类水滑石衍生锌基氧化物高温煤气脱硫过程中COS释放行为及其抑制研究

doi:10.11949/0438-1157.20221524

化工学报 ›› 2023, Vol. 74 ›› Issue (4): 1772-1780.DOI: 10.11949/0438-1157.20221524

类水滑石衍生锌基氧化物高温煤气脱硫过程中COS释放行为及其抑制研究

白天昊¹^,²(), 王晓雯¹^,², 杨梦滋¹^,², 段新伟¹^,², 米杰¹^,², 武蒙蒙¹^,²()

^1.太原理工大学省部共建煤基能源清洁利用国家重点实验室，山西太原 030024
^2.太原理工大学煤科学与技术教育部重点实验室，山西太原 030024

收稿日期:2022-11-23 修回日期:2023-03-08 出版日期:2023-04-05 发布日期:2023-06-02
通讯作者: 武蒙蒙
作者简介:白天昊（1997—），男，硕士研究生，1521725917@qq.com
基金资助:
国家自然科学基金面上项目(22278294);山西省自然科学基金面上项目(20210302123191)

Study on release and inhibition behavior of COS during high-temperature gas desulfurization process using Zn-based oxide derived from hydrotalcite

Tianhao BAI¹^,²(), Xiaowen WANG¹^,², Mengzi YANG¹^,², Xinwei DUAN¹^,², Jie MI¹^,², Mengmeng WU¹^,²()

^1.State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Key Laboratory of Coal Science and Technology, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2022-11-23 Revised:2023-03-08 Online:2023-04-05 Published:2023-06-02
Contact: Mengmeng WU

摘要/Abstract

摘要：

高温煤气脱硫是煤炭清洁转化过程中的关键技术之一。前期研究表明，锌铝类水滑石基衍生氧化物可高效脱除高温煤气中的H₂S，但其脱硫过程中COS释放规律缺乏定性定量研究。探讨了类水滑石衍生锌基氧化物脱硫过程COS释放的可能途径，包括反应热力学分析及实验研究，提出采用镍掺杂策略以抑制脱硫剂脱硫过程中生成COS。研究表明，锌铝类水滑石基衍生氧化物脱除煤气中H₂S时产生COS的主要途径是H₂S与CO₂间的气固相催化反应，该途径所释放COS量占总释放量的78%。通过镍助剂的掺杂使得锌铝类水滑石基衍生氧化物既保持了原有结构形貌，也有效抑制了其脱硫过程中COS的释放；其中最佳镍掺杂量(Zn/Ni摩尔比为30)脱硫剂穿透前的COS释放量减少88%，而硫容仅降低1.5%。

关键词: 热煤气, 类水滑石, 硫化氢, 羰基硫, 催化, 脱硫

Abstract:

High-temperature coal gas desulfurization is one of the key technologies for coal clean conversion process. Previous studies have shown that Zn-based oxide derived from Zn-Al hydrotalcite (ZnAl-HTO) can efficiently remove H₂S from high-temperature gas. However, there is a lack of qualitative and quantitative studies on the law of COS release during the desulfurization process. In this study, the possible pathways of COS release in the desulfurization process of ZnAl-HTO were investigated, the thermodynamic analysis and experimental study were also carried out. A nickel doping strategy was proposed to inhibit the formation of COS during the desulfurization process. It was shown that the main way to generate COS when zinc-aluminum hydrotalcite-based oxides to remove CO₂ from gas is the gas-solid phase catalytic reaction between H₂S and CO₂, and the amount of COS released by this way accounts for 78% of the total release. The doping of a small amount of nickel additives into the ZnAl-HTO results in no significant change in the morphology. It also effectively inhibits the COS release during desulfurization process. Under the optimal molar ratio of Zn/Ni (30), the overall desulfurization performance of ZnAl-HTO is significantly improved. Compared to sorbents without Ni-doping, the amount of COS released before H₂S-breakthrough reduced by 88%, while the corresponding sulfur capacity declined by only 1.5%.

Key words: hot coal gas, hydrotalcite-like compounds, hydrogen sulfide, carbonyl sulfide, catalysis, desulfurization

中图分类号:

TQ 546.5

白天昊, 王晓雯, 杨梦滋, 段新伟, 米杰, 武蒙蒙. 类水滑石衍生锌基氧化物高温煤气脱硫过程中COS释放行为及其抑制研究[J]. 化工学报, 2023, 74(4): 1772-1780.

Tianhao BAI, Xiaowen WANG, Mengzi YANG, Xinwei DUAN, Jie MI, Mengmeng WU. Study on release and inhibition behavior of COS during high-temperature gas desulfurization process using Zn-based oxide derived from hydrotalcite[J]. CIESC Journal, 2023, 74(4): 1772-1780.

