容器内自蔓延高温合成固化过程的热力学数值模拟

doi:10.11949/j.issn.0438-1157.20171111

摘要/Abstract

摘要：

自蔓延高温合成固化是一种利用氧化还原反应放热处理高放废物煅烧灰、污染土壤等固体放射性废物的方法，在密封容器内对放射性废物采用自蔓延高温合成固化技术可有效提高产物的致密度并控制有害气溶胶的扩散。通过分析自蔓延化学反应机理和过程，建立容器内自蔓延高温合成固化数值模拟模型，对固化过程容器内温度-压力变化特征进行分析。利用COMSOL有限元分析软件，确定模型尺寸、单元类型和边界条件，计算得到点火后7200 s的容器内温度和压力随时间变化曲线。与相同条件的容器内SHS固化实验测量结果对比分析，数值模拟与实测情况一致性较强，能够较好反映SHS固化过程点火、燃烧、熄火、保温的四阶段性特征；模拟结果可作为容器安全性设计的参考数据。

关键词: 自蔓延高温合成固化, 热力学, 数值模拟, COMSOL, 废物处理, 安全

Abstract:

Self-propagating high-temperature synthesis (SHS) is a high-efficiency and low-cost thermal technology that uses the energy released during exothermic oxidation-reduction reactions to immobilize solid radioactive wastes, such as high-level radioactive calcined ash and contaminated soil. It is effective to increase the product's density and control the diffusion of the hazardous aerosol by using SHS immobilization in a sealed container. By the analysis of the chemical reaction mechanism and process of the SHS immobilization, the numerical simulation model for the in-container treatment was established and the variation characteristics of the temperature and pressure during the immobilization were studied. By using the COMSOL finite element analysis software with the preset model size, unit type and boundary condition, the in-container temperature-time and pressure-time variation curves in 7200 s after SHS ignition were solved. The simulation is compared with the experiment data in the same in-container immobilization condition, and the results have strong consistency and show staged difference among ignition, burning, flameout and thermal insulation of the SHS immobilization process. The numerical simulation conclusion could act as the reference data for the container safety design.

Key words: self-propagating high-temperature synthesis immobilization, thermodynamics, numerical simulation, COMSOL, waste treatment, safety

中图分类号:

TQ021.2

陶钧, 张继军, 毛仙鹤, 赵建伟, 张东亮, 蔡溪南. 容器内自蔓延高温合成固化过程的热力学数值模拟[J]. 化工学报, 2018, 69(5): 1846-1853.

TAO Jun, ZHANG Jijun, MAO Xianhe, ZHAO Jianwei, ZHANG Dongliang, CAI Xinan. Thermodynamics analysis of in-container self-propagating high-temperature synthesis immobilization process using numerical simulation[J]. CIESC Journal, 2018, 69(5): 1846-1853.

