三氟化硼低温精馏法富集10B工艺的模拟

doi:10.16085/j.issn.1000-6613.2025-0305

摘要/Abstract

摘要：

¹⁰B是一种极为重要的稳定同位素，具有很强的吸收中子能力，因此其在核电领域应用广泛。工业上普遍采用化学交换法生产¹⁰B，但该方法存在产量低、络合剂毒性大、设备腐蚀严重等问题，而低温精馏法具有产量高、无污染、运行稳定的技术优势。为了满足核电发展对高丰度¹⁰B产品的大量需求，研究开发低温精馏法生产¹⁰B的工艺能够在提高产量的同时减少对设备的腐蚀，具有可观的经济价值。本文结合中国原子能科学研究院低温精馏法分离硼同位素的中试实验，采用经典化工模拟软件Aspen Plus模拟二塔级联的低温精馏塔分离¹⁰BF₃和¹¹BF₃同位素体系的过程，经过计算获得了BF₃同位素化合物的物性参数，建立了硼同位素分离的工艺模型。采用理想（IDEAL）和Peng-Robinson（PR）两种物性方法进行模拟，其中PR状态方程法修正了气相非理想性和液相相互作用，其模拟结果（误差3.04%）显著优于理性模型（误差8.99%）。模拟结果表明，降低操作压力、减小出料量、增加回流比和理论塔板数均可以增大塔底产品丰度，其中增加理论塔板数对丰度的提升效果更显著。本文的研究结果可以为后续¹⁰B同位素工业化生产提供理论指导。

关键词: 低温精馏法, 硼同位素, Aspen Plus, 分离, 计算机模拟, 气液平衡

Abstract:

¹⁰B is an extremely important stable isotope with a strong ability to absorb neutrons, and thus is widely used in the nuclear power field. The chemical exchange method is commonly used in industry to produce ¹⁰B, but this method has problems such as low output, high toxicity of complexing agents, and severe equipment corrosion. In contrast, the low-temperature distillation method has the technical advantages of high output, no pollution, and stable operation. To meet the large demand for high-abundance ¹⁰B products in nuclear power development, the research and development of the low-temperature distillation method for producing ¹⁰B can increase output while reducing equipment corrosion, which has considerable economic value. This paper, in combination with the pilot-scale test of boron isotope separation by low-temperature distillation at the China Institute of Atomic Energy, used the classic chemical engineering simulation software Aspen Plus to simulate the process of separating ¹⁰BF₃ and ¹¹BF₃ isotopes in a two-column cascade low-temperature distillation tower. Through calculation, the physical property parameters of BF₃ isotopic compounds were obtained, and a process model for boron isotope separation was established. Two physical property methods, IDEAL and PR, were used for simulation. Among them, the PR equation of state method corrected the non-ideality of the gas phase and the interaction in the liquid phase, and its simulation results (error 3.04%) were significantly better than the ideal model (8.99%). The simulation results showed that reducing the operating pressure, decreasing the feed rate, increasing the reflux ratio and the number of theoretical plates could all increase the abundance of the bottom product, among which increasing the number of theoretical plates had a more significant effect on the abundance improvement. The research results of this paper could provide theoretical guidance for the subsequent industrial production of ¹⁰B isotopes.

Key words: cryogenic distillation, boron isotope, Aspen Plus, separation, computer simulation, vapor liquid equilibrium

中图分类号:

TQ028.1

郭栩豪, 叶一鸣, 齐鑫, 胡石林, 张平柱. 三氟化硼低温精馏法富集¹⁰B工艺的模拟[J]. 化工进展, 2025, 44(S1): 74-83.

GUO Xuhao, YE Yiming, QI Xin, HU Shilin, ZHANG Pingzhu. Simulation of enrichment of ¹⁰B by cryogenic distillation of boron trifluoride[J]. Chemical Industry and Engineering Progress, 2025, 44(S1): 74-83.