图/表 12

图1 脱硫性能测试装置

Fig.1 Desulfurization performance test device

图2 模拟煤气气氛和简单气氛下ZnAl-HTO穿透曲线（a）及模拟煤气气氛下硫容与COS释放量（b）

Fig.2 Breakthrough curve of ZnAl-HTO under simulated gas atmosphere and simple atmosphere (a), and sulfur capacity and COS release amount under simulated gas atmosphere (b)

表1 ZnAl-HTO脱硫过程中COS生成可能的途径及相应的热力学参数

Table 1 Possible COS formation pathways and corresponding thermodynamic parameters

反应编号	反应方程式	ΔH/ （kJ/mol）	K^Ө	X/%
1	H₂S+CO $̿$ COS+H₂	-2.6	3.3×10^-2	79
2	H₂S+CO₂ $̿$ COS+H₂O	34.6	6.6×10^-3	33
3	H₂S $̿$ S+H₂	34.1	8.6×10^-4	0.008
4	S+CO $̿$ COS	-36.7	38.4	99.6
5	2S+2CO₂ $̿$ COS+SO₂+CO	222.8	4.5×10^-8	69.2
6	ZnS+CO $̿$ COS+Zn	181.1	1.0×10^-11	7.2×10^-7
7	ZnS+CO₂ $̿$ COS+ZnO	108.0	7.3×10^-8	7.2×10^-5

表1 ZnAl-HTO脱硫过程中COS生成可能的途径及相应的热力学参数

Table 1 Possible COS formation pathways and corresponding thermodynamic parameters

反应编号	反应方程式	ΔH/ （kJ/mol）	K^Ө	X/%
1	H₂S+CO $̿$ COS+H₂	-2.6	3.3×10^-2	79
2	H₂S+CO₂ $̿$ COS+H₂O	34.6	6.6×10^-3	33
3	H₂S $̿$ S+H₂	34.1	8.6×10^-4	0.008
4	S+CO $̿$ COS	-36.7	38.4	99.6
5	2S+2CO₂ $̿$ COS+SO₂+CO	222.8	4.5×10^-8	69.2
6	ZnS+CO $̿$ COS+Zn	181.1	1.0×10^-11	7.2×10^-7
7	ZnS+CO₂ $̿$ COS+ZnO	108.0	7.3×10^-8	7.2×10^-5

图3 CO/CO2+H2S+N2气氛下ZnAl-HTO穿透曲线（a）及COS释放量（b）

Fig.3 Breakthrough curve (a) and COS release amount (b) of ZnAl-HTO under CO/CO2+H2S+N2 atmosphere

图4 镍掺杂ZnAl-HTLCs（a）及其氧化物ZnAl-HTO（b）的XRD谱图

Fig.4 XRD patterns of the Ni-doped ZnAl-HTLCs (a) and its oxide ZnAl-HTO (b)

图5 镍掺杂前后脱硫剂的氮吸脱附等温曲线（a）及孔径分布曲线（b）

Fig.5 Isothermal adsorption-desorption curve (a) and pore size distribution curve (b) of Ni-doped desulfurizer

表2 镍掺杂前后脱硫剂孔结构参数

Table 2 Structural parameters of desulfurizer holes before and after nickel doping

样品	比表面积/（m²/g）	孔容/（cm³/g）
ZnAl-HTO	31	0.09
Zn30Ni1Al-HTO	37	0.22
Zn20Ni1Al-HTO	41	0.20
Zn10Ni1Al-HTO	43	0.27

图6 ZnAl-HTO（a）、Zn30Ni1Al-HTO（b）、Zn20Ni1Al-HTO（c）和Zn10Ni1Al-HTO（d）的扫描电镜图

Fig.6 SEM images of ZnAl-HTO (a), Zn30Ni1Al-HTO (b), Zn20Ni1Al-HTO (c), and Zn10Ni1Al-HTO (d)

图7 ZnNiAl-HTO对应的出口H2S/COS曲线（a）及吸硫饱和时对应的饱和硫容与COS释放量（b）

Fig.7 The outlet H2S / COS curve (a) corresponding to ZnNiAl-HTO and the corresponding saturated sulfur capacity and COS release amount (b) during sulfur absorption saturation

图8 ZnNiAl-HTO穿透前对应的穿透曲线(a)；穿透硫容及COS释放量(b)

Fig.8 Breakthrough curve before ZnNiAl-HTO breakthrough (a) and breakthrough capacity and COS release amount (b)

图9 Zn30Ni1Al-HTO中Ni 2p的XPS谱图

Fig.9 Ni 2p XPS profile of Zn30Ni1Al-HTO

图10 ZnAl-HTO及Zn30Ni1Al-HTO的Zn 2p3/2和O 1sXPS谱图

Fig.10 Zn 2p3/2 and O 1s XPS profiles of ZnAl-HTO and Zn30Ni1Al-HTO

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类水滑石衍生锌基氧化物高温煤气脱硫过程中COS释放行为及其抑制研究

Study on release and inhibition behavior of COS during high-temperature gas desulfurization process using Zn-based oxide derived from hydrotalcite

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