参考文献 30

[1]	Ojovan M I, Lee W E, Sobolev I A, et al. Thermochemical processing using powder metal fuels of radioactive and hazardous waste[J]. Journal of Process Mechanical Engineering, 2004, 218(4):261-269.
[2]	殷声. 燃烧合成[M]. 北京:冶金工业出版社, 2004:1-45. YIN S. Combustion Synthesis[M]. Beijing:Metallurgic Industry Press, 2004:1-45.
[3]	Galina X, George V. An overview of some environmental applications of self-propagating high-temperature synthesis[J]. Advances in Environmental Research, 2001, 5:117-128.
[4]	Ojovan M I, Lee W E. An Introduction to Nuclear Waste Immobilization[M]. London:Elsevier, 2005:229-232.
[5]	Karlina O K, Varlackova G A, Ojovan M I, et al. Conditioning of radioactive ash residue in a wave of solid-phase exothermal reactions[J]. Atomic Energy, 2001, 90(1):43-48.
[6]	张瑞珠, 郭志猛, 高峰. 用SHS将核废物固定于类矿石[J]. 稀有金属, 2005, 29(1):25-29. ZHANG R Z, GUO Z M, GAO F. Solidification of HLW into mineral-like materials by SHS method[J]. Chinese Journal of Rare Metals, 2005, 29(1):25-29.
[7]	Barinova T V, Borovinskaya I P. SHS immobilization of radioactive wastes[J]. Key Engineering Materials, 2002, 217:193-200.
[8]	路新, 郭志猛, 罗上庚, 等. 自蔓延高温合成固定放射性废物[J]. 硅酸盐学报, 2003, 31(2):205-208. LU X, GUO Z M, LUO S G, et al. Self-propagating high temperature synthesis of radioactive waste immobilization[J]. Journal of the Chinese Ceramic Society, 2003, 31(2):205-208.
[9]	Ojovan M I, Lee W E. Self sustaining vitrification for immobilisation of radioactive and toxic waste[J]. Glass Technology, 2003, 44(6):218-224.
[10]	Glagovsky E M, Kouprine A V, Pelevine L F. Study of matrices synthesised by a self-propagating high-temperature synthesis[J]. Czechoslovak Journal of Physics, 2002, 12(53) (Suppl. A):A657-A663.
[11]	张瑞珠. 利用自蔓延高温合成技术固化放射性废物[D]. 北京:北京科技大学, 2005. ZHANG R Z. Self-propagation high-temperature synthesis for radioactive waste immobilization[D]. Beijing:University of Science and Technology Beijing, 2005.
[12]	Glagovskii E M, Yudintsev S V, Kuprin A V, et al. Crystalline host phases for actinides, obtained by self-propagating high-temperature synthesis[J]. Radiochemistry, 2001, 43(6):632-638.
[13]	张瑞珠, 郭志猛, 贾成广, 等. 自蔓延高温合成钙钛矿型人造岩石固化体[J]. 北京科技大学学报, 2004, 26(5):485-488. ZHANG R Z, GUO Z M, JIA C G, et al. Synthesis of perovskite synroc by SHS for immobilization of high level radioactive[J]. Journal of University of Science and Technology Beijing, 2004, 26(5):485-488.
[14]	Barinova T V, Borovinskaya I P, Ratnikov V I, et al. Self-propagating high-temperature synthesis for immobilization of high-level waste in mineral-like ceramics(Ⅰ):Synthesis and study of titanate ceramics based on perovskite and zirconolite[J]. Radiochemistry, 2008, 50(3):316-320.
[15]	Barinova T V, Borovinskaya I P, Ratnikov V I, et al. Self-propagating high-temperature synthesis for immobilization of high-level waste in mineral-like ceramics(Ⅱ):Immobilization of cesium in ceramics based on perovskite and zirconolite[J]. Radiochemistry, 2008, 50(3):321-323.
[16]	Vinokurov S E, Kulyako Y M, Perevalov S A, et al. Immobilization of actinides in pyrochlore-type matrices produced by self-propagating high-temperature synthesis[J]. Comptes Rendus Chimie, 2007, 10:1128-1130.
[17]	Glagovskii E M, Yudintsev S V, et al. Crystalline host phases for actinides obtained by self-propagating high-temperature synthesis[J]. Radiochemistry, 2001, 43(6):557-562.
