: 144-150.
25	Luo H T, Liang K, Li W S, et al. Comparison of pressure-swing distillation and extractive distillation methods for isopropyl alcohol/diisopropyl ether separation[J]. Industrial & Engineering Chemistry Research, 2014, 53(39): 15167-15182.
26	Shan B M, Sun D F, Zheng Q, et al. Dynamic control of the pressure-swing distillation process for THF/ethanol/water separation with and without thermal integration[J]. Separation and Purification Technology, 2021, 268: 118686.
27	Luyben W L. Distillation Design and Control Using Aspen Simulation[M]. 2nd ed. Hoboken: Wiley, 2013.
28	Luyben W L. Tuning proportional-integral-derivative controllers for integrator/deadtime processes[J]. Industrial & Engineering Chemistry Research, 1996, 35(10): 3480-3483.

参数	公式或数据	单位
冷凝器
传热系数U_C	0.852	kW/(m²·K)
换热温差ΔT	T_塔顶-T_冷冻剂	K
换热面积A	Q_C/(U_C×ΔT)	m²
设备费用	7296×7.14×A^0.65	CNY
再沸器
传热系数U_R	0.568	kW/(m²·K)
换热温差ΔT	T_冷冻剂-T_塔底	K
换热面积A	Q_R/(U_R×ΔT)	m²
设备费用	7296×7.14×A^0.65	CNY
塔设备
设备费用	17640×7.14×D^1.066×L^0.802	CNY
塔高L	1.2×0.609×(理论板数-2)	m
塔径D	由Aspen的Column internals计算	m
能耗费用
冷冻剂（-75℃）	298.5	CNY/GJ
冷冻剂（-150℃）	963.9	CNY/GJ
冷冻剂（-175℃）	1827.8	CNY/GJ
年能耗费用	8000×3600×Q_C×10^-6×冷冻剂价格	CNY/a

参数	公式或数据	单位
冷凝器
传热系数U_C	0.852	kW/(m²·K)
换热温差ΔT	T_塔顶-T_冷冻剂	K
换热面积A	Q_C/(U_C×ΔT)	m²
设备费用	7296×7.14×A^0.65	CNY
再沸器
传热系数U_R	0.568	kW/(m²·K)
换热温差ΔT	T_冷冻剂-T_塔底	K
换热面积A	Q_R/(U_R×ΔT)	m²
设备费用	7296×7.14×A^0.65	CNY
塔设备
设备费用	17640×7.14×D^1.066×L^0.802	CNY
塔高L	1.2×0.609×(理论板数-2)	m
塔径D	由Aspen的Column internals计算	m
能耗费用
冷冻剂（-75℃）	298.5	CNY/GJ
冷冻剂（-150℃）	963.9	CNY/GJ
冷冻剂（-175℃）	1827.8	CNY/GJ
年能耗费用	8000×3600×Q_C×10^-6×冷冻剂价格	CNY/a

组分	摩尔分数	常压沸点/℃
H₂	0.5×10^-6	-252.8
N₂	0.511995	-195.8
NF₃	0.4853528	-129.1
CF₄	5×10^-6	-128.1
N₂O	0.002637	-88.5
CO₂	3.1×10^-6	-78.5
HF	0.6×10^-6	19.5
H₂O	6×10^-6	100.0

组分	摩尔分数	常压沸点/℃
H₂	0.5×10^-6	-252.8
N₂	0.511995	-195.8
NF₃	0.4853528	-129.1
CF₄	5×10^-6	-128.1
N₂O	0.002637	-88.5
CO₂	3.1×10^-6	-78.5
HF	0.6×10^-6	19.5
H₂O	6×10^-6	100.0

参数	顺式分离序列流程	反式分离序列流程	热集成顺式分离序列流程	热集成反式分离序列流程
冷凝器总负荷/kW	-44.1	-43.8	-31.6	-26.1
再沸器总负荷/kW	27.2	5.7	26.9	9.6
ΔTIC/万元	35.0	22.8	35.7	30.0
TOC/（万元/年）	226.3	186.4	160.7	132.1
ΔTAC/（万元/年）	238.5	194.2	172.1	142.1