生物质锅炉氯腐蚀的密度泛函理论研究

doi:10.11949/0438-1157.20190487

摘要/Abstract

摘要：

氯气的活化氧化腐蚀是生物质锅炉过热器腐蚀的主要原因之一。为探究活化氧化腐蚀循环中FeCl₂与O₂的反应机理，本文利用Material Studio中的DMOl³模块，基于密度泛函和过渡态理论，优化了各反应物、产物、中间体和过渡态的几何构型。通过频率分析证实了中间体和过渡态的真实性。结果表明，FeCl₂与O₂反应生成Fe₃O₄的过程中逐次生成3个Cl₂分子，其中第三个Cl₂逸出生成Fe₃O₄需要吸收高达300.4 kJ/mol的能量，为反应路径的速率决定步骤。

关键词: 生物质燃料, 过热器, Cl₂, 活化氧化, 腐蚀, 分子模拟, 密度泛函理论

Abstract:

Activated oxidative corrosion of chlorine is one of the main causes of corrosion in biomass boiler superheaters. To investigate the reaction mechanism of FeCl₂ and O₂in the activated oxidation corrosion cycle, the DMOl³ module in Material Studio was used to optimize the geometry of each reactant, product, intermediate and transition state based on density functional theory and transition state theory. The authenticity of the intermediates and transition states was confirmed by frequency analysis. The results show that three Cl₂ molecules are successively formed during the reaction of FeCl₂ with O₂ to form Fe₃O₄. The third Cl₂ escaping to form Fe₃O₄needs to absorb up to 300.4 kJ/mol, which is the rate determining step of the reaction pathway.

Key words: biofuel, superheater, chlorine, activated oxidation, corrosion, molecular simulation, density functional theory

中图分类号:

TK 6

吕泽康, 龙慎伟, 李冠兵, 牛胜利, 路春美, 韩奎华, 王永征. 生物质锅炉氯腐蚀的密度泛函理论研究[J]. 化工学报, 2019, 70(11): 4370-4376.

Zekang LYU, Shenwei LONG, Guanbing LI, Shengli NIU, Chunmei LU, Kuihua HAN, Yongzheng WANG. Density functional theory study on chlorine corrosion of biomass furnace[J]. CIESC Journal, 2019, 70(11): 4370-4376.

图/表 8

表1 反应路径中各驻点的能量及过渡态的振动虚频

Table 1 Energies of various compounds and imaginary frequency of transition states

Species	E/Ha	Frequency/cm^-1	Species	E/Ha	Frequency/ cm^-1
O₂	-150.39	—	IM11	-1508.00	—
Cl₂	-920.42	—	IM12	-587.58	—
FeCl₂	-1063.80	—	IM13	-587.52	—
Fe₃O₄	-730.92	—	IM14	-1651.46	—
IM1	-1214.22	—	IM15	-1651.46	—
IM2	-1214.26	—	IM16	-1651.34	—
IM3	-2278.09	—	TS1	-1214.19	-869.50
IM4	-2278.16	—	TS2	-2278.08	-390.80
IM5	-2278.13	—	TS3	-2278.13	-119.00
IM6	-2278.03	—	TS4	-2278.03	-86.00
IM7	-1357.61	—	TS5	-1508.03	-817.10
IM8	-1508.06	—	TS6	-1508.02	-316.66
IM9	-1508.10	—	TS7	-1507.99	-22.66
IM10	-1508.04	—	TS8	-1651.43	-85.00

表2 反应物、生成物平均键长的计算值和文献值对比

Table 2 Average bond length of calculated values and literature values for reactant and product

Species	Bond type	Bond length/nm
Species	Bond type	Calculated	Literature
O₂	r(O—O)	0.1237	0.1220^[26]
Cl₂	r(Cl—Cl)	0.2076	0.2053^[27]
FeCl₂	r(Fe—Cl)	0.2156	0.2200^[28]
Fe₃O₄	r(Fe—O)	0.1843	0.1860^[29]

图1 中间体Cl2Fe2O2形成过程中各中间体和过渡态的几何构型（O:红色，Cl:绿色，Fe:蓝色；键长单位：nm)

Fig.1 Geometries of the intermediates and transition states involved in Cl2Fe2O2 formation(O: red, Cl: green, Fe: blue, bond length unit:nm)

图2 中间体Cl2Fe2O2形成过程的能量分布

Fig.2 Energy profiles of formation of Cl2Fe2O2

图3 Fe2O4形成过程中各中间体和过渡态的几何构型(键长单位：nm)

Fig.3 Geometries of the intermediates and transition states involved in Fe2O4 formation(bond length unit: nm)

图4 Fe2O4与Fe3O4形成过程中的能量分布

Fig.4 Energy profiles of formation of Fe2O4 and Fe3O4

图5 Fe3O4形成过程中各中间体和过渡态的几何构型(键长单位：nm)

Fig.5 Geometries of the intermediates and transition states involved in Fe3O4 formation(bond length unit: nm)

图6 FeCl2与O2反应机理示意图

Fig.6 Schematic illustration of reaction mechanism of FeCl2 and O2

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