三氟化氮精馏分离流程的设计与控制

doi:10.11949/0438-1157.20240738

摘要/Abstract

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

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

中图分类号:

TQ 117

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.

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.

图/表 18

表1 计算ΔTAC时使用的公式和参数

Table 1 Formulas and parameters used in calculating ΔTAC

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

表2 流程模拟进料组成和各物质常压沸点

Table 2 Feed composition of simulated processes and normal boiling points of components

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

图1 顺式分离序列流程优化框图

Fig.1 Block diagram of optimization for direct separation sequence process

图2 顺式分离序列流程的优化设计

Fig.2 Optimized design of direct separation sequence process

图3 反式分离序列流程的优化设计

Fig.3 Optimized design of indirect separation sequence process

图4 热集成顺式分离序列流程的优化设计

Fig.4 Optimized design of heat-integrated direct separation sequence process

图5 热集成反式分离序列流程的优化设计

Fig.5 Optimized design of heat-integrated indirect separation sequence process

表3 各流程比较

Table 3 Comparison of processes

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

图6 各流程的冷冻剂需求

Fig.6 Refrigerant requirements for processes

图7 各塔温度分布曲线

Fig.7 Temperature profiles for columns

表4 各塔灵敏板位置

Table 4 Sensitivity stages for columns

流程名称	塔名称	灵敏板位置
顺式分离序列流程	脱轻塔	3
顺式分离序列流程	脱重塔	16
热集成反式分离序列流程	脱重塔	11，13
热集成反式分离序列流程	脱轻塔	4

图8 顺式分离序列流程的动态控制结构

Fig.8 Dynamic control structure of direct separation sequence process

图9 热集成反式分离序列流程的动态控制结构

Fig.9 Dynamic control structure of heat-integrated indirect separation sequence process

表5 流量、压力和液位控制器参数

Table 5 Parameters of flow， pressure， and liquid level controllers

控制器	增益常数	积分时间/min
流量控制器	0.5	0.3
压力控制器	20	9999
液位控制器	12	20

表6 温度控制器参数

Table 6 Parameters of temperature controllers

流程	控制器	增益常数	积分时间/min
顺式分离序列	TC1	82.71	7.92
顺式分离序列	TC2	33.33	5.28
热集成反式分离序列	TC1	137.29	9.24
	TC2	21.29	5.28
	TC3	2.04	9.24

表7 添加组分扰动时的进料组成

Table 7 Feed composition with added component distribution

组分	+10%组分扰动时摩尔分数	-10%组分扰动时摩尔分数
H₂	0.5×10^-6	0.5×10^-6
N₂	0.4637334	0.560284
NF₃	0.5338881	0.4368175
CF₄	5×10^-6	5×10^-6
N₂O	0.002377	0.002897
CO₂	3.1×10^-6	3.1×10^-6
HF	0.6×10^-6	0.6×10^-6
H₂O	6×10^-6	6×10^-6

图10 顺式分离序列流程的动态响应

Fig.10 Dynamic responses of direct separation sequence process

图11 热集成反式分离序列流程的动态响应

Fig.11 Dynamic responses of heat-integrated indirect separation sequence process

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