[18]	徐亚红, 徐中慧, 蒋灶, 等. 镁热剂/铝热剂体系SHS法固化处理无钙焙烧铬渣[J]. 化工学报, 2017, 68(11):4309-4315. XU Y H, XU Z H, JIANG Z, et al. Immobilization of COPR from lime-free roasting process by self-propagating high-temperature synthesis of Al-Fe2O3 and Mg-Fe2O3 systems[J]. CIESC Journal, 2017, 68(11):4309-4315.
[19]	娄光普, 赵忠民. 热燃烧温度对超重力场自蔓延离心熔铸TiB2-TiC-(Ti, W)C组织及性能的影响[J]. 硅酸盐学报, 2016, 44(12):1724-1728. LOU G P, ZHAO Z M. Effects of adiabatic temperature on microstructure and properties of TiB2-TiC-(Ti, W)C prepared by combustion synthesis in high-gravity field[J]. Journal of the Chinese Ceramic Society, 2016, 44(12):1724-1728.
[20]	ZHU C C, ZHU J, WU H, et al. Synthesis of Ti3AlC2 by SHS and thermodynamic calculation based on first principles[J]. Rare Metals, 2015, 34(2):107-110.
[21]	尹丹凤. 自蔓延高温合成金属钒的热力学研究[J]. 有色金属(冶炼部分), 2014, (1):37-39. YIN D F. Study on thermodynamics of vanadium self-propagating high-temperature synthesis[J]. Nonferrous Metals(Extractive Metallurgy), 2014, (1):37-39.
[22]	王丹, 周小平. 机械合金化制备Al2O3-AlB12陶瓷粉体的热力学分析[J]. 稀有金属, 2016, 40(4):334-338. WANG D, ZHOU X P. Thermodynamic analysis of Al2O3-AlB12 ceramic powder prepared by mechanical alloying[J]. Chinese Journal of Rare Metals, 2016, 40(4):334-338.
[23]	LI Z R, FENG G J, WANG S Y, et al. High-efficiency joining of Cf/Al composites and TiAl alloys under the heat effect of laser-ignited self-propagating high-temperature synthesis[J]. Journal of Materials Science and Technology, 2016, 32:1111-1116.
[24]	毛仙鹤, 秦志桂, 武斌. 铝热剂SHS合成模拟核废物固化产物的组成结构分析[J]. 硅酸盐学报, 2010, 38(2):310-315. MAO X H, QIN Z G, WU B. Composition and structure analysis of simulated radioactive waste form immobilized with thermit by self-propagating high temperature synthesis[J]. Journal of the Chinese Ceramic Society, 2010, 38(2):310-315.
[25]	王刚, 安琳. COMSOL Multiphysics工程实践与理论仿真:多物理场数值分析技术[M]. 北京:电子工业出版社, 2012. WANG G, AN L. COMSOL Multiphysics Engineering Practice and Theory Simulation:Multi-physics Numerical Analysis Technology[M]. Beijing:Electronics Industry Press, 2012.
[26]	王百惠, 夏卫生, 吴丰顺, 等. Al/Ni薄膜自蔓延反应连接温度场模拟及分析[J]. 电子工艺技术, 2014, 35(1):6-10. WANG B H, XIA W S, WU F S, et al. Simulation and analysis of temperature field of self-propagating reaction connection based on Al/Ni film[J]. Electronics Process Technology, 2014, 35(1):6-10.
[27]	李刚, 金红梅, 韩凤, 等. Ni75Al25激光诱导自蔓延烧结合金温度场数值模拟[J]. 材料热处理学报, 2014, 35(3):218-222. LI G, JIN H M, HAN F, et al. Numerical simulation of temperature field of Ni75Al25 alloy prepared by laser induced self-propagating sintering[J]. Transaction of Materials and Heat Treatment, 2014, 35(3):218-222.
[28]	许爱国, 张广财, 应阳君. 燃烧系统的离散Boltzmann建模与模拟研究进展[J]. 物理学报, 2015, 64(18):184701(1)-184701(24). XU A G, ZHANG G C, YING Y J. Progress of discrete Boltzmann modeling and simulation of combustion system[J]. Acta Physica Sinica, 2015, 64(18):184701(1)-184701(24).
[29]	YING G B, HE X D, DU S Y, et al. Kinetics and numerical simulation of self-propagating high-temperature synthesis in Ti-Cr-Al-C systems[J]. Rare Metals, 2014, 33(5):527-533.
[30]	叶大伦, 胡建华. 实用无机物热力学数据手册[M]. 2版. 北京:冶金工业出版社. 2002. YE D L, HU J H. Handbook of Thermodynamic Data of Practical Inorganic Substances[M]. 2nd ed. Beijing:Metallurgical Industry Press, 2002.