图/表 16

表1 BF3同位素组分安托因方程参数一览表

参数	¹⁰BF₃	¹¹BF₃
C₁	168.504	168.613
C₂	-12179.500	-12667.000
C₃	47.325	51.412
C₄	-0.131	-0.128
C₅	-15.831	-15.636
C₆	3.543×10^-7	1.580×10^-7
C₇	3.058	3.187
C₈	144.790	144.790
C₉	260.900	260.900

表2 BF3同位素分子物性参数计算值

参数	¹⁰BF₃	¹¹BF₃
分子量	67	68
正常沸点/K	172.84	172.71
临界温度/K	260.90	260.68
临界压力/kPa	4991.97	4977.64
偏心因子	0.4349	0.4302

图1 10BF3双塔级联实验装置B—再沸器；C—冷凝器；LNG—液化天然气；VJ—真空夹套；DC—低温精馏塔；TP—涡轮分子泵；VP—真空泵

图2 10BF3分离工艺流程

图3 温度-富集因子对应关系[12]

表3 CD1和CD2全回流工况下参数计算结果

精馏塔编号	塔顶丰度 $x T$ （摩尔分数）/%	塔底丰度 $x B$ （摩尔分数）/%	分离因子S	全塔平均相对挥发度 $α$	最小理论塔板数N
CD1	14.2	30.1	2.602	1.00716	134
CD2	13.4	31.9	3.027	1.00778	142

表3 CD1和CD2全回流工况下参数计算结果

精馏塔编号	塔顶丰度 $x T$ （摩尔分数）/%	塔底丰度 $x B$ （摩尔分数）/%	分离因子S	全塔平均相对挥发度 $α$	最小理论塔板数N
CD1	14.2	30.1	2.602	1.00716	134
CD2	13.4	31.9	3.027	1.00778	142

表4 Aspen Plus模拟参数初值一览表

参数	CD1	CD2
¹⁰BF₃进料组成（摩尔分数）/%	19.8	31.8
填料高度/m	180	180
理论塔板数/块	180	180
进料流量/kg·h^-1	1.065	0.36
塔底流量/kg·h^-1	0.36	0.012
进料压力/kPa	225	180
操作压力/kPa	180	150
塔釜加热功率/kW	7	7
塔顶冷凝形式	全冷凝

图4 10BF3-11BF3溶液的T-y-x图

图5 α为定值的理想溶液恒压相平衡曲线

表5 模拟结果与实验结果对比

结果及对比	一级塔		二级塔
结果及对比	塔顶¹⁰BF₃丰度	塔底¹⁰BF₃丰度	塔顶¹⁰BF₃丰度	塔底¹⁰BF₃丰度
实验结果/%	12.60	34.00	32.90	69.00
IDEAL模拟结果/%	13.63	31.85	30.78	62.80
IDEAL相对误差/%	8.17	6.32	6.44	8.99
PR模拟结果/%	12.36	34.31	33.04	71.10
PR相对误差/%	1.90	0.91	0.43	3.04

