污泥燃烧中H2O、SO2和CO2对PbO在CaO表面吸附的影响

史一林; 何学富; 王彦霖; 乔晓磊; 贾里; 金燕

doi:10.19906/j.cnki.JFCT.2023001

污泥燃烧中H₂O、SO₂和CO₂对PbO在CaO表面吸附的影响

doi: 10.19906/j.cnki.JFCT.2023001

太原理工大学电气与动力工程学院, 山西太原 030024

基金项目: 国家自然科学基金（U1910214）资助

详细信息

通讯作者:
E-mail: jinyan@tyut.edu.cn

中图分类号: TQ534
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- 被引次数: 0
出版历程
- 收稿日期: 2022-11-24
- 修回日期: 2022-12-21
- 录用日期: 2022-12-27
- 网络出版日期: 2023-01-10
- 刊出日期: 2023-09-30

Effect of H₂O, SO₂ and CO₂on PbO adsorption in CaO surface during sewage sludge combustion

School of Electrical and Power Engineering, Taiyuan University of Technology, Taiyuan 030024, China

Funds: The project was supported by the National Natural Science Foundation of China (U1910214)

摘要

摘要: 采用密度泛函理论研究了污泥燃烧过程中烟气组分对PbO在CaO（001）表面吸附的影响。计算结果表明，CaO（001）表面的 O顶位是PbO、H₂O、SO₂和CO₂分子吸附的活性位点。H₂O、SO₂和CO₂分子的存在分别使PbO分子在CaO（001）表面的吸附能较洁净表面增大了71.42、19.589和46.431 kJ/mol。H₂O分子在吸附过程中形成的OH基团和局部Ca（OH）₂表面结构有利于PbO分子的吸附。SO₂分子中的O_S原子和CaO（001）表面的O_surf原子的态密度轨道均与Pb原子轨道产生重叠，使得PbO分子在表面的吸附更加稳定。CO₂分子预吸附在CaO（001）表面形成的CO₃基团对PbO分子存在强吸附作用，使得PbO分子更稳定的吸附在CaO（001）表面。
- DFT /
- 烟气组分 /
- PbO /
- CaO /
- 吸附
Abstract: The effect of flue gas components on the adsorption of PbO on the surface of CaO(001) during sewage sludge combustion was studied by DFT (Density Functional Theory). The calculation results show that O apex on the surface of CaO(001) is the active site of the adsorption of PbO molecules, H₂O molecules, SO₂ molecules and CO₂ molecules. The presences of H₂O molecules, SO₂ molecules and CO₂ molecules increase the adsorption energy of PbO molecules on the surface of CaO(001) by 71.42, 19.589 and 46.431 kJ/mol, respectively. OH group and local Ca(OH)₂ surface structure formed by H₂O molecules during the adsorption process are conducive to the adsorption of PbO molecules. Density of state orbitals of O_S atom in SO₂ molecule and O_surf atom on the surface of CaO(001) overlap with the orbitals of Pb atom, making the adsorption of PbO molecules on the surface more stable. CO₃ group formed by CO₂ molecules pre-adsorbed on the surface of CaO(001) has a strong adsorption effect on PbO molecules, making PbO molecules more stable adsorption on the surface of CaO(001).
- DFT /
- flue gas components /
- PbO /
- CaO /
- adsorption

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FIG. 2667. FIG. 2667.

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图 1 CaO(001)周期性板块模型

Figure 1 CaO (001) periodic plate model

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图 2 PbO在CaO（001）表面优化前后的吸附结构示意图

Figure 2 Adsorption structure of PbO before and after optimization on CaO(001) surface

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图 3 PbO分子在CaO（001）表面吸附的电子密度和PDOS谱图

Figure 3 Electron density map and PDOS of PbO molecules on the surface of CaO(001)

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图 4 H₂O在CaO（001）表面优化前后的吸附结构示意图

Figure 4 Adsorption structure of H₂O before and after optimization on the surface of CaO (001)

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图 5 H₂O分子稳定吸附于CaO（001）表面的电子密度和差分电荷密度

Figure 5 Electron density map and differential charge density map of H₂O molecules stably adsorbed on the surface of CaO(001)

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图 6 SO₂在CaO（001）表面优化前后的吸附结构示意图

Figure 6 Adsorption structure of SO₂ before and after optimization on CaO(001) surface

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图 7 SO₂分子稳定吸附于CaO（001）表面的电子密度和差分电荷密度

Figure 7 Electron density map and differential charge density map of SO₂ molecules stably adsorbed on the surface of CaO(001)

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图 8 CO₂在CaO（001）表面优化前后的吸附结构示意图

