富铁飞灰耦合Fe-Zn/Al2O3脱除沼气H2S研究

doi:10.11949/0438-1157.20250181

摘要/Abstract

摘要：

Fe-Zn/Al₂O₃吸附剂在H₂S脱除方面展现了良好的性能，但其高昂的原料成本和复杂的制备过程增加了在大型沼气净化设施中的应用成本。为降低成本，本研究将富铁飞灰（FA）部分替代耦合Fe-Zn/Al₂O₃吸附剂，以改善沼气脱硫效果。研究结果表明，Zn/Fe摩尔比为3∶1的Zn-Fe/Al₂O₃复合吸附剂在室温条件下具有最佳的H₂S脱除性能，其穿透容量达到3.234 mg/g。进一步加入FA作为粗脱硫剂，通过二段式吸附过程，显著提高了整体H₂S穿透容量，增幅达到7.4%。结果表明，FA的添加能够有效降低沼气脱硫的成本，具有较好的应用前景。

关键词: 复合吸附剂, 焚烧飞灰：H₂S脱除, 二段式吸附

Abstract:

Fe-Zn/Al₂O₃ adsorbents exhibit good performance in H₂S removal; however, the high raw material cost and complex preparation process increase the application costs in large-scale biogas purification systems. To reduce these costs, this study explores the potential of partially replacing Fe-Zn/Al₂O₃ adsorbents with fly ash (FA) from sewage sludge incineration to enhance biogas desulfurization. The results show that the Zn-Fe/Al₂O₃ composite adsorbent with a Zn/Fe molar ratio of 3∶1 has the best H₂S removal performance at room temperature, and its penetration capacity reaches 3.234 mg/g. Further addition of FA as a preliminary desulfurizer in a two-step adsorption process significantly increased the overall H₂S breakthrough capacity by 7.4%. This study demonstrates that incorporating FA can effectively reduce biogas desulfurization costs, offering a promising approach for large-scale applications.

Key words: composite adsorbent, fly ash, H₂S removal, two-step adsorption

中图分类号:

TQ 028.1

史松伟, 赵诚, 刘帅, 应雨轩, 严密. 富铁飞灰耦合Fe-Zn/Al₂O₃脱除沼气H₂S研究[J]. 化工学报, 2025, 76(8): 4239-4247.

Songwei SHI, Cheng ZHAO, Shuai LIU, Yuxuan YING, Mi YAN. Removal of biogas H₂S using iron-rich fly ash coupled with Fe-Zn/Al₂O₃[J]. CIESC Journal, 2025, 76(8): 4239-4247.

图/表 12

表1 富铁FA中主要金属氧化物的含量

Table 1 Concentration of major metal oxides in iron-rich FA

成分	含量/%（质量）
Na₂O	2.29
Al₂O₃	14.28
CaO	4.64
TiO₂	1.2
Fe₂O₃	53.85
ZnO	1.5
其他	22.24

图1 H2S脱除实验装置

Fig.1 Diagram of the H2S removal experiment

图2 不同Zn/Fe摩尔比吸附剂的H2S穿透曲线（a）和H2S穿透容量（b）

Fig.2 H2S breakthrough curves (a) and H2S breakthrough capacity (b) of adsorbents with different Zn/Fe ratios

图3 不同Zn/Fe摩尔比的Zn-Fe/Al2O3吸附剂的N2吸脱附曲线（a）和计算得到的BJH孔径分布（b），不同Zn/Fe摩尔比的Zn-Fe/Al2O3吸附剂的FTIR光谱（c）

Fig.3 N2 adsorption/desorption curves (a) and calculated BJH pore distributions (b) of Zn-Fe/Al2O3 adsorbents with different Zn/Fe ratios, FTIR spectra of Zn-Fe/Al2O3 adsorbents with different Zn/Fe ratios (c)

表2 不同Zn/Fe摩尔比的Zn-Fe/Al2O3的孔隙特性

Table 2 Pore characteristics of Zn-Fe/Al2O3 with different Zn/Fe ratio

样品	比表面积/(m²/g)	孔容/(cm³/g)	平均孔径/nm
Al₂O₃	165.94	0.26	6.74
1ZnFe	182.85	0.44	7.12
2ZnFe	182.82	0.45	7.06
3ZnFe	181.53	0.44	7.10

图4 3-1ZnFe吸附剂的SEM图像：（a）新鲜吸附剂；（b）穿透后的吸附剂

Fig.4 SEM images of 3-1ZnFe adsorbent: (a) fresh adsorbent; (b) adsorbent after breakthrough

表3 新鲜吸附剂和穿透后吸附剂的元素分析

Table 3 Concentration of each element in fresh and spent adsorbent

元素	含量/%（质量）
元素	新鲜吸附剂	废吸附剂
Zn	11.24	10.78
Fe	3.56	3.02
Al	44.96	43.56
O	40.06	41.81
S	0.08	0.73

表4 穿透前后吸附剂的孔隙特性

Table 4 Pore characteristics of adsorbents before and after breakthrough

吸附剂	比表面积/(m²/g)	孔容/(cm³/g)	平均孔径/nm
新鲜吸附剂	181.53	0.44	7.10
废吸附剂	148.39	0.41	7.31

图5 不同质量下初始FA的H2S穿透曲线（a）和H2S穿透容量（b）

Fig.5 H2S breakthrough curves (a) and H2S breakthrough capacity (b) of original FA with different masses

图6 FA&Zn-Fe/Al2O3二段式吸附的H2S穿透曲线（a）和H2S穿透容量（b）

Fig.6 H2S breakthrough curves (a) and H2S breakthrough capacity (b) of two-step FA&Zn-Fe/Al2O3 adsorption

图7 单独使用ZnFe吸附剂及FA-ZnFe二段式吸附的拟一阶动力学拟合（a）和拟二阶动力学拟合（b）

Fig.7 Proposed first-order kinetic fit (a) and proposed second-order kinetic fit (b) for ZnFe adsorbent alone and FA-ZnFe binary adsorption

表5 动力学拟合结果汇总

Table 5 Summary of the results of the kinetic fitting

项目	拟一阶动力学			拟二阶动力学
项目	k₁	q_e	R²	k₂	q_e	R²
ZnFe	6.44×10^-5	130.69	0.9999	8.31×10^-7	-100	0.9999
FA-ZnFe	4.24×10^-5	49.27	0.9999	2.08×10^-7	-100	0.9999

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富铁飞灰耦合Fe-Zn/Al₂O₃脱除沼气H₂S研究

Removal of biogas H₂S using iron-rich fly ash coupled with Fe-Zn/Al₂O₃

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