图6 CD1内丰度分布

图7 CD2内丰度分布

图8 原料进料量对产品丰度的影响

图9 产品出料量对产品丰度的影响

图10 CD2塔顶压力对产品丰度的影响

图11 理论塔板数和回流比对产品丰度的影响

参考文献 26

[1]	GOULD Paula. Medical isotope shortage reaches crisis level[J]. Nature, 2009, 460(7253): 312-313.
[2]	AGGARWAL Jugdeep, Judith HABICHT-MAUCHE, JUAREZ Chelsey. Application of heavy stable isotopes in forensic isotope geochemistry: A review[J]. Applied Geochemistry, 2008, 23(9): 2658-2666.
[3]	A Yu SMIRNOV, SULABERIDZE G A, XIE Q, et al. Design of cascade with locally enlarged flow for enrichment of intermediate components of multi-isotope mixtures[J]. Chemical Engineering Research and Design, 2015, 95: 47-54.
[4]	LEMARCHAND D, GAILLARDET J, GÖPEL C, et al. An optimized procedure for boron separation and mass spectrometry analysis for river samples[J]. Chemical Geology, 2002, 182(2/3/4): 323-334.
[5]	HEALY R M, PALKO A A. Separation of boron isotopes. Ⅰ. Boron trihalide addition compounds[J]. The Journal of Chemical Physics, 1958, 28(2): 211-213.
[6]	郑学家. 核工业用硼化物[M]. 北京: 化学工业出版社, 2015.
	ZHENG Xuejia. Boride for nuclear industry[M]. Beijing: Chemical Industry Press, 2015.
[7]	费罗杰. 漳州能源富集¹⁰B应用的可行性分析[J]. 中国核电, 2022, 15(6): 888-892.
	FEI Luojie. Feasibility analysis of Zhangzhou energy enrichment of boron-10 application[J]. China Nuclear Power, 2022, 15(6): 888-892.
[8]	韩檬, 赵博, 张卫江. 硼-10酸的合成[J]. 化学工程, 2007, 35(8): 70-73.
	HAN Meng, ZHAO Bo, ZHANG Weijiang. Synthesis of boric-10 acid[J]. Chemical Engineering (China), 2007, 35(8): 70-73.
[9]	周贝霖, 胡石林. 硼同位素分离研究进展[J]. 化学工程与技术, 2023(3): 161-173.
	ZHOU Beilin, HU Shilin. Research progress in boron isotope separation[J]. Chemical Engineering and Technology, 2023(3): 161-173.
[10]	张廷克, 李闽榕, 尹卫平. 中国核能发展报告(2022)[M]. 北京: 社会科学文献出版社, 2022: 219.
	ZHANG Tingke, LI Minrong, YIN Weiping. China nuclear energy development report (2022)[M]. Beijing: Social Sciences Academic Press, 2022: 219.
[11]	王之肖, 谢恩飞, 牛文华, 等. “华龙一号”富集硼选择技术研究[J]. 核科学与工程, 2024, 44(6): 1337-1342.
	WANG Zhixiao, XIE Enfei, NIU Wenhua, et al. Enrichment boron selection technology for “Hualong One”[J]. Nuclear Science and Engineering, 2024, 44(6): 1337-1342.
[12]	AMIRKHANOVA I B, BORISOV A V, GVERDTSITELI I G, et al. Relative difference of the vapour pressures of ¹¹BF₃ and ¹⁰BF₃ [J]. Journal of Nuclear Energy Parts A/B Reactor Science and Technology, 1966, 20(7): 591-597.
[13]	IVANOV Vladimir A, KATALNIKOV Sergei G. Physico-chemical and engineering principles of boron isotopes separation by using BF₃-anisole. BF₃ system[J]. Separation Science and Technology, 2001, 36(8/9): 1737-1768.
[14]	SONG Shuang, MU Yujun, LI Xiaofeng, et al. Advances in boron-10 isotope separation by chemical exchange distillation[J]. Annals of Nuclear Energy, 2010, 37(1): 1-4.
[15]	SEVRYUGOVA N N, UVAROV O V, ZHAVORONKOV N M. Separation of the stable isotopes of boron[J]. The Soviet Journal of Atomic Energy, 1961, 9(2): 614-629.
[16]	JOSEPH M, MANORAVI P. Boron isotope enrichment in nanosecond pulsed laser-ablation plume[J]. Applied Physics A, 2003, 76(2): 153-156.
[17]	ZHAO Hanxue, GAO Ruichang, BAI Peng. Advances in boron isotope separation by ion exchange chromatography[J]. Asian Journal of Chemistry, 2014, 26(8): 2187-2190.
[18]	李虎林, 巨永林, 李良君, 等. 低温精馏分离稳定同位素¹³C的模拟优化研究[J]. 原子能科学技术, 2009, 43(S1): 54-58.
	LI Hulin, JU Yonglin, LI Liangjun, et al. Simulation and optimization of stable isotope ¹³C separation by carbon monoxide cryogenic distillation[J]. Atomic Energy Science and Technology, 2009, 43(S1): 54-58.
[19]	黄华江. 实用化工计算机模拟——MATLAB在化学工程中的应用[M]. 北京: 化学工业出版社, 2004.
	HUANG Huajiang. Practical computer simulation of chemical engineering: Application of MATLAB in chemical engineering[M]. Beijing: Chemical Industry Press, 2004.
[20]	UREY Harold C. The thermodynamic properties of isotopic substances[J]. Journal of the Chemical Society (Resumed), 1947: 562-581.
[21]	田叶盛, 李虎林, 姜永悦, 等. 稳定同位素¹³C分离二塔级联耦合优化设计与实验研究[J]. 同位素, 2016, 29(3): 152-157.
	TIAN Yesheng, LI Hulin, JIANG Yongyue, et al. Coupling optimization design and experimental study on stable isotope ¹³C separation of the double-stage cascade[J]. Journal of Isotopes, 2016, 29(3): 152-157.
[22]	陈玉岩, 秦川江, 肖斌, 等. 减压精馏分离稳定同位素¹⁸O的模拟优化研究[J]. 原子能科学技术, 2012, 46(5): 533-536.
	CHEN Yuyan, QIN Chuanjiang, XIAO Bin, et al. Simulation and optimization of stable isotope ¹⁸O separation by water vacuum distillation[J]. Atomic Energy Science and Technology, 2012, 46(5): 533-536.
[23]	JOBACK K G, REID R C. Estimation of pure-component properties from group-contributions[J]. Chemical Engineering Communications, 1987, 57(1/2/3/4/5/6): 233-243.
[24]	ARMSTRONG D E, BRIESMEISTER A C, MCINTEER B, et al. Carbon-13 production plant using carbon monoxide distillation[R]. Los Alamos Scientific Lab., 1970.
[25]	吉永喆, 巨永林, 李虎林. 同位素¹³C分离二塔级联模拟研究[J]. 同位素, 2016, 29(2): 103-107.
	JI Yongzhe, JU Yonglin, LI Hulin. Simulation research of isotope ¹³C separation by double-stage cascade[J]. Journal of Isotopes, 2016, 29(2): 103-107.
[26]	FENSKE M R. Fractionation of straight-run Pennsylvania gasoline[J]. Industrial & Engineering Chemistry, 1932, 24(5): 482-485.