Figure 8 Adsorption structure of CO₂ before and after optimization on CaO(001) surface

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图 9 CO₂分子稳定吸附于CaO（001）表面的电子密度和差分电荷密度

Figure 9 Electron density map and differential charge density map of CO₂ molecules stably adsorbed on the surface of CaO(001)

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图 10 H₂O对PbO在CaO表面吸附的影响

Figure 10 Effect of H₂O on the adsorption of PbO on CaO surface

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图 11 PbO分子在H₂O + CaO（001）表面吸附后的电子密度

Figure 11 Electron density diagram of PbO molecules after adsorption on the surface of H₂O + CaO(001)

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图 12 SO₂对PbO在CaO表面吸附的影响

Figure 12 Effect of SO₂ on the adsorption of PbO on CaO surface

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图 13 Pb、O_S原子和O_surf原子的PDOS

Figure 13 PDOS of Pb, O_S atom and O_surf atom

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图 14 CO₂对PbO在CaO表面吸附的影响

Figure 14 Effect of CO₂ on the adsorption of PbO on CaO surface

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图 15 Pb、O_surf原子和O_C原子的PDOS

Figure 15 PDOS of Pb, O_surf atom and O_C atom

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表 1 结构和能量收敛标准

Table 1 Structural and energy convergence criteria

Parameter	Convergence criteria
SCF tolerance	1.0 × 10⁻⁶ eV/atom
Energy tolerance	1.0 × 10⁻⁵ eV/atom
Maximum displacement tolerance	0.001 Å
Maximum force tolerance	0.03 eV/Å

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表 2 各分子优化后的键长和键角

Table 2 Optimized bond length and bond angle for each molecule

Molecule	Key ength / key angle	Optimize value / (Å·(°)⁻¹)	Reference value / (Å·(°)⁻¹)	Relative error/%
CaO	Ca−O	4.909	4.805	2.164
	α=β=γ	90	90	0.000
H₂O	H−O	0.978	0.96	1.875
	H−O−H	103.741	104.5	0.726
SO₂	S−O	1.457	1.43	1.889
	O−S−O	119.401	119.5	0.083
CO₂	C−O	1.173	1.163	0.860
	O−C−O	179.990	180	0.006
PbO	Pb−O	1.946	1.92	1.354

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表 3 PbO在CaO表面吸附的参数

Table 3 Parameters of PbO after adsorption on CaO surface

Adsorption structure	E_ad/ （kJ·mol⁻¹）	Pb−O bond length /Å	Pb−O_surf bond length /Å	q（PbO）/e
1-a	−143.540	2.014	2.329	−0.16
1-b	−126.894	2.013	2.291	−0.19
1-c	−143.867	2.012	2.329	−0.16
1-d	−143.676	2.011	2.330	−0.16

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表 4 H₂O分子在CaO（001）表面吸附的参数

Table 4 Parameters of H₂O after adsorption on CaO surface

Adsorption structure	E_ad/ （kJ·mol⁻¹）	H−O bond length /Å	q（H₂O）/e
2-a	−74.208	1.037	−0.23
2-b	−85.220	0.972	−0.25
2-c	−91.450	0.974	−0.26
2-d	−28.368	0.980	0.01

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表 5 SO₂在CaO（001）表面吸附的参数

Table 5 Parameters of SO₂ after adsorption on CaO surface

Adsorption structure	E_ad /（kJ·mol⁻¹）	S−O_surf distance /Å	q（SO₂） /e
3-a	−231.085	3.088	−0.08
3-b	−235.952	3.232	−0.16
3-c	−396.992	1.697	−0.28
3-d	−228.541	3.615	−0.06

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表 6 CO₂在CaO（001）表面吸附的参数

Table 6 Parameters of CO₂ after adsorption on CaO surface

Adsorption structure	E_ad /（kJ·mol⁻¹）	C−O_surf distance /Å	q（CO₂） /e
4-a	−17.187	−	−0.04
4-b	−122.797	1.407	−0.63
4-c	−122.845	1.406	−0.61
4-d	0.304	−	−0.03

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表 7 PbO在H₂O/SO₂/CO₂ + CaO（001）表面吸附的吸附能、键参数和电荷转移

Table 7 Adsorption energy, bond parameters and charge transfer of PbO adsorption on the surface of H₂O/SO₂/CO₂ + CaO(001)

Adsorption structure	E_ad / （kJ·mol⁻¹）	Pb−O_surf bond length /Å	Pb−O_surf population
H₂O	−215.287	2.564	0.14
SO₂	−163.456	2.836	0.11
CO₂	−190.298	2.459	0.18

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