三氟化硼低温精馏法富集¹⁰B工艺的模拟

Simulation of enrichment of ¹⁰B by cryogenic distillation of boron trifluoride

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 16

参考文献 26

相关文章 15

编辑推荐

Metrics

本文评价

[1]	武锦怡, 赵睿恺, 邓帅, 张家麒, 高春霄, 刘葳桦, 赵力. 混合绝缘气体变温吸附分离回收SF₆的数值模拟[J]. 化工进展, 2025, 44(S1): 19-28.
[2]	邹先志, 廖亚龙, 杨双宇. 铜电解液净化除杂研究进展[J]. 化工进展, 2025, 44(S1): 492-503.
[3]	王晓光, 董青, 郎文丽, 洪翔鑫, 黄振祥, 谭凤玉, 雷以柱, 余子夷. 超低浓度甲烷减排与资源化利用研究进展[J]. 化工进展, 2025, 44(9): 5363-5376.
[4]	秦睦轩, 张玮, 王盈锦, 李梓良. 基于迁移学习的微反应器大气液比Aspen模型构建[J]. 化工进展, 2025, 44(9): 4908-4916.
[5]	符红梅, 刘定华, 刘晓勤. MOF材料在芳烃同分异构体分离中的研究进展[J]. 化工进展, 2025, 44(9): 5006-5017.
[6]	洪凯, 樊欢, 田佳, 张荥斐. 硫化沉淀法处理铜砷多金属酸性废水研究进展[J]. 化工进展, 2025, 44(9): 5301-5314.
[7]	杜璇, 王战宏, 郑彬, 许卫, 王硕, 石鹏, 高国. 钴铁酸浸液分离及电池级磷酸铁回收技术进展[J]. 化工进展, 2025, 44(9): 5327-5338.
[8]	汪国超, 丁晖殿, 师丽, 李强, 夏涛, 苑杨. 复合精馏序列的温度推断控制[J]. 化工进展, 2025, 44(8): 4720-4731.
[9]	冯思瑶, 潘艳秋, 马佳宁, 孙延吉. 柴油分子重构模型及分子水平柴油加氢精制反应动力学模型构建[J]. 化工进展, 2025, 44(8): 4852-4861.
[10]	龙凯, 陈飞国, 熊勤钢. 低雷诺数高克努森数下的双圆柱绕流阻力/升力系数[J]. 化工进展, 2025, 44(8): 4526-4535.
[11]	杨傲, 邓苇, 黎勇, 罗婧, 王梓霖, 张俊, 申威峰. 基于热力学拓扑理论的三塔变压精馏分离四氢呋喃/甲醇/乙醇多目标优化设计[J]. 化工进展, 2025, 44(8): 4582-4593.
[12]	高岩, 李永帅, 李高洋, 潘慧, 凌昊. Agrawal分壁精馏塔的动态控制[J]. 化工进展, 2025, 44(8): 4594-4605.
[13]	杨证禄, 杨立峰, 路晓飞, 锁显, 张安运, 崔希利, 邢华斌. 机器学习加速多孔吸附剂筛选发现的研究进展[J]. 化工进展, 2025, 44(8): 4288-4301.
[14]	陈倩, 仝坤, 谢加才, 邵志国, 聂凡, 李成涛. 含聚油泥处理技术研究进展[J]. 化工进展, 2025, 44(7): 4158-4168.
[15]	杨文明, 谢林生, 王玉, 马玉录, 李果. SPH-DEM耦合模拟方法在啮合型双螺杆挤出机中的应用[J]. 化工进展, 2025, 44(7): 3